imidazole and triazole coordination chemistry for antifouling

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Imidazole and Triazole Coordination Chemistry for Antifouling Coatings

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Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 946739 23 pageshttpdxdoiorg1011552013946739

Review ArticleImidazole and Triazole Coordination Chemistry forAntifouling Coatings

Markus Andersson Trojer1 Alireza Movahedi1 Hans Blanck2 and Magnus Nydeacuten13

1 Applied Surface Chemistry Department of Chemical and Biological EngineeringChalmers University of Technology 412 96 Goteborg Sweden

2Department of Biological and Environmental Sciences University of Gothenburg 405 30 Goteborg Sweden3 Ian Wark Research Institute University of South Australia Adelaide SA 5001 Australia

Correspondence should be addressed to Markus Andersson Trojer markusanderssonchalmersse

Received 29 April 2013 Accepted 9 July 2013

Academic Editor Suleyman Goksu

Copyright copy 2013 Markus Andersson Trojer et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

Fouling of marine organisms on the hulls of ships is a severe problem for the shipping industry Many antifouling agents are basedon five-membered nitrogen heterocyclic compounds in particular imidazoles and triazoles Moreover imidazole and triazoles arestrong ligands for Cu2+ and Cu+ which are both potent antifouling agents In this review we summarize a decade of work withinour groups concerning imidazole and triazole coordination chemistry for antifouling applications with a particular focus on thevery potent antifouling agent medetomidine The entry starts by providing a detailed theoretical description of the azole-metalcoordination chemistry Some attention will be given to ways to functionalize polymers with azole ligands Then the effect ofmetal coordination in azole-containing polymers with respect to material properties will be discussed Our work concerning thecontrolled release of antifouling agents in particular medetomidine using azole coordination chemistry will be reviewed Finallyan outlookwill be given describing the potential for tailoring the azole ligand chemistry in polymerswith respect toCu2+ adsorptionand Cu2+ rarrCu+ reduction for antifouling coatings without added biocides

1 Introduction

A major problem for the shipping industry is fouling ofmarine organisms such as algae mussels and barnacles onship hulls [1ndash5] As the ship moves through the water thehull is subjected to form drag and skin friction drag Sincefouling increases the surface roughness the skin friction dragis increased which subsequently results in increased fuelconsumption and reduced manoeuvrability [3] Traditionalcountermeasures against marine fouling are coatings con-taining antifouling toxicants that have had severe environ-mental consequences on marine ecosystems The most well-known examples are organometallic paint systems (compris-ing lead arsenic mercury etc) which met the market in theearly 1960s The notorious tributyltin self-polishing coating(TBT-SPC) was developed in the 1970s [1 6] The reason forthe success of the TBT-SPC paints is that the rate of releasecan be controlled on amolecular level Generally these paints

are based on acrylic or methacrylic copolymers The activesubstance (TBT) is covalently attached to the carboxylicgroup of the polymer which is hydrolytically instable inslightly alkaline conditions (as in seawater) [1 4 6] Toxiccopper pigment is also included in the TBT-SPC paintsystems which in combinationwith TBT provides protectionagainst the entire spectrum of fouling organisms since somealgae are tolerant to TBT but not to copper and vice versa[7] As the use of TBT containing paints increased marinelife in the vicinity of harbours and marinas was severelyaffected [8 9] The hazardous nature of TBT for the marineenvironment is ascribed to its weakening of fish immunesystems causing imposex and sterility in female gastropods(at such low concentration as 1 ngL) as well as its bioac-cumulative properties in mammals [1 4 6] Starting withTBT ban for pleasure craft in France 1982 TBT-contain-ing paint systems were successively phased out in the 1990s

2 Journal of Chemistry

and finally banned by IMO (the International MaritimeOrganization) [10 11]

A number of tin-free alternatives have been developeddue to the restrictive legislation regarding TBT paints Thesecan crudely be divided into biocide-release and biocide-freeantifouling systems Biocide-free approaches are dominatedby paint systems called foul-release coatings The antifoulingmechanism lies in the low surface energy and smoothnessof the coating The binders in these coatings are siliconepolymers for example PDMS (polydimethylsiloxane) and tosome extent fluoropolymers with both possessing very lowsurface energy

In tin-free SPC paints tin is replaced by other elementssuch as copper zinc and silicon Even though the side groupof a few tin-free SPC paint binders also possess biocidalproperties no alternative is nearly as effective as TBT [4 6]To provide full and long-term fouling protection it is nownecessary to add other biocides so called boosters generallyin combination with copper The most frequently employedboosters are conventional agrochemicals some of whichfor example irgarol have been under scrutiny due to lowrate of biodegradation as well as toxicity towards nontargetorganisms [1 4 6 10ndash18] Since also the use of copper hasbeen under debate recently a number of other pigments areused such as Zn(II) Fe(III) and Ti(IV) oxides [1 3 4 6]

A generic problem with tin-free SPC paints is prematureleakage of the booster biocides [3] These are not anchoredto the binder as TBT is and are hence subjected to free dif-fusion within the paint matrix The immediate consequenceof premature leakage is loss of antifouling effect prior to thehydrolysis-dependent lifetime of the coating

A lot of research and development has been conducted onSPC paints from an environmental perspective For instancethe antifouling substances secreted by marine organism thatis natural biocides have recently attracted attention from thescientific community The antifouling mechanisms of thesenatural biocides are generally much more intricate and spe-cific compared to those of conventional booster biocides[3 4 6] Some examples of natural antifoulants are worthmentioning Furanon originating from red seaweed is forinstance 100 times more effective than TBT as antifoulantagainst barnacle [3] Bufalin (a toad poison) is for exampleconsidered to be 100 times more toxic than TBT and 6000times more efficacious against barnacles [6] Most sub-stances are found in the phyla Porifera (sponges) AlgaeCnidaria (eg corals sea anemones and hydroids) Echin-odermata (eg sea urchins) Bryozoa (moss animals) andbacteria [3 6] Many antimicrobial substances are basedon five-membered aromatic heterocycles such as Seanineand OIT (see Scheme 1) Moreover triazole-based biocidesrepresent a wide spectrum of in particular antifungals such asfluconazole and itraconazole (see Scheme 1) [19ndash27]The imi-dazole fungicide clotrimazole (see Scheme 1) used as humanand veterinary pharmaceutical has been found in the marineenvironment at concentrations affecting sterol metabolism inmarine microalgal communities [28] The interdisciplinaryresearch program Marine Paint [2] in which our group hasbeen a part has since 2001 been investigating the substance

medetomidine [29] (see Scheme 1) which is based on imi-dazole for antifouling purposes [30ndash32] Medetomidine isexceptionally efficient against fouling barnacles [33] whichis one of the most problematic foulants in the north Atlanticyet without seriously affecting nontarget organisms [34ndash37]

In this review we will summarize a decade of researchconcerning azole (primarily imidazole) coordination chem-istry for antifouling coatings The work spans a variety ofchemistry disciplines includingmolecularmodelling [38 39]surface and colloidal chemistry [40ndash43] controlled release[30 31 40ndash42 44ndash46] coordination chemistry [39 40 47]polymer synthesis [47ndash50] and material science [39 47]Some references from other groups will be provided how-ever it is important to note that very few studies haveaddressed azole coordination for antifouling purposes andthe area is still rather unexplored The azole coordinationapproaches implemented by us with respect to antifoulingcoatings can be divided into three main categories (1)antifoulant immobilization (2) triggered release and (3)Cu2+Cu+ mediated antifouling as described later

11 Antifoulant Immobilization Booster biocides includingthe azole-based molecules already mentioned are typicallysmall molecules which are molecularly dispersed in theantifouling paint [3 51] As a consequence the biocides leachout from the coating within a couple of weeks (diffusiverelease from thin coatingssim100120583m) [52]This results in a pre-mature loss of fouling protection which is a severe problemsince the desired lifetime of a marine coating is sim5 years [34] However when the biocides are immobilized on macro-molecules or colloids (with negligible diffusion coefficientsgiven there large sizes) the effective diffusion coefficientwill be reduced by the magnitude of the stability constantfor immobilization [53] We have explored the possibilityto immobilize the very efficient antifoulant medetomidineon polymers and nanoparticles by exploiting the strong andspecific coordination chemistry of the moleculersquos imidazolemoiety This is treated in Section 5

12 Triggered Release and Imidazole-Cu2+ Coordination Theapproach discussed in the previous section is obviouslyonly applicable for azole-based biocidesantifoulants Mostbooster biocides do not contain a strong ligand moietyfor coordination chemistry We have therefore developedmore generic release systems based on polymeric poly(meth-yl methacrylate) microcapsules [52ndash60] with some noveladvances involving ultrathin polyelectrolyte multilayers forsustained release [53 60ndash66] However in order to maintainprotection against fouling it is important that the biocideconcentration reaches high enough concentrations at thecoating surface (see Scheme 2) Consequently it would bebeneficial if the release of the antifouling substance couldbe triggered by some physical or chemical parameters atthe hull-water interface We have explored the possibility toachieve triggered release by incorporating salt in the otherwiserather hydrophobic microcapsule shell using azole coordina-tion chemistry The salt will initiate swelling of the shell byincreasing the free volume of the polymer [54] and hence

Journal of Chemistry 3

Im-EHEC

n

O

N OO

NNH

O

N OO

NNH

n

n

N

N

OO

OO

O

OO

OO

O

OH

NHN

OH

991

OH

HO

n

ma cn

SO OOH

SO OOH

b

ma cn b

4 96

44 56

4 96 PMMA

P(1-VIm)

PVM-4

PVM-44

P4VM-4

PHMI P(E-alt-HMI)

N

HN

Medetomidine

PSEBS

SPSEBS

N

NIm H H

CH3

H

H

Polymers

Biopolymers

Synthetic polymers

O O

nm

NNH

NO O

n

Nm

n

O O

NS

O

Isothiazolinones

H

Cl Cl

HOcthilinone

Fluconazole

OHF

F

N

N N

N

N N

Itraconazole

NNNN

O

NOO

O

Cl

ClN

NN

Imidazole-modified ethyl(hydroxyethyl)cellulose

Poly(1-vinylimidazole)

Polymethylmethacrylate

Poly(maleoyl-histidine)

Polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene

Sulphonated polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene

Poly(4-vinylimidazole-co-methylmethacrylate)


Monomeric imidazoles and five-membered nitrogen heterocyclic antifouling biocides

Dichloroctylisothiazolinon

OIT

DCOIT

N

N

ClClotrimazole

Poly(ethylene-alt-N-histidyl maleimide)

Selectope

Seanine

Me(1)-Im

Me(4)-Im

Imidazole

1-methylimidazole

4-methylimidazole

R2O R2O

R2

R2

R2R2

R3

R3

R1

R1

R1

R1

CH3

C8H17

C8H17

R2 = H CH3

(()

)[ ]

( () )

( () ) ( )

( ) ( ) ( )( ) ( )

( ) ( )[

[ [ [

[ []

] ] ]

] ]

Scheme 1 Molecular structure names and abbreviations of polymers used for azole coordination and low molecular weight imidazolecontaining substances and five-membered nitrogen heterocyclic biocides investigated in this review Potential nitrogen coordinatingborderline ligands (imidazole triazole) or hard ligands (amines) oxygen coordinating hard ligands and sulphur coordinating soft ligandsare marked with blue purple red and yellow respectively Weak ligands such as organic halides have not been marked

trigger the release from the microcapsule shell as a functionof contact with water or moisture (see Scheme 2) Thefunctionalization of polymers with azoles (mainly imidazole)is treated in Section 3 and the material properties and watersorption with respect to the presence of metal ions (in partic-ular Cu2+ and Zn2+) in the polymer matrix are treated inSection 4

The azole coordination has also been used to trigger therelease of medetomidine This is treated in Section 51

13 Towards Cu2+Cu+ Catalysis in Novel Biocide-Free MarineCoatings Copper is a potent antifouling biocide for in par-ticular marine organisms [67 68] Yet copper is also a traceelement and constitutes an essential part of many enzymeswhere redox reactions are the central function Howeverexcess copper concentrations are lethal for the organism sincevital biological processes (disruption of cell homeostasis suchas pHbalancemembrane potential and osmosis) are affectedvia the inactivation of enzymes and by the precipitation


Releasedbiocide

Dissolvedpigment Dissolved

binder

Biocide inmicrocapsule

Pigment

Binder

- pH- Temp- Ionic strength- Flow

Erodinglayer

Unreactedpaint

Seawater(H2O NaCl)

Topcoat(antifouling)

Swollen shell ofmicrocapsule

Leakage of biocidethrough ldquoopenedrdquo

polymer shell

The shell isswelled by water

Microcapsule shellcontaining salt (CuCl2)

(a)

(b)

Scheme 2 Triggered release mechanism for (a) a self-polishing paint and (b) containing microcapsules

cytoplasmic proteins into metal-protein aggregates [69 70]Many studies are pointing towards the fact that copper crossesthe biological membranes as Cu+ which is subsequently thebiologically most active oxidation state [69] However Cu+ isunstable in an aqueous environment and disproportionatesto Cu2+ and Cu0 [71 72] Moreover only free ions of Cu2+and Cu+ are considered to be bioavailable [73ndash75] A lot ofrecent focus in the catalysis and microbiology communityis addressing Cu+ stabilization by altering the Cu2+Cu+redox potential via the proper choice of ligand environmentboth with respect to chemistry and geometry (see Section 2)[76ndash79] Here the ligand environment in copper proteinsincluding both the Cu(I) [77ndash79] and the Cu(II) [79ndash94]oxidation statse is a continuous source of inspiration

Encouraged by our findings concerning azole-Cu2+ coor-dination mentioned in the previous Section and recentadvances in Cu2+Cu+ stabilization we have developed a

generic concept of biocide-free antifouling coatings By incor-porating azole-type ligands in the antifouling coating thepool of free and sequestered Cu2+ in the marine environmentmay be absorbed It is important that the interaction is strongenough since a large fraction of the dissolved copper in thesea is associated with organic ligands Typically weak ligandsare considered to have stability constants of the order 109 andstrong ligands of the order 1013 [73ndash75] However this con-cept is still feasible given the fact that azole-type ligands havestability constants for copper coordination ranging between1014ndash1020 depending on chelate properties and chemistry asdiscussed in Sections 2 and 6 and the references withinFurthermore regarding the antifouling coating the presenceof strongly Cu+ stabilizing ligands for example nitrilesand sulphur-containing ligands may catalyse the reductionof Cu2+ to Cu+ This will produce high concentrations ofCu2+ and Cu+ both of which are efficient antifouling agents


[67 68] at the coating interface without any net additionof biocides to the environment (see Scheme 3) The azolespecificity towards Cu2+ is treated in Section 41 and the Cu+stabilization including our on-going work with the triazoleligand is briefly discussed in Section 62

2 Theoretical Considerations of Imidazole andTriazole Coordination Chemistry

In this work the coordination of azole ligands (mainly imi-dazole) by Cu2+ Cu+ and Zn2+ ions has been investigated aspresented in Scheme 4 It is therefore pertinent to describethe fundamentals for the strong interaction between the pre-viously mentioned species In the following subsections theazole coordination chemistrywill be briefly reviewed in termsof coordination geometry molecular orbitals and electronicstructure covalency aromaticity and so forth

21 HSAB Principles and 120590-Interaction The strong metal-ligand bonding between the metal ions Zn2+ Cu+ (dia-magnetic d10 full d-shell configuration) Cu2+ (paramagneticd9 configuration) and the imidazole or triazole ligand (seeScheme 5) may be qualitatively explained by HSAB (HardSoft Acid Base) principles [95 98 99] To begin with onlythe electron lone pair donation from the base (ligand) to theacid (metal) 120590-bonding will be considered

Hard bases preferentially bond to hard acids via ionicbonding whereas soft bases favourably bond to soft acidsvia covalent bonding [98 99] In the ligand field depiction(see Scheme 7) this implies that the energy levels of themetal (M) and ligand (L) orbitals (the d120590- and 120590-levels) willbe similar [100 101] The ensuing M-L molecular orbitalswill have almost equivalent proportions of metal and ligandcharacter respectively and the electrons spend their time atthe metal and ligand equally [100] Ionic bonding denoteslarge orbital energy differences with essentially no electronsharing [98ndash100]

Hard acids and bases are small hard to polarize with lowand high electronegativity respectively [98 99]They possesslarge HOMO-LUMO (Highest Occupied Molecular OrbitalLowest Unoccupied Molecular Orbital) gaps favouring ionicbonding [100] Soft acids and bases are large and polarizablewith intermediate electronegativity and with small HOMO-LUMO gaps [98 99] Note that Cu+ is considered a soft acidand that triazole is softer than imidazole A high oxidationstate usually renders the transition metal hard whereas thesoft has low oxidation state (le2) [100] With regard to basesunsaturation usually makes them softer [99] For regular 120590-donors the coordinate bondmay be viewed as polar covalentespecially with regards to borderline acids and bases (seebelow) [99 100]The selectivity of differentmetal-ligandpairsin polymers is treated in Section 41

22 120587-Interaction 120587-bonding is another important interac-tion (besides 120590-bonding) in transition metal complexes (seeSchemes 5 and 7) [100] Ligands with more than one lonepair labelled 120587-donors or 120587-bases (see Schemes 5 and 7)for example Clminus and ROminus may donate additional electron

density to a metal d orbital (120587-acid) of proper symmetry(see Scheme 7 120587-bond) [100] This interaction is typicallyconsidered hard and destabilizes the metal d-orbitals butwill be favourable for hard electropositive (especially d0)transition metals [100] Certain ligands labelled 120587-acceptoror 120587-acid have low-lying vacant LUMOs of proper symmetrywith regard to the metal d120587-orbitals (120587-base) susceptible formetal to ligand 120587-bonding (back donation) an interactiontypically considered soft This interaction may be favourablesince it alleviates the metal of some electron density in thecoordination compound For unsaturated ligands the anti-bonding 120587lowast-orbital typically accepts electron from the metald120587-orbitals which is favourable for electron-rich metals inlow oxidation states with high energy d-orbitals that are basicin character [100]

23 Coordination Geometry Imidazole is coordinated byCu2+ in an essentially square planar geometry Cu(Im)

4

2+sdot

Xminus2 similar to pyridine (see Schemes 6(a) and 6(c)) with the

imidazole rings occupies coplanar positions with respect toCu(II) [95]This favours120587-interaction between the imidazolering orbitals and metal d120587 orbitals and locates the electronhole in a distinctly separated orbital (see Scheme 6(a))[79 95] In the case of Zn2+ or Cu+ tetrahedral geometryis frequently encountered (common for d10 metals [101])Zn(Im)

4

2+sdot Xminus2(see Scheme 7(b)) Octahedral geome-

try (see Scheme 5(c)) Zn(Im)6

2+sdot Xminus2 is also possible for

Zn(II) but not for Cu(I) The coordination is less dependenton electronic factors for Zn(II) and more on steric factors incontrast to Cu2+ complexes [95 101] As an example Zn2+with Clminus as counterion coordinates unsubstituted imidazolein octahedral geometry of 119874

ℎsymmetry [Zn(Im)

6]2+ (see

Section 61) [38] However the addition of a methyl groupat position 1 or 4 on the imidazole ring which gives aslight steric hindrance results in the formation of pseu-dotetrahedral complexes [Zn(Me-Im)

2Cl2] of 1198622V symmetry

even at large excess of imidazole ligands [38] It shouldbe noted that the nature of the counterion has an effecton the type of complex formed and that octahedral (119874

ℎ

symmetry) and tetrahedral (119879119889symmetry) complexes of Zn2+

and methylated imidazoles have been reported [95]The coordination geometries for triazole ligands aremore

complicated Since triazole is bidentate with the possibilityto bind to two metal centers the coordination usually resultsin polymeric (1D 2D or 3D) structures [102ndash105] This is apopularmethod to producemetal-organic frameworkswhichis also possible for imidazole ligands at sufficiently high pH[38 95] However this is outside the scope of this reviewandwill not be further treatedMononuclear coordinate com-plexes comprising triazole ligands do exist provided that thetriazole is substituted with sufficiently bulky groups In thesesituations the triazole displays the same type of coordinationgeometries as the imidazole ligand [102ndash104] (see Scheme 6)

24 Comparison with Other Nitrogen Ligands Azoles andother unsaturated nitrogen ligands such as pyridine arecategorized as borderline bases while Cu2+ and Zn2+ areborderline acids in contrast to Cu+ which is soft [95 98 99]


Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im

Cu2+ stabilizing ligand Cu+ stabilizingligand

Scheme 3 Mechanism for ligand-mediated absorption and redox reaction

N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5

Scheme 4 Structure and numbering of the imidazole 124-triazoleand 123-triazole N

1is labelled pyrrole nitrogen andN

3(imidazole)

and N2N4(triazole) are labelled pyridine nitrogen Note that N

1is

also sp2 hybridized and the free electron pair is donated to the ring120587-orbital system in order to obtain aromaticity The lone electronpair of N

3is however free rendering of this nitrogen basic and the

predominant site for coordination [95]

Consequently these borderline acid-base pairs formfavourable bonds with bond properties which are intermedi-ate to those of soft and hard acid-base pairs [98ndash100]Imidazole is generally considered to be a moderate 120590-donorand a weak 120587-acceptor with 120590-donor and 120587-acceptor abilitiesin between saturated amines such as ammonia (NH

3) and

unsaturated amines such as pyridine [95] This positionsimidazole above oxygen donors and below ammonia andpyridine in the spectrochemical series [95 106] In rare cases120587-donor abilities from the imidazole-ring 120587-orbital havebeen reported [107 108]

The series of nitrogen donor ligands with increasingbasicity follows the order NH

3gt imidazole gt pyridine

whereas the order of increasing 120587-acceptor ability is thereversed [95] For Cu(II) and Zn(II) the bond strength

follows the order imidazole gt NH3gt pyridine reflecting a

dominating importance of 120590-bonding but also a significantcontribution from 120587-bonding [95]

Triazoles are softer ligands than the corresponding imi-dazoles with stronger 120587-acceptor interaction and weaker 120590-donor (basicity) interaction [109] For azoles the series ofincreasing 120590-basicity and decreasing 120587-acidity follows theorder 124-triazole gt pyrazole gt thiazole ≫ imidazole [110]Consequently triazole ligands are better than imidazole instabilizing Cu+ in favour of Cu2+

3 Functionalization of Polymers

For the antifouling coatings containing azole ligands asdescribed in Sections 12 and 13 it is necessary to developsuitable synthetic routes in order to functionalize polymerswith azole ligands All polymers and low molecular weightimidazole containing substances used in this work are pre-sented in Scheme 1 We have investigated both N- and C-substituted azoles The attachment position of the polymerbackbone (the substituent) on the azole ring has importantconsequences for the coordination chemistry as described inSection 61

31 Imidazole Functionalization A popular technique tofunctionalize polymers is to graft functional groups onto anactive site on the polymer backbone [111ndash116] It is often easierto polymerize a smaller monomer with an active site thana large bulky monomer with the functional group alreadyattached This type of functionalization is sometimes calledpostpolymerization modification [115 116]

An epoxide route was used in order to functionalizeethyl(hydroxyethyl)cellulose (EHEC) with imidazole groups[49] In short the procedure involved 4 steps protection of


M-L 120590-bond

M-L 120587-bonddxy (Cu2+)

120590-donorOrbital of the lone pair onN3

120587-donorHighest occupied 120587-orbital

120587-acceptorLowest unoccupied 120587lowast-orbital

eminus

eminus

eminus

eminus

eminus

eminus

Antibonding ring120587lowast-orbital

dxy

sp2 hybridized lonepair orbital

M-L 120590-bond

M-L 120587-bonds Ring 120587-orbitaldxy

NH120590-donor120590-acceptor

Cu2+

120587-donor120587-acceptor

Cu2+

120587-acceptor120587-donor

z x

y

Cu2+

Cu2+Cu2+

x

y

z

Molecular orbitalsBonding modes

Coordination complex Ligand orbitals

N

N

N

dx2minusy2

dx2minusy2 (Cu2+)

Scheme 5 Coordinate bonding modes (left) and molecular orbitals (right) envisaged for azole-Cu(II) in square planar geometry as obtainedfrom DFT calculations [38] The bonding principles are generic and applied also for Zn(II) and Cu(I) complexes

Zn2+Zn2+Cu2+

(a) (b) (c)

Scheme 6 Coordination geometries for imidazole-Cu(II) or -Zn(II) complexes [38] (a) Square planar [Cu(Im)4]2+ (b) Tetrahedral

[Zn(Im)4]2+ (c) Octahedral [Zn(Im)

6]2+


3d

4p

4s

Crystal field splitting

120590-bonds

120587lowast-antibond

120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex

Cu(II) square planar ligand field

Nonbonding -orbitalsand

120590 levels

Bonding 120587-interaction with eitherligand electrons (120587-donor ligand) orstabilized electrons (120587-acceptor ligand)

by 120587-donor ligandDestabilized -orbitals

120590lowast levels

120587lowast levels

E

dx2minusy2d120590lowast

d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587


Destabilized and-orbitals by 120587-donor ligand

Metal d-orbital splitting

120587-interaction with 120587-donor ligand

Nonbonding -orbitals

120587-interaction

120587-interaction with 120587-acceptor ligand

Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

ComplexZn(II) and Cu(I) tetrahedral ligand field

(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590

Scheme 7 (a) Molecular orbitals and ligand field splitting of Cu(II) in a square planar complex and of (b) Zn(II) or Cu(I) in a tetrahedralcomplex [96] (a) With regard to cupric complexes there is possibility for weakly bound counterions or coordinating solvent molecules inaxial position and the geometry is then labelled tetragonal (distorted octahedral symmetry) However the ligand field splitting will be similarin tetragonal and square planar symmetry if one accounts for the important 4s-3dz2 mixing which effectively lowers the metal dz2 orbital inboth symmetries [97] (b) The ligand field splitting in tetrahedral complexes is the inverse of an octahedral one but with some mixing of thed120590and p-orbitals The situation with 120587-interaction is however more complicated since the 120587-interacting ligand orbitals may form both 120590-

and 120587-bonds and the effect on the ligand field splitting will be a reflection of both bonding modes [96 97]

the pyrrole nitrogen reduction of the aldehyde to epoxideepoxide opening and attachment to the polymer backboneand finally removal of the protective group (see Scheme 8)The modified polymer and its interaction with Cu2+ areevaluated in Section 422

We have also developed a synthesis procedure to attachthe biological amino acid histidine to a polymer backbone as

well as to a polymerizable monomer using maleimide chem-istry [48] The synthetic routes comprised both grafting ontobymaleimide bond formation on amaleic anhydride polymer(see Scheme 8) and conventional radical polymerization (seeScheme 8) The successful grafting of histidine onto P(E-alt-MAh) (poly(ethylene-alt-maleicanhydride)) was confirmedby the formation of the maleimide bond The DS (degree of


O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2

1 or 2HMI maleoyl histidineP(E-alt-HMI) poly(ethylene-alt-N-histidyl maleimide) P(E-alt-HMI) methylester (see Figure 11)

HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4

PVM P(1-VIm) P4VMPHMI PMMA (see Figure 11)

1 2

4 Im-EHEC (see Figure 11)

3

1-step grafting without protective group

Monomers for AIBN initiated radical polymerization

lowast( )

[]

4-step grafting with protective group

Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)

Scheme 8 Imidazole functionalization of polymers and monomers [48 49] and monomers used for AIBN initiated radical polymerization[39 47 48]

substitution) ranging from80ndash90was estimated fromNMRspectra and elemental analysis In conclusion imide bondformation between amine and anhydride is an efficient wayof grafting histidine onto a polymer backbone [48]

Radical or anionic polymerization of maleimide mon-omers is an established synthesis procedure thoroughlyinvestigated [120ndash128] Since the maleimide group is stronglyelectron withdrawing effectively reducing the electron den-sity at the maleic double bond it is custom to copolymerizeit with for example styrene or other monomers containing

electron donating groups Such a copolymerization results inrather alternating copolymers [120] This copolymerizationtechnique is also common for polymerization of maleicanhydride which is not possible to homopolymerize [120]However it is still possible to homopolymerize maleimideseven though the reaction rate is very slow [125] The reactionrate in this case is additionally decreased since the histidineside group renders the monomer large and bulky [122129] Both routes were successful but the maleimide routefacilitates both grafting onto and radical polymerization


Furthermore themaleimide route is conveniently carried outin one step without the necessity of protective groups [48]

Another way of functionalizing polymers is to copoly-merize with the monomer of the polymer with a smallfraction a functional comonomer We have functionalizedPMMA with imidazole moieties by simple copolymerizationusing AIBN as initiator (see Scheme 8) Copolymers ofMMA (methylmethacrylate) and 1-VIm (1-vinylimidazoleor N-vinylimidazole) (poly(1-VIm-co-MMA or poly(N-VIm-co-MMA) abbreviated PVM) [47] as well as 4-VIm(4-vinylimidazole) (poly(4-VIm-co-MMA) were polymer-ized using conventional AIBN radical polymerization (seeScheme 8)with the rationale of functionalizing PMMAwhichis the most commonly used microcapsule shell material [4757ndash59 63] (see Section 11) The polymerization results instatistical copolymers with a higher reactivity ratio for MMAcompared with 1-VIm as demonstrated by Wu et al [130]

32 Triazole Functionalization and Click Chemistry In con-formity with the vinylimidazole-based polymer polymersbased on vinyltriazoles (1-vinyl-124-triazole [131] 1-vinyl-123-triazole [132] and 4-vinyl-123 triazole [132]) may beprepared by conventional AIBN-initiated radical polymeriza-tion [131 132]These polymers have found use as heavy metalbinding resins for waste water treatments [131] and protonconductors (C-substituted 4-vinyl-123 triazole) [132]

However triazole synthesis is most synonymous withthe copper catalyzed alkyne-azide huisgen cycloaddition(CuAAC) reaction [117] (see Scheme 9) This reaction is awell-known example of a class of chemical reactions calledldquoclick reactionsrdquo defined for the first time by Kolb et al[133] Click reactions are characterized by high quantitativeyields and tolerance towards the use of functional groupsThereactions are also relatively insensitive to the solvent systemConsequently these characteristics make click reactions avery good tool for polymer synthesis and modifications

It is obvious that theCuAAC reaction can be used for tria-zole functionalization of azide or alkyne containing polymerswhich has been investigated by us [50] However the CuAACreaction can also be used to synthesize triazole-based vinylmonomers Thibault synthesized vinyl containing triazolemonomers (R

1= vinyl in Scheme 9) which were polymerized

via reversible addition chain-transfer (RAFT) reaction [134]Using this methodology a variety of monodisperse polymerscarrying different functional group were synthesized [134]

4 Properties of Coordinated Polymers

The coordination of polymers carrying ligand sites by metalions has a profound effect on the polymeric material [135ndash139] which includes properties and functions such as opticalelectrical rheological molecular self-assembly and solubilityproperties [137ndash141] The basis for the majority of propertiesand functions relies on the specificity and strength of coor-dination for a given set of metal ion and ligand Thereforeregarding the use of these materials in antifouling coatings(triggered release or Cu2+ sorptionredox reaction) it isimportant to understand the details of the coordinate inter-actions on both a microscopic and a macroscopic levels

N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2

Scheme 9 Dipolar 13-cycloaddition of an azide and an alkyneThe regular Huisgen 13 dipolar cycloaddition between an azide andan alkyne results in a mixture of 14- and 15 substituted triazoles[117]TheCuAAC reaction is stereospecific and yields 14 substitutedtriazoles [118] The reaction can also be catalysed by Ru(II) whichyields 15 substituted triazoles [119]

In our group the coordinate interaction of the materialshas been characterized using EPR vibrational spectroscopy(far-FTIR and mid-FTIR) ab initio and DFT (Density Func-tional Theory) calculations The material properties havebeen characterized using mainly DSC (differential scanningcalorimetry) and vibrational spectroscopy

41 Bond Strength and Selectivity Regarding the PVM copol-ymers discussed in Section 31 the polymer contains twopossible metal-coordinating ligands the imidazole and theester groups (see Scheme 1) The carbonyl group is regardedas a hard ligand with the oxygen atom as the ligating groupalthough with a theoretical possibility of acting as a soft120587-bond donor [100] However the metal ions exclusivelycoordinate the imidazole ligand of the polymer [47] This isevident since only imidazole bands in FTIR are altered uponcoordination (see Figure 1) [39 47] Regarding copper com-plexes EPR affirms this fact since complexation of PMMAresults in no signal (see Figure 2(c))The EPR results concernonly Cu2+ complexes Zn2+ is diamagnetic and hence EPRsilent Furthermore the environment appears to be squareplanar (or tetragonal) due to the resemblance between theEPR spectra of square planar [Cu(Me(1)-Im)

4]2+ and PVM-

4-Cu2+ This result is quite spectacular since the enforcedcoordination symmetry results in a high entropic penalty forthe polymer chain It should be noted that the EPR param-eters and spectrum of PVM-4-Cu2+ are especially similar toimidazolemethylated at position 1 (Me(1)-Im) coordinated byCu2+ (see Figure 2) [38 47]

Publications on polymers containing the C4substituted

4-vinylimidazole are rare in comparison with N1substituted

1-vinylimidazole yet interesting due to the unsubstituted pyr-role nitrogen (see Schemes 1 and 8) Note that biological imi-dazole moieties such as histidine are never N

1-substituted

[38] (see Section 61) Sato et al have studied homopolymers


4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)

Figure 1 FTIR spectra of PVM-44 (c) coordinated by Cu2+ (a) orZn2+ (b) [47] As a result of complexation some FTIR bands ofthe imidazole (marked blue) are shifted in particular the in-planeskeletal vibrations of the imidazole ring However the carbonylstretch of the MMAmethylester (marked red) remains unaltered

of poly(4(5)-vinylimidazole) [142ndash144] which appeared tobe coordinated by Cu2+ in a square planartetragonal geom-etry The copolymers investigated by us poly(4(5)-VIm-co-MMA) appeared to form stronger bonds than the cor-responding P(1-VIm-co-MMA) polymers as manifested bya complete insolubility of the resulting metal complex Incontrast themetal complexes of P(1-VIm-co-MMA)were sol-uble in strongly coordinating solvents for example DMSOMeCN or DMF [47]

42 Coordinate Crosslinks The coordinate bonds betweenthe imidazole ligand and the metal ions generate crosslinksbetween the polymer chains [47] The crosslinks cause theglass transition temperature 119879

119892 to increase since the chain

segments in proximity of a crosslink are stiffened due tothe reduced rotational freedom (see Figure 3) [47 145] Thestiffness depends on the strength of the crosslink Hence theincrease of 119879

119892will depend on both the number of effective

crosslinks as well as the strength of the crosslinking bond [47135 136 146] Regarding the polymers the increase of 119879

119892is

more pronounced for PVM-44 than PVM-4 due to the largernumber of possible crosslinks However when the effect ofthe particular metal ion is inspected it is observed that Cu2+raises119879

119892more than Zn2+ for PVM-4while the opposite holds

for PVM-44 This may appear contradictory but is explainedby coordination bond strength and coordination numberThe bond strength between imidazole and Cu2+ which isstronger than the bond strength between imidazole and Zn2+which is most important for PVM-4 with a low numberof imidazole ligands However the total number of possible

1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )

Figure 2 Cu2+ EPR spectra in MeCN of (a1) PVM-4 (a2) Im (a3)Me(1)-Im (a4)Me(4)-Im (b1) PVM-44 (b2) PVM-44 half field sig-nal (c1) PMMA and (c2) H

2O [38 47] The paramagnetic centers

that is the Cu(II) ions of PVM-44 are closer together compared toPVM-4 which is reasonable due to the larger fraction of imidazoleligands per polymer chain To be more precise the coordinationcomplexes are separated by less than 20 A (see Figure 2(b2)) whichis indicated by the EPR half field signal (see Figure 2(b2))


100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated

P(1-VIm) PVM-44 PVM-4 PMMA

Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers

Figure 3 Glass transition of polymers and polymer complexes [47]

crosslinks may be higher for Zn2+ complexes since this metalallows for octahedral geometry (see Section 23) whereasCu2+ is restricted to square planar geometry This explainswhy PVM-44 with a high number of imidazole ligands coordi-nated to Zn2+ acquires a higher119879

119892than PVM-44 coordinated

to Cu2+ despite a weaker coordinate bond

421 Hygroscopicity and Metal Coordination The hygro-scopicity of a PVM polymer containing a metal ion salt ishighly dependent on the fraction of imidazole containingmonomers In addition the water molecules can crosslinktwo imidazole groups of a PVM polymer in a similar manneras the metal cation The hydrogen-bond interaction is tooweak to alter the thermal properties of the polymer yet thechange of the polarization of the water molecules is evidentby the blue shift of the 120575(HOH) water bending vibration(see Figure 4) However when metal ions are introducedthis population of bridged water molecules disappears andis replaced by bridging metal ions (see Figure 4) [39 47]For PVM-4 with a low fraction of imidazole ligands theintroduction of metal ions results in a significant increase ofsolitary water as indicated by the area of the V(OH) waterstretching vibrations [39] However for PVM-44 with a highfraction of imidazole ligands the metal ion coordinationresults in a decrease of the amount of sorbed water [39]Note that this polymer is already rather polar due to the highfraction of N-VIm monomers Consequently the triggeredrelease effect discussed in Section 12 is more applicable forhydrophobic polymers which are functionalized with cross-linking metal ions

422 Coordination-Mediated Multilayer Assembly Thestrong coordinate cross-links discussed previously can beused to assemble polymer multilayers Polymer multilayersare most synonymous with the polyelectrolyte layer-by-layertechnique which has received a lot of attention during the last

decade [64] However coordination chemistry is a feasibletool to assemble multilayers with anisotropic properties asprovided by the restricted coordination geometry of a givenmetal ion Hedin et al studied the bilayer formation ofthe imidazole functionalized biopolymer Im-EHEC (seeScheme 1) using QCM-D [49] Although Im-EHEC wasfunctionalizedwith only 1 imidazolemoieties permonomerunit the introduction of copper resulted in a slight cross-linking of the adsorbed polymer layer and the subsequentaddition of Im-EHEC solution gave an additional adsorbedmonolayer of Im-EHEC (see Figure 5)

5 Antifoulant Immobilization andControlled Release

In the following subsections ways to immobilize and controlthe release of antifouling agents using coordinate interac-tions with a special focus on medetomidine will be pre-sentedThe immobilization of medetomidine has been evalu-ated using HPLC NMR and vibrational spectroscopy as wellas monitored in situ in model systems using QCM-D andSPR The controlled release has been monitored from realcoatings using liquid scintillation spectrometry (14C

minusprobed

release substances) as well as from model surfaces using thesurface sensitive techniques QCM-D and SPR

51 Polymer Coordination Triazole derivatives represent awide class of antimicrobial substances (see Scheme 1) [19ndash27] as mentioned in the Introduction Their use in antifoul-ing coatings has been claimed in a number of patents [147ndash150] As an example Tanaka and coworkers immobilized an-tifoulants based on triazole thiadiazole and benzotriazolein resins containing a high fraction of carboxylate groups[147]

In a similar manner Shtykova et al studied the immo-bilization of the imidazole containing medetomidine (seeScheme 1) on an alkyd resin using NMR diffusometry [44] Itwas found that the self-diffusion coefficient of medetomidinewas decreased by more than one order of magnitude dueto immobilization of medetomidine on the alkyd resin Itwas proposed that the mechanism of immobilization washydrogen bonding between the protonated imidazolium ionofmedetomidine and deprotonated carboxylate groups of thealkyd resin [44]

This concept was further developed by Handa et alto encompass polymers with very strong Lewis acid sitesMedetomidine was immobilized and released from thesulphonated polymer SPSEBS (see Scheme 1 the nonsul-phonated polymer PSEBS was used as a reference) as mon-itored in situ using QCM-D [41] In the solvent xylene largeamounts ofmedetomidine were adsorbed almost irreversiblywhich was ascribed to a coulombic charge-transfer reactionin the hydrophobic solventThe interactionwasmuchweakerin artificial seawater with less adsorbed medetomidine and apronounced release upon rinsing [41]This system could con-sequently be used as a triggered release system (see Scheme 2)as discussed in Sections 11 and 12


M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm

Coordinate cross-linkM2+ ion(Cu2+ or Zn2+)

Pendant imidazole group

Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water

Figure 4 Schematic drawing of Im-H2O-Im bridged water and subsequent replacement by Cu2+ or Zn2+ including the most important

markers for H2O and Im respectively as well as the electrostatic potential energy surface of the [Cu(Im)

4X2] complex as obtained from ab

initio calculations [39]

First Im-EHEC adsorption layer

Second Im-EHEC adsorption layer

0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)

Figure 5 Bilayer formation of Im-EHEC (see Scheme 1) withCuCl2(measured using QCM-D andmodeled using a Voight-based

viscoelastic model) The second layer is thin and corresponds to amonolayer Reprinted from [49]

52 Metal Ion and Metal Oxide Nanoparticle CoordinationThe hydrogen bonds mentioned in the previous section arerelatively strong interactions yet the strength of coordinatemetal-ligand bonds discussed in Section 2 is significantlyhigher Therefore the Nyden group explored the feasibilityof using transition metal coordination for medetomidineimmobilization Fant et al investigated the adsorption andcontrolled release of medetomidine from PVM polymers(see Scheme 1 PVM-44) coordinated by Cu2+ or Zn2+ using

QCM-D [40] Cu2+ was adsorbed in much higher amountsthan Zn2+ by the PVM polymer which is in line with the sta-bility constants Moreover the metal ion adsorption resultedin a pronounced swelling of the PVM polymer by waterwhich corroborates its feasibility to be used as a material fortriggered release applications as discussed in Sections 12 and421 The subsequent addition of medetomidine resulted insignificant adsorption for both PVM coordinated by Cu2+and Zn2+ (see Figure 6) Note that the resulting complexcontains imidazole ligands from both the PVM polymer andmedetomidine However the interaction of medetomidinewith Zn2+ wasmore reversible than with Cu2+ and resulted ina much faster release (see Figure 6) Thus the release profilemay be tailored by coordinating the PVM polymer withmixtures of Zn2+ and Cu2+ [40]

In addition to polymers coordinated by metal ionsmetal oxide nanoparticles are feasible vehicles for antifoulantimmobilization using coordination chemistry [45 46]Shtykova and coworkers studied the immobilization of somecommon booster biocides including medetomidine and Sea-nine (see Scheme 1) ondifferent types ofmetal oxide nanopar-ticles (see Figure 7) It was apparent that the booster biocidescontaining ligand moieties (medetomidine irgarol diuronand Seanine) gave the strongest adsorption Note that theisothiazolinone Seanine (see Scheme 1) has the possibilityto bind via hard interaction (carbonyl oxygen) or via softinteraction (sulphur free electron pair) Regarding the nitro-gen which is of pyrrole type interaction at this position isonly possible at very high pH for isothiazolinones which


Rinsing

Medetomidine addition 0

100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

Cu2+-PVM21nm QCM-DZn2+-PVM21nm QCM-DCu2+-PVM21nm SPR

Zn2+-PVM21nm SPRPVM21nm SPRPVM21nm QCM-D

Figure 6 Medetomidine absorption (measured using QCM-D andSPR) to a Cu2+ doped Zn2+ doped andmetal free 21 nm thick PVMfilm It is apparent that metal coordination significantly enhancesmedetomidine adsorption and that the coordination to Cu2+ isstronger and less reversible Reprinted from [40] The combinationof QCM-D and SPR measurements can be used to estimate theamount of sorbed solvent in an adsorbed film The acoustic QCM-D technique probes the entire adsorbed viscoelastic layer includingbound solvent In contrast the SPR method measures changes inrefractive index at the surface and consequently takes only the massof the adsorbent into accountThe difference in adsorbedmass fromQCM-D and SPR measurements can therefore be related to theamount of solvent

are unsubstituted at position 2 However the affinity ofmedetomidine for the metal oxide particles was substan-tially higher than that of any other biocide This indicatesthat the imidazole group of medetomidine is key for itssuccessful immobilization (see Figure 7(a)) The order ofincreasing interaction strength with the imidazole ligand wasslightly different for the metal oxides compared with thecorresponding metal ions (see Figure 7(b) and ZnO displaysa stronger interaction with medetomidine than CuO) [42]This is reasonable since the metal centers in the oxides aremuch more electron-rich compared to the free metal ionsThe immobilization of medetomidine on ZnO nanoparticles(which are common pigments in antifouling marine paints)resulted in a significant decrease in the release rate from avarnish coating as comparedwithmedetomidinemolecularlydispersed in the same coating (see Figure 7(c)) [42]

6 Effect of Ligand Substituent Position andLigand Chemistry

The coordinate interaction as described in Section 2 is notonly dependent on the type of ligand used but also on thesubstituents attached at the azole ring This has been investi-gated by us in detail using vibrational spectroscopy EPR abinitio and DFT calculations and is presented in Section 61

In Section 62 these results are discussed with respect toCu2+Cu+ stabilization as presented in Section 13

61 ldquoNaturalrdquo versus Synthetic Ligands When inspecting thepolymers discussed in Section 3 (see Scheme 1) it is observedthat the imidazole ligand is attached to the polymer backboneat either position 1 or 4 and this holds for in principle anyarbitrary imidazole-containing polymer Moreover regard-ing imidazole from biological sources such as histidine theimidazole ring is always substituted at position 4 This is incontrast to synthetic imidazole-containing polymers wherethe imidazole ring is usually attached to the backbone at posi-tion 1 that is via the pyrrole nitrogen Subsequently it maybe speculated why nature has chosen this particular positionfor substituent attachment To investigate this themethylatedimidazole model compounds Me(1)-Im and Me(4)-Im (seeSchemes 1 and 10) were analysed with respect to similaritiesand differences in coordination strength coordination geom-etry covalency and so forth [38]

Both compounds display profound covalence in the 120590-bond (1205722 = 71 according to DFT calculations) which is alsoevident by the hyperfine splitting in the EPR spectrum (seeFigure 8) [38] An even better indication of the high degreeof covalence is the 120587-interaction coefficient (EPR 1205732 asymp[065 069] ab initio 1205732 asymp [051 060]) [38 151] Small dif-ferences as an effect of position regarding the coordinateinteraction are evident since the Me-C

4bond is slightly more

polarizable than the Me-N1bond As a consequence Me(4)-

Im is a stronger base than both Me(1)-Im and Im sincethe methyl substituent is an electron-donating group (seeScheme 10) [38] However the stability constant is lower forthe corresponding Me(4)-Im complex compared to Me(1)-Im and Im [38 152] which suggest a significant 120587-acceptorinteraction in addition to the 120590-donor interaction in thecoordinate complex [38] as discussed in Section 2 Howevermuch larger effects were obtained by changing the type ofsubstituent as was apparent from ab initio calculation Bysystematically changing the position of the substituent as wellas the substituting group it was observed thatΔ119864 (the energyof complexation) and 120592

119886(M-L) (metal-ligand asymmetric

stretch vibration) were more affected by the chemistry of thegroup than its actual position

The coordination geometries forMe(1)-Im andMe(4)-Imare more or less identical For instance the steric hindranceof the methyl group upon coordination is the same for bothmethylated imidazoles (see Schemes 1 and 10 and Figure 9)since Me(4)-Im actually coordinates as Me(5)-Im [38 154]due to tautomerism and steric restrictions As a consequencethe coordination geometries for the methylated imidazoleligands are very similar both for Cu2+ andZn2+ complexes incontrast to unsubstituted imidazole (see Figure 9) Howeveran important difference between Me(1)- and Me(4)-Im isthe reduced ldquodegrees of freedomrdquo for Me(1)-Im Me(4)-Imequivalent to Im or triazoles contains two potential sites forcoordination or protonation Consequently Me(4)-Im andIm may as a function of ligand metal ratio and pH formcoordination polymers which is restricted to Me(1)-Im [38]


0

20

40

60

80

100Ad

sorp

tion

()

0 05 1 15 2 25Surface area ZnO (m2)

MedetomidineDiuronIrgarolSeanine

TolylfluanidChlorothalonilDichlofluanid

(a)

0

20

40

60

80

100

Adso

rptio

n (

)

0 2 4 6 8 10Surface area (m2)

ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)

Figure 7 (a) Immobilization efficiency of various booster biocides including medetomidine (see Scheme 1) on ZnO nanoparticles as afunction of total particle surface area (a) Immobilization efficiency of medetomidine on various metaloxide nanoparticles as a functionof total particle surface area (c) Effect on release of free (varnish 1 998787) and ZnO immobilized (varnish 2 I) medetomidine from coatingsReprinted from [42]

If the polymeric imidazole ligands used in this work arecompared that is 1-VIm and histidine the position of thesubstituent in the imidazole ring is not the most importantfactor (see Scheme 11)The chemical nature of the substituentmore precisely its electron withdrawing or electron donating

abilities is more important with respect to the coordinateinteraction However the position of the ring substituent isimportantwhen it comes to bidentate coordination the possi-bility to conduct protons between adjacent imidazole ligandsand ring polarization due to coordinating nucleophiles [38]


Position of substituent

Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im

Chemistry of substituent

Electron donating groups

Electron withdrawing groups

Scheme 10 Imidazole derivatives with various substituents at different ring positions The molecules have been geometry-optimized usingDFT [38]

HN HN HN HNN N N N

CH3HO

O

NH2N

120590-donor (simbase strength)

120587-acceptor

Electron withdrawing group


Electron donating group

Ceminus eminus

eminus

Scheme 11 The effect of the substituent with respect to electron do-natingaccepting capacity on the coordinate interaction

62 Cu2+Cu1+ Stabilization As mentioned in the introduc-tion Cu+ is highly unstable in water and disproportionates toCu2+ and Cu0 This is a consequence of the hydrate complexwhere water which is a hard base (see Section 21) stronglystabilizes Cu2+ (border line acid) over Cu+ (soft acid) How-ever it is possible to alter the redox potential in favor of Cu+by changing the ligand environment [100 158] In Figure 104mM CuCl

2has been dissolved in waterglycerol (hard

ligands) or acetonitrile (MeCN soft ligand) [38] The area ofthe EPR signal is proportional to the concentration of Cu(II)ions The MeCN system displays a smaller area compared tothe waterglycerol systemwhich indicates reduction of Cu(II)to the EPR silent Cu(I) It is well known that nitriles stronglystabilize Cu+ in favour of Cu2+ [38 47 76 159ndash161]

However soft ligands such as nitriles prevent the catalyticability of Cu2+Cu+ by stabilizing the Cu(I) oxidation statetoo well [76] In order to find a proper ligand environmentscientists are once again finding inspiration in biologicalsystems in particular copper containing enzymes [76 79]Regarding the efficient catalytic activity and the electrontransfer capability found in type 1 blue copper proteins the

ligand set of the copper complex contains both Cu2+ andCu+ stabilizing ligands (histidine and cysteinemethionineresp) [79 162] In addition the coordination geometryis forced into a distorted tetrahedral symmetry which isan intermediate geometry between square planartetragonal(Cu2+ coordination) and tetrahedral (Cu+ coordination seeScheme 6) [79] This has been suggested to facilitate the easeof electron transfer and oxidationreduction of the copper ion[79 162]

We are currently investigating triazole-based ligands forCu+ stabilization [50] as described in Section 13 with respectto antifouling properties The polymers are synthesized bya grafting onto approach as described for imidazoles [48] inSection 31 using the CuAAC click reaction (see Section 32)The triazole ligand have in accordance with imidazole avery high affinity for Cu2+ Yet triazole ligands may alsostabilize Cu+ Moreover the coordination geometry can betuned by the proper spatial distribution of ligands of differentchemical nature By tailoring the ligand environment andthe subsequent coordination geometry in triazole containingpolymers our intention is to prepare antifouling hydrophilicpolymers [163] inspired by copper enzymes which mayabsorb Cu2+ from the sea as well as facilitate the Cu2+ rarrCu+reduction

7 Conclusion and Outlook

Azole coordination chemistry shows great potential withrespect to antifouling coatings for a number of reasonsManyantifouling agents contain azole moieties The imidazolecontaining biocide medetomidine is promising antifoulingagent with respect to protection against fouling of barnaclesThe fact that the azole moiety is a ligand can be used toimmobilize these biocides on macromolecules or nanopar-ticle and thus control their release (both sustained andtriggered release are possible) Moreover the polymericmaterials used for the purpose of controlling the release ofantifouling agents can be given new properties via transition


H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12

Figure 8 Me-Im in waterglycerol (a) EPR signal of Me(1)-Im (green) and Me(4)-Im (blue) (b) Derivative of the EPR signal with inset(b1) displaying the fine structure at 119898

119897= +32 [38] The fine structure indicates four equivalent ligands However some signals appear to be

doublets which may be explained by the Cu2+ isotope mixture [79 153]

metal coordination of pendant azole ligands in the polymerHowever the most promising antifouling approach lies inthe very strong affinity of azoles for Cu2+ which is a potentantifouling biocide An antifouling coating containing azoleligands can subsequently absorb large amounts of naturallyabundant copper and obtain antifouling protection withoutany net release of biocide Moreover the Cu2+ rarrCu+ redoxpotential may be altered towards reduction to Cu+ whichis the most bioactive oxidation state This can be achievedby tailoring the ligand chemistry where triazole ligands arepromising for these purposes We believe that the potentialof this bioinspired approach has not been fully explored A

lot of inspiration can be found in nature in particular copperenzymesThese enzymes are optimised through evolution forcopper absorption as well as copper reduction by using aproper choice of ligand chemistry and ligand geometry

Conflict of Interests

Theresearch in this work has been financed by the foundationfor environmental strategic research MISTRA which isadministrated by the Swedish state In the paper the brandnames of two antifouling biocides are mentioned Selectopeand Seanine It is hereby stated that neither of the authors


Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)

Figure 9 Coordination geometries [38] (a) Tetrahedral [Zn(Me-Im)2Cl2] (b) octahedral [ZnIm

6]2+ and (c) tetragonal [CuIm

4Cl2] and

[Cu(Me-Im)4Cl2] R1and R

2are defined as in Scheme 1 The coordination geometry for Cu2+ complexes is tetragonal D4 h symmetry for

the methylated imidazoles equivalent to unsubstituted imidazole The imidazole ligands are almost perpendicular to the coordination axisand the chlorides are weakly bound axially [38 154ndash156] However regarding Zn2+ complexes unsubstituted imidazole forms octahedralcomplexes [38 155] [Zn(Im)

6]2+ whereas the methylated imidazoles form tetrahedral C2v complexes [38 156 157] [Zn(Me-Im)

2Cl2] despite

the large excess of imidazole ligand

2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0

[Cu(Me(1)-Im)4]2+ in MeCN[Cu(Me(1)-Im)4]2+ in H2Oglycerol

Figure 10 EPR spectra of a tetragonal Cu(II) complex with 1-methylated imidazole in a mixture of water and glycerol (mdash) andacetonitrile (- - -)

is in any financial relations with the previously mentionedcommercial identities Therefore no conflict of interestsexists

Acknowledgments

The foundation for environmental strategic research MIS-TRA is acknowledged for financial support The authors are

also grateful to all coworkers in the Marine Paint ResearchProgram

References

[1] E Almeida T C Diamantino and O de Sousa ldquoMarine paintsthe particular case of antifouling paintsrdquo Progress in OrganicCoatings vol 59 no 1 pp 2ndash20 2007

[2] T Backhaus and A ArrheniusMarine Paint Final Report 2003ndash2011 UO Gothenburg Gothenburg Sweden 2012

[3] L D Chambers K R Stokes F C Walsh and R J K WoodldquoModern approaches to marine antifouling coatingsrdquo Surfaceand Coatings Technology vol 201 pp 3642ndash3652 2006

[4] I Omae ldquoGeneral aspects of tin-free antifouling paintsrdquo Chem-ical Review vol 103 no 9 pp 3431ndash3448 2003

[5] International Maritime Organization International Conven-tion on the Control of Harmful Anti-fouling Systems on Ships2011 httpwwwimoorg

[6] I Omae ldquoOrganotin antifouling paints their alternatives andmarine environmentrdquo Kagaku Kogyo vol 54 p 646 2003

[7] C Hellio andD YebraAdvances inMarine Antifouling Coatingsand Technologies Woodhead Publishing 2009

[8] M A Champ and P F Seligman ldquoResearch information re-quirements associatedwith the environmental fate and effects ofcompoundsrdquo in Organotin pp 601ndash614 1996

[9] M A Champ and P F SeligmanOrganotin Environmental Fateand Effects 1996

[10] H Blanck and B Dahl ldquoRecovery of marine periphyton com-munities around a Swedish marina after the ban of TBT use inantifouling paintrdquo Marine Pollution Bulletin vol 36 no 6 pp437ndash442 1998

[11] M Gustafsson I Dahllof H Blanck P Hall S Molander andK Nordberg ldquoBenthic foraminiferal tolerance to tri-n-butyl-tin (TBT) pollution in an experimental mesocosmrdquo MarinePollution Bulletin vol 40 no 12 pp 1072ndash1075 2000

[12] A Arrhenius T Backhaus F Groenvall M Junghans MScholze and H Blanck ldquoEffects of three antifouling agents


on algal communities and algal reproduction mixture toxicitystudies with TBT irgarol and sea-ninerdquo Archives of Environ-mental Contamination and Toxicology vol 50 no 3 pp 335ndash345 2006

[13] H Blanck K M Eriksson F Gronvall et al ldquoA retrospectiveanalysis of contamination and periphyton PICT patterns for theantifoulant irgarol 1051 around a small marina on the Swedishwest coastrdquoMarine Pollution Bulletin vol 58 no 2 pp 230ndash2372009

[14] B Dahl and H Blanck ldquoToxic effects of the antifouling agentIrgarol 1051 on periphyton communities in coastal water micro-cosmsrdquo Marine Pollution Bulletin vol 32 no 4 pp 342ndash3501996

[15] I Dahllof H Blanck and P Hall ldquoShort-term effects of tri-n-butyl-tin on marine sediment samples using nutrient fluxes aseffect indicatorsrdquo Environmental Toxicology and Chemistry vol18 no 5 pp 850ndash857 1999

[16] K M Eriksson A Antonelli R H Nilsson A K Clarke andH Blanck ldquoA phylogenetic approach to detect selection on thetarget site of the antifouling compound irgarol in tolerant peri-phyton communitiesrdquo Environmental Microbiology vol 11 no8 pp 2065ndash2077 2009

[17] K M Eriksson A K Clarke L-G Franzen M KuylenstiernaKMartinez andH Blanck ldquoCommunity-level analysis of psbAgene sequences and irgarol tolerance in marine periphytonrdquoApplied and Environmental Microbiology vol 75 no 4 pp 897ndash906 2009

[18] P Johansson K M Eriksson L Axelsson and H BlanckldquoEffects of seven antifouling compounds on photosynthesis andinorganic carbon use in sugar kelp Saccharina iatissima (Lin-naeus)rdquo Archives of Environmental Contamination and Toxicol-ogy vol 63 no 3 pp 365ndash377 2012

[19] D George and S van Epps ldquoBenzyl triazole-based aromataseinhibitors for the treatment of breast cancerrdquo Bioact Compd Clp 275 2012

[20] P Worthington ldquoSterol biosynthesis inhibiting triazole fungi-cidesrdquo Bioactive Heterocyclic Compound Classes p 129 2012

[21] R Kharb P C Sharma and M S Yar ldquoPharmacological sig-nificance of triazole scaffoldrdquo Journal of Enzyme Inhibition andMedicinal Chemistry vol 26 no 1 pp 1ndash21 2011

[22] I P Korbila and M E Falagas ldquoInvestigational antimicrobialdrugs for blood stream infectionsrdquo Current Opinion in Investi-gational Drugs vol 9 no 8 pp 871ndash878 2008

[23] R C Moellering Jr J R Graybill J E McGowan Jr andL Corey ldquoAntimicrobial resistance prevention initiative anupdate proceedings of an expert panel on resistancerdquo TheAmerican Journal of Medicine vol 120 no 7 pp S4ndashS25 2007

[24] M M Pearson P D Rogers J D Cleary and S W ChapmanldquoVoriconazole a new triazole antifungal agentrdquo Annals ofPharmacotherapy vol 37 no 3 pp 420ndash432 2003

[25] CW Roberts RMcLeod DW RiceM Ginger M L Chanceand L J Goad ldquoFatty acid and sterol metabolism potentialantimicrobial targets in apicomplexan and trypanosomatidparasitic protozoardquoMolecular andBiochemical Parasitology vol126 no 2 pp 129ndash142 2003

[26] D S Schiller and H B Fung ldquoPosaconazole an extended-spectrum triazole antifungal agentrdquo Clinical Therapeutics vol29 no 9 pp 1862ndash1886 2007

[27] N Singhal P K Sharma R Dudhe and N Kumar ldquoRecentadvancement of triazole derivatives and their biological signifi-cancerdquo Journal of Chemical and Pharmaceutical Research vol 3no 2 pp 126ndash133 2011

[28] T Porsbring H Blanck H Tjellstrom and T Backhaus ldquoTox-icity of the pharmaceutical clotrimazole to marine microalgalcommunitiesrdquo Aquatic Toxicology vol 91 no 3 pp 203ndash2112009

[29] i-tech marine paint about selektope 2012 httpwwwi-techseentechnology and productaspx

[30] A Hilvarsson C Ohlauson H Blanck and A Granmo ldquoBioac-cumulation of the new antifoulant medetomidine in marineorganismsrdquo Marine Environmental Research vol 68 no 1 pp19ndash24 2009

[31] COhlauson KM Eriksson andH Blanck ldquoShort-term effectsof medetomidine on photosynthesis and protein synthesis inperiphyton epipsammon andplankton communities in relationto predicted environmental concentrationsrdquo Biofouling vol 28no 5 pp 491ndash499 2012

[32] M Dahlstrom L G E Martensson P R Jonsson T Arne-brant and H Elwing ldquoSurface active adrenoceptor compoundsprevent the settlement of cyprid larvae of Balanus improvisusrdquoBiofouling vol 16 no 2ndash4 pp 191ndash203 2000

[33] M Nyden and K Holmberg ldquoStoppa havstulpanernardquo Kemi-varlden Biotech Med Kemisk Tidskrift vol 5 pp 22ndash24 2006

[34] A Lennquist N Asker E Kristiansson et al ldquoPhysiology andmRNA expression in rainbow trout (Oncorhynchus mykiss)after long-term exposure to the new antifoulantmedetomidinerdquoComparative Biochemistry and Physiology C vol 154 no 3 pp234ndash241 2011

[35] A Lennquist M C Celander and L Foerlin ldquoEffects of me-detomidine on hepatic EROD activity in three species of fishrdquoEcotoxicology and Environmental Safety vol 69 no 1 pp 74ndash792008

[36] A Lennquist A Hilvarsson and L Foerlin ldquoResponses in fishexposed to medetomidine a new antifouling agentrdquo MarineEnvironmental Research vol 69 supplement 1 pp S43ndashS452010

[37] A Lennquist L G E Martensson Lindblad D Hedberg EKristiansson and L Forlin ldquoColour andmelanophore functionin rainbow trout after long term exposure to the new antifoulantmedetomidinerdquo Chemosphere vol 80 no 9 pp 1050ndash10552010

[38] M Andersson J Hedin P Johansson J Nordstroem andM Nyden ldquoCoordination of imidazoles by Cu(II) and Zn(II)as studied by NMR relaxometry EPR far-FTIR vibrationalspectroscopy and Ab initio calculations effect of methyl sub-stitutionrdquo Journal of Physical Chemistry A vol 114 no 50 pp13146ndash13153 2010

[39] MAnderssonTrojer AMaartensson andMNyden ldquoReplace-ment of H-bonded bridged water by transition metal ionsin poly(1-vinylimidazole-co-methylmethacrylate) copolymersa vibrational spectroscopy study usingmid-FTIR far-FTIR andab initio calculationsrdquo Vibrational Spectroscopy vol 61 pp 38ndash42 2012

[40] C Fant P Handa and M Nyden ldquoComplexation chemistryfor tuning release from polymer coatingsrdquo Journal of PhysicalChemistry B vol 110 no 43 pp 21808ndash21815 2006

[41] P Handa C Fant and M Nyden ldquoAntifouling agent releasefrom marine coatings-ion pair formationdissolution for con-trolled releaserdquo Progress in Organic Coatings vol 57 no 4 pp376ndash382 2006

[42] L Shtykova C Fant P Handa et al ldquoAdsorption of antifoulingbooster biocides onmetal oxide nanoparticles effect of differentmetal oxides and solventsrdquo Progress in Organic Coatings vol 64no 1 pp 20ndash26 2009


[43] H Elwing M Dahlstrom T Arnebrant et al ldquoTest process forbioactive additives in antifouling paint comprises quantifyingbinding ability of test substance to surface coating on flat sensorin aqueous medium or organic solvent 2004-1097 52668420040429rdquo 2005

[44] L S Shtykova D Ostrovskii P Handa K Holmberg andM Nyden ldquoNMR diffusometry and FTIR in the study of theinteraction between antifouling agent and binder in marinepaintsrdquo Progress in Organic Coatings vol 51 no 2 pp 125ndash1332004

[45] M Nyden and C Fant ldquoMethod and use of nanoparticles tobind biocides in paints 2006-SE318 2006096128 20060313rdquo2006

[46] M Nyden C Fant K Holmberg and L Swanson ldquoMethod anduse of acidified modified polymers to bind biocides in paints2006-372522 7531581 20060310rdquo 2009

[47] MAnderssonOHansson LOehrstroemA Idstroem andMNyden ldquoVinylimidazole copolymers coordination chemistrysolubility and cross-linking as function of Cu2+ and Zn2+complexationrdquo Colloid and Polymer Science vol 289 no 12 pp1361ndash1372 2011

[48] M Andersson Trojer D Isaksson and M Nyden ldquoSynthe-sis and polymerisation of maleoyl-L-histidine monomers andaddition of histidine to an ethylene-alt-maleic co-polymerrdquoJournal of Polymer Research vol 19 Article ID 9821 2012

[49] J Hedin D Isaksson M Andersson and M Nyden ldquoBi-layerformation of imidazole-modified ethyl(hydroxyethyl)celluloseat a hydrophobic surface as monitored by QCM-Drdquo Journal ofColloid and Interface Science vol 336 no 2 pp 388ndash392 2009

[50] A Movahedi N Kann K Moth-Paulsen and B M NydenldquoSynthesis of chelating Cu(I)stabilizing polymeric ligandsrdquo

[51] Marine Paint Annual Report 2008 Gothenburg Sweden 2009[52] L Nordstierna A A Abdalla M Masuda G Skarnemark and

M Nyden ldquoMolecular release from painted surfaces free andencapsulated biocidesrdquo Progress in Organic Coatings vol 69 no1 pp 45ndash48 2010

[53] ldquoPolymeric core-shell particles physicochemical properties andcontrolled releaserdquo in Encyclopedia of Surface and ColloidScience P Somasundaran Ed Taylor and Francis New YorkNY USA 2013

[54] J Bergek M Andersson Trojer A Mok and L Nord-stierna ldquoControlled release of microencapsulated 2-n-octyl-4-isothiazolin-3-one from coatings effect of macroscopic andmicroscopic poresrdquo Colloids and Surfaces A In press

[55] J Bergek M Andersson Trojer H Uhr and L NordstiernaldquoControlled release of microencapsulated 2-n-octyl-4-isothi-azolin-3-one from coatings polyelectrolyte multilayers as aglobal a rate-determining barrierrdquo Journal of Materials Chem-istry B Submitted

[56] A Enejder F Svedberg L Nordstierna andM Nyden ldquoChem-ical release from single PMMA microparticles monitored byCARS microscopyrdquo in Multiphoton Microscopy in the Biomed-ical Sciences Proceedings of SPIE January 2011

[57] LNordstiernaAAAbdallaMNordin andMNyden ldquoCom-parison of release behaviour from microcapsules and micro-spheresrdquo Progress in Organic Coatings vol 69 no 1 pp 49ndash512010

[58] L Nordstierna A Movahedi and M Nyden ldquoNew route formicrocapsule synthesisrdquo Journal of Dispersion Science and Tech-nology vol 32 no 3 pp 310ndash311 2011

[59] B M Nyden L O Nordstierna E M Bernad and A M AA Abdalla ldquoSlow releasing microcapsules and microspherescomprising an biocidal substancerdquo 2010-EP56735 201013354820100517 2010

[60] M Andersson Trojer L Nordstierna M Nordin B M Nydenand K Holmberg ldquoPhysical Chemistry chemical physicsrdquoEncapsulation of Actives For Controlled Release 2013

[61] M Andersson Trojer H Andersson Y Li et al ldquoChargedmicrocapsules for controlled release of hydrophobic activesPart III the effect of polyelectrolyte brush- and multilayers onsustained releaserdquo Physical Chemistry Chemical Physics vol 15no 17 pp 6456ndash6466 2013

[62] M Andersson Trojer K Holmberg and M Nyden ldquoTheimportance of proper anchoring of an amphiphilic dispersantfor colloidal stabilityrdquo Langmuir vol 28 no 9 pp 4047ndash40502012

[63] M A Trojer Y Li C Abrahamsson et al ldquoCharged micro-capsules for controlled release of hydrophobic actives PartI encapsulation methodology and interfacial propertiesrdquo SoftMatter vol 9 no 5 pp 1468ndash1477 2013

[64] M Andersson Trojer Y Li M Wallin K Holmberg andM Nyden ldquoCharged microcapsules for controlled release ofhydrophobic actives Part II surface modification by LbLadsorption and lipid bilayer formation on properly anchoreddispersant layersrdquo Journal of Colloid and Interface Science vol409 no 1 pp 8ndash17 2013

[65] M Andersson Trojer A Mohamed and J Eastoe ldquoA highlyhydrophobic anionic surfactant at the oil-water water-polymerand oil-polymer interfaces implications on spreading coeffi-cients polymer interactions and microencapsulation via inter-nal phase separationrdquo Colloids and Surfaces A vol 436 no 5pp 1048ndash1059 2013

[66] M A Trojer A Wendel K Holmberg and M Nyden ldquoTheeffect of pHon charge swelling and desorption of the dispersantpoly(methacrylic acid) from poly(methyl methacrylate) micro-capsulesrdquo Journal of Colloid and Interface Science vol 375 no 1pp 213ndash215 2012

[67] E Ytreberg J Karlsson and B Eklund ldquoComparison of toxicityand release rates of Cu and Zn from anti-fouling paints leachedin natural and artificial brackish seawaterrdquo Science of the TotalEnvironment vol 408 no 12 pp 2459ndash2466 2010

[68] S R Nadella J L Fitzpatrick N Franklin C Bucking S Smithand C M Wood ldquoToxicity of dissolved Cu Zn Ni and Cd todeveloping embryos of the blue mussel (Mytilus trossolus) andthe protective effect of dissolved organic carbonrdquo ComparativeBiochemistry and PhysiologyC vol 149 no 3 pp 340ndash348 2009

[69] S Niyogi and C M Wood ldquoBiotic ligand model a flexible toolfor developing site-specific water quality guidelines for metalsrdquoEnvironmental Science and Technology vol 38 no 23 pp 6177ndash6192 2004

[70] A Viarengo M Pertica G Mancinelli B Burlando L Canesiand M Orunesu ldquoIn vivo effects of copper on the calciumhomeostasis mechanisms of mussel gill cell plasma mem-branesrdquo Comparative Biochemistry and Physiology vol 113 no3 pp 421ndash425 1996

[71] L Ciavatta D Ferri and R Palombari ldquoOn the equilibriumCu2+ + Cu(s) 9994489994712Cu+ rdquo Journal of Inorganic and Nuclear Chem-istry vol 42 no 4 pp 593ndash598 1980

[72] M G Simmons C L Merrill L J Wilson L A Bottomleyand K M Kadish ldquoThe Bis-26-[1-(2-imidazol-4-ylethylim-ino)ethyl]pyridinecopper(I) cation A synthetic CuI oxygencarrier in solution as a potential model for oxyhemocyaninrdquo


Journal of the Chemical Society Dalton Transactions no 10 pp1827ndash1837 1980

[73] L Kiaune and N Singhasemanon ldquoPesticidal copper (I) oxideenvironmental fate and aquatic toxicityrdquo Reviews of Environ-mental Contamination and Toxicology vol 213 pp 1ndash26 2011

[74] S J Brooks and MWaldock ldquoThe use of copper as a biocide inmarine antifouling paintsrdquo in Advances in Marine AntifoulingCoatings and Technologies pp 492ndash521 2009

[75] E Cotou M Henry C Zeri G Rigos A Torreblanca andV A Catsiki ldquoShort-term exposure of the European sea bassDicentrarchus labrax to copper-based antifouling treated netscopper bioavailability and biomarkers responsesrdquoChemospherevol 89 no 9 pp 1091ndash1097 2012

[76] T R Chan R Hilgraf K B Sharpless and V V Fokin ldquoPoly-triazoles as copper(I)-stabilizing ligands in catalysisrdquo OrganicLetters vol 6 no 17 pp 2853ndash2855 2004

[77] Y Rondelez M-N Rager A Duprat and O ReinaudldquoCalix[6]arene-based cuprous ldquofunnel complexesrdquo a mimic forthe substrate access channel to metalloenzyme active sitesrdquoJournal of the American Chemical Society vol 124 no 7 pp1334ndash1340 2002

[78] Y Rondelez G Bertho andO Reinaud ldquoThe first water-solublecopper(I) calix[6]arene complex presenting a hydrophobicligand binding pocket a remarkable model for active sitesin metalloenzymesrdquo Angewandte Chemie International Editionvol 41 no 6 pp 1044ndash1046 2002

[79] T Vanngard H M Swartz J R Bolton and D C BorgApplications of Electron Spin Resonance John Wiley and SonsNew York NY USA 1972

[80] M Branden ANamslauer OHansson RAasa andP Brzezin-ski ldquoWater-hydroxide exchange reactions at the catalytic site ofheme-copper oxidasesrdquo Biochemistry vol 42 no 45 pp 13178ndash13184 2003

[81] M M Ivkovic-Jensen G M Ullmann S Young et al ldquoEffectsof single and double mutations in plastocyanin on the rate con-stant and activation parameters for the rearrangement gatingthe electron-transfer reaction between the triplet state of zinccytochrome c and cupriplastocyaninrdquo Biochemistry vol 37 no26 pp 9557ndash9569 1998

[82] F Jacobson A Pistorius D Farkas et al ldquopH dependence ofcopper geometry reduction potential and nitrite affinity innitrite reductaserdquo Journal of Biological Chemistry vol 282 no9 pp 6347ndash6355 2007

[83] H Jansson andO Hansson ldquoCompetitive inhibition of electrondonation to photosystem 1 by metal-substituted plastocyaninrdquoBiochimica Et Biophysica Acta vol 1777 no 9 pp 1116ndash11212008

[84] H Jansson M Oekvist F Jacobson M Ejdebaeck O HanssonandL Sjoelin ldquoThe crystal structure of the spinach plastocyanindouble mutant G8DL12E gives insight into its low reactivitytowards photosystem 1 and cytochrome frdquo Biochimica et Bio-physica Acta vol 1607 no 2-3 pp 203ndash210 2003

[85] D La Mendola R P Bonomo S Caminati et al ldquoCopper(II)complexes with an avian prion N-terminal region and theirpotential SOD-like activityrdquo Journal of Inorganic Biochemistryvol 103 no 2 pp 195ndash204 2009

[86] D LaMendola D Farkas F Bellia et al ldquoProbing the copper(II)binding features of angiogenin Similarities and differencesbetween a N-terminus peptide fragment and the recombinanthuman proteinrdquo Inorganic Chemistry vol 51 no 1 pp 128ndash1412012

[87] D La Mendola A Magrı T Campagna et al ldquoA doppel 120572-helixpeptide fragment mimics the copper(II) interactions with thewhole proteinrdquo Chemistry vol 16 no 21 pp 6212ndash6223 2010

[88] D L Mendola A Magrı L I Vagliasindi O Hansson R PBonomo and E Rizzarelli ldquoCopper(II) complex formationwitha linear peptide encompassing the putative cell binding site ofangiogeninrdquo Dalton Transactions vol 39 no 44 pp 10678ndash10684 2010

[89] D L Mendola A Magrı O Hansson R P Bonomo andE Rizzarelli ldquoCopper(II) complexes with peptide fragmentsencompassing the sequence 122-130 of human doppel proteinrdquoJournal of Inorganic Biochemistry vol 103 no 5 pp 758ndash7652009

[90] S Modi M Nordling L G Lundberg O Hansson and D SBendall ldquoReactivity of cytochromes c and f with mutant formsof spinach plastocyaninrdquo Biochimica et Biophysica Acta vol1102 no 1 pp 85ndash90 1992

[91] K Olesen M Ejdeback and O Hansson ldquoElectron transferfrom genetically modified plastocyanin to photosystem 1rdquo inProceedings of the 11th International photosynthesis Photosyn-thesis mechanisms and effects Congress pp 1597ndash1600 1998

[92] K Sigfridsson M Ejdeback and M Sundahl ldquoElectron trans-fer in ruthenium-modified spinach plastocyanin mutantsrdquoArchives of Biochemistry and Biophysics vol 351 no 2 pp 197ndash206 1998

[93] K Sigfridsson S Young and O Hansson ldquoElectron transferbetween spinach plastocyanin mutants and photosystem 1rdquoEuropean Journal of Biochemistry vol 245 no 3 p 805 1998

[94] Y Xue M Okvist O Hansson and S Young ldquoCrystal structureof spinach plastocyanin at 1 7 A resolutionrdquo Protein Science vol7 no 10 pp 2099ndash2105 1998

[95] R J Sundberg and R B Martin ldquoInteractions of histidineand other imidazole derivatives with transition metal ions inchemical and biological systemsrdquo Chemical Reviews vol 74 no4 pp 471ndash517 1974

[96] C J Jones D- and F-Block Chemistry The Royal Society ofChemistry Birmingham England 2001

[97] B N Figgis and M A Hitchman ldquoLigand field theory and itsapplicationsrdquo Journal of Chemical Education vol 79 no 9 p1072 2002

[98] R G Pearson ldquoHard and soft acids and basesrdquo Journal of theAmerican Chemical Society vol 85 no 22 pp 3533ndash3539 1963

[99] R G Pearson ldquoAbsolute electronegativity and hardness corre-lated with molecular orbital theoryrdquo Proceedings of the NationalAcademy of Sciences of the USA vol 83 no 22 pp 8440ndash84411986

[100] R H CrabtreeThe Organometallic Chemistry of the TransitionMetals John Wiley and Sons New York NY USA 4th edition2005

[101] Y Jean Molecular Orbitals of Transition Metal ComplexesOxford University Press New York NY USA 2005

[102] K Liu W Shi and P Cheng ldquoThe coordination chemistryof Zn(II) Cd(II) and Hg(II) complexes with 124-triazolederivativesrdquoDalton Transactions vol 40 no 34 pp 8475ndash84902011

[103] W Ouellette S Jones and J Zubieta ldquoSolid state coordinationchemistry of metal-124-triazolates and the related metal-4-pyridyltetrazolatesrdquo CrystEngComm vol 13 no 14 pp 4457ndash4485 2011

[104] J G Haasnoot ldquoMononuclear oligonuclear and polynuclearmetal coordination compounds with 1 2 4-triazole derivatives


as ligandsrdquo Coordination Chemistry Reviews vol 200-202 pp131ndash185 2000

[105] J P Zhang Y B Zhang J B Lin andXM Chen ldquoMetal azolateframeworks from crystal engineering to functional materialsrdquoChemical Reviews vol 112 no 2 pp 1001ndash1033 2012


[107] L M Epstein D K Straub and C Maricondi ldquoMossbauerspectra of some porphyrin complexes with pyridine piperidineand imidazolerdquo Inorganic Chemistry vol 6 no 9 pp 1720ndash17241967

[108] N S Rannulu R Amunugama Z Yang and M T RodgersldquoInfluence of s and d orbital occupation on the binding of metalions to imidazolerdquo Journal of Physical Chemistry A vol 108 no30 pp 6385ndash6396 2004

[109] D Reddy K J Akerman M P Akerman and D Jaganyi ldquoAkinetic investigation into the rate of chloride substitution fromchloro terpyridine platinum(II) and analogous complexes by aseries of azole nucleophilesrdquoTransitionMetal Chemistry vol 36no 6 pp 593ndash602 2011

[110] B Barszcz M Gabryszewski J Kulig and B Lenarcik ldquoPoten-tiometric studies on complexes of silver(I) in solutions Part2 Correlation between the stability of the silver(I)-azole com-plexes and the ligand basicityrdquo Journal of the Chemical SocietyDalton Transactions no 10 pp 2025ndash2028 1986

[111] D Hourdet J A Gadgil K Podhajecka M V Badiger ABrulet and P P Wadgaonkar ldquoThermoreversible behavior ofassociating polymer solutions thermothinning versus ther-mothickeningrdquo Macromolecules vol 38 no 20 pp 8512ndash85212005

[112] M Prabaharan and J F Mano ldquoChitosan derivatives bearingcyclodextrin cavitiesas novel adsorbentmatricesrdquoCarbohydratePolymers vol 63 no 2 pp 153ndash166 2006

[113] R Souzy B Ameduri B Boutevin G Gebel and P CapronldquoFunctional fluoropolymers for fuel cellmembranesrdquo Solid StateIonics vol 176 no 39-40 pp 2839ndash2848 2005

[114] M M Nasef and E S A Hegazy ldquoPreparation and applicationsof ion exchange membranes by radiation-induced graft copoly-merization of polar monomers onto non-polar filmsrdquo Progressin Polymer Science vol 29 no 6 pp 499ndash561 2004

[115] Q Chen and B-H Han ldquoPrepolymerization and postpolymer-ization functionalization approaches to fluorescent conjugatedcarbazole-based glycopolymers via click chemistryrdquo Journal ofPolymer Science A vol 47 no 11 pp 2948ndash2957 2009

[116] M A Gauthier M I Gibson and H A Klok ldquoSynthesisof functional polymers by post-polymerization modificationrdquoAngewandte Chemie International Edition vol 48 no 1 pp 48ndash58 2008

[117] R Huisgen ldquo13-Dipolar cycloadditionsrdquo Proceedings of theChemical Society pp 357ndash369 1961

[118] V V Rostovtsev L G Green V V Fokin and K B SharplessldquoA stepwise Huisgen cycloaddition process copper(I)-catalyzedregioselective ldquoligationrdquo of azides and terminal alkynesrdquo Ange-wandte Chemie International vol 41 no 14 pp 2596ndash25992002

[119] B C Boren S Narayan L K Rasmussen et al ldquoRuthenium-catalyzed azide-alkyne cycloaddition scope and mechanismrdquoJournal of the American Chemical Society vol 130 no 28 pp8923ndash8930 2008

[120] D Braun and F Hu ldquoPolymers from non-homopolymerizablemonomers by free radical processesrdquo Progress in PolymerScience vol 31 no 3 pp 239ndash276 2006

[121] R C P Cubbon ldquoThe free radical and anionic polymerizationof some N-substituted maleimidesrdquo Polymer vol 6 no 8 pp419ndash426 1965

[122] D J T Hill L Y Shao P J Pomery and A K Whittaker ldquoTheradical homopolymerization of N-phenylmaleimide N-n-hexylmaleimide and N-cyclohexylmaleimide in tetrahydrofu-ranrdquo Polymer vol 42 no 11 pp 4791ndash4802 2001

[123] C Hulubei and S Morariu ldquoSynthesis and radical polymeriza-tion of N-(3-acetyl-4-carboxy-phenyl)-maleimiderdquo High Per-formance Polymers vol 12 no 4 pp 525ndash533 2000

[124] T Oishi H Nagata and H Tsutsumi ldquoSynthesis and polymer-ization of N-substituted maleimides based on L-alanine esterrdquoPolymer vol 39 no 17 pp 4135ndash4146 1998

[125] TM Pyriadi andA S Hamad ldquoPreparation of new copolymersof vinyl acetate andN-substitutedmaleimidesrdquo Polymer vol 37no 23 pp 5283ndash5287 1996

[126] P O Tawney R H Snyder C E Bryan et al ldquoThe chemistry ofmaleimide and its derivatives I N-carbamylmaleimiderdquo Jour-nal of Organic Chemistry vol 25 no 1 pp 56ndash60 1960

[127] P O Tawney R H Snyder R P Conger K A Leibbrand CH Stiteler and A R Williams ldquoThe chemistry of maleimideand its derivatives II Maleimide and N-methylolmaleimiderdquoJournal of Organic Chemistry vol 26 no 1 pp 15ndash21 1961

[128] J Z Yang and T Otsu ldquoReactivities of citraconic anhy-dride N-alkylcitraconimides dialkyl citraconates and dialkylmesaconates in radical copolymerization with vinyl acetateand characterization of the resulting copolymersrdquo EuropeanPolymer Journal vol 27 no 10 pp 1081ndash1086 1991

[129] J M G Cowie Polymers Chemistry and Physics of ModernMaterials CRC Press 2nd edition 1991

[130] K H Wu T C Chang Y T Wang Y S Hong and T S WuldquoInteractions and mobility of copper(II)-imidazole-containingcopolymersrdquo European Polymer Journal vol 39 no 2 pp 239ndash245 2003

[131] N L Mazyar V V Annenkov V A Kruglova et al ldquoAcid-baseproperties of poly(1-vinylazoles) in aqueous solutionrdquo RussianChemical Bulletin vol 49 no 12 pp 2013ndash2017 2000

[132] E N Danilovtseva M A Chafeev and V V AnnenkovldquoNew polyelectrolytes based on 4-vinyl-123-triazole and 1-vinylimidazolerdquo Journal of Polymer Science A vol 50 no 8 pp1539ndash1546 2012

[133] H C Kolb M G Finn and K B Sharpless ldquoClick chemistrydiverse chemical function from a few good reactionsrdquo Ange-wandte Chemie International Edition vol 40 no 11 pp 2004ndash2021 2001

[134] R JThibault K Takizawa P Lowenheilm et al ldquoA versatile newmonomer family functionalized 4-vinyl-123-triazoles via clickchemistryrdquo Journal of the American Chemical Society vol 128no 37 pp 12084ndash12085 2006

[135] L A Belfiore andM PMcCurdie ldquoReactive blending viametal-ligand coordinationrdquo Journal of Polymer Science B vol 33 no 1pp 105ndash124 1995

[136] L A Belfiore M P McCurdie and P K Das ldquoMacromolecule-metal complexes ligand field stabilization and thermophysicalproperty modificationrdquo Polymer vol 42 no 25 pp 9995ndash10006 2001

[137] T Kaliyappan and P Kannan ldquoCo-ordination polymersrdquoProgress in Polymer Science vol 25 no 3 pp 343ndash370 2000

[138] R Hoogenboom D Fournier and U S Schubert ldquoAsymmetri-cal supramolecular interactions as basis for complex responsivemacromolecular architecturesrdquo Chemical Communications no2 pp 155ndash162 2008


[139] V Marin E Holder R Hoogenboom and U S SchubertldquoFunctional ruthenium(II)- and iridium(III)-containing poly-mers for potential electro-optical applicationsrdquo Chemical Soci-ety Reviews vol 36 no 4 pp 6618ndash6635 2007

[140] C S KMak andWKChan ldquoElectroluminescence frommetal-containing polymers and metal complexes with functional lig-andsrdquo inHighly Efficient OLEDsWith Phosphorescent Materialsp 329 2008

[141] H K Reimschuessel ldquoPolymer-metal halide interactions nylon6-zirconium tetrafluoride systemrdquo Colloid and Polymer Sciencevol 260 no 9 pp 842ndash850 1982

[142] M Sato K Kondo and K Takemoto ldquoFunctional monomersand polymers 43 ESR study on the copper(II) complexes ofpolymers containing imidazolyl groups and of theirmonomericanalogsrdquo Die Makromolekulare Chemie vol 179 no 3 pp 601ndash610 1978

[143] M Sato K Kondo and K Takemoto ldquoFunctional monomersand polymers 56 Effects of ionic strength on the structure ofCu(II) poly(vinylimidazole) and Cu(II) imidazole complexesin aqueous solutionrdquoDieMakromolekulare Chemie vol 180 no3 pp 699ndash704 1979

[144] M Sato K Kondo and K Takemoto ldquoESR studies on the dimerformation between copper ions in the poly(vinylimidazole)copper(II) complexrdquo Polymer Bulletin vol 2 no 5 pp 305ndash3081980

[145] A B Strong Plastics Materials and Processing Pearson Educa-tion New Jersey NJ USA 3rd edition 2006

[146] V A Berstein andVM EgorovDifferential Scanning Calorime-try of Polymers Ellis Horwood Chichester UK 1994

[147] H Tanaka S Tai K Kamijima et al ldquoAntifouling paint contain-ing compounds to improve viscosity stability and durability offilms in seawater 1994-309674 659848 19941222rdquo 1995

[148] U Gerigk and D Ventur ldquoPreparation of thiadiazole com-pounds as antifouling agents 1992-4230955 19920916rdquo 1994

[149] M Mechtel W Podszun and K H Kaesler ldquoAntifouling agentsand coatings and their preparation 1997-EP5626 981773219971013rdquo 1998

[150] F Kunisch M Kugler H Schrage and H L Elbe ldquoAntifoulingagents comprising benzothiophene-2-carboxamide S S-dioxidederivs 1995-19534868 19950920rdquo 1997

[151] R Neiman and D Kivelson ldquoESR line shapes in glasses ofcopper complexesrdquoThe Journal of Chemical Physics vol 35 no1 pp 149ndash155 1961

[152] F Jiang J McCracken and J Peisach ldquoNuclear quadrupoleinteractions in copper(II)-diethylenetriamine-substituted imi-dazole complexes and in copper(II) proteinsrdquo Journal of theAmericanChemical Society vol 112 no 25 pp 9035ndash9044 1990

[153] H J Scholl and J Huettermann ldquoESR and ENDOR of cop-per(II) complexes with nitrogen donors probing parameters forprosthetic group modeling of superoxide dismutaserdquo Journal ofPhysical Chemistry vol 96 no 24 pp 9684ndash9691

[154] C-C Su H C Jan H Kuo-Yih et al ldquoBonding propertiesof Cu(II)-imidazole chromophores spectroscopic and elec-trochemical properties of monosubstituted imidazole cop-per(II) complexes Molecular structure of [Cu(4-methylimid-azole)4(ClO

4)2]rdquo Inorganica Chimica Acta vol 196 no 2 pp

231ndash240 1992[155] B C Cornilsen and K Nakamoto ldquoMetal isotope effect on

metal-ligand vibrations-XII imidazole complexes with Co(II)Ni(II) Cu(II) and Zn(II)rdquo Journal of Inorganic and NuclearChemistry vol 36 no 11 pp 2467ndash2471 1974

[156] J Reedijk ldquoPyrazoles and imidazoles as ligands II Coordina-tion compounds ofN-methyl imidazolewithmetal perchloratesand tetrafluoroboratesrdquo Inorganica ChimicaActa vol 3 pp 517ndash522 1969

[157] C Perchard and A Novak ldquoThe low-frequency infrared andRaman spectra of ammonia and imidazole complexes of zinc(II)halidesrdquo Spectrochimica Acta A vol 26 no 4 pp 871ndash881 1970

[158] A B P Lever ldquoElectrochemical parametrization of metal com-plex redox potentials using the ruthenium(III)ruthenium(II)couple to generate a ligand electrochemical seriesrdquo InorganicChemistry vol 29 no 6 pp 1271ndash1285 1990

[159] S Ahrland K Nilsson and B Tagesson ldquoThermodynamicsof the copper(I) halide and thiocyanate complex formation inacetonitrilerdquo Acta Chemica Scandinavica A vol 37 pp 193ndash2011983

[160] R R Bessette and J W Olver ldquoMeasurement of diffusion coef-ficients for the reduction of copper(I) and (II) in acetonitrilerdquoJournal of Electroanalytical Chemistry and Interfacial Electro-chemistry vol 21 no 3 pp 525ndash529 1969

[161] D C Gould andA Ehrenberg ldquoCu2+ in non axial-field amodelfor Cu2+ in copper enzymesrdquo European Journal of Biochemistryvol 5 no 4 pp 451ndash455 1968

[162] J T Rubino and K J Franz ldquoCoordination chemistry of copperproteins how nature handles a toxic cargo for essential func-tionrdquo Journal of Inorganic Biochemistry vol 107 no 1 pp 129ndash143 2012

[163] J L Dalsin and P B Messersmith ldquoBioinspired antifoulingpolymersrdquoMaterials Today vol 8 no 9 pp 38ndash46 2005

Submit your manuscripts athttpwwwhindawicom

Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2013


Carbohydrate Chemistry

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom


Analytical ChemistryVolume 2013

ISRN Chromatography


Hindawi Publishing Corporation httpwwwhindawicom Volume 2013Hindawi Publishing Corporation httpwwwhindawicom Volume 2013

The Scientific World Journal

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2013


CatalystsJournal of

ISRN Analytical Chemistry


ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2013


Advances in

Physical Chemistry

ISRN Physical Chemistry


SpectroscopyInternational Journal of


ISRN Inorganic Chemistry



Journal of

Chemistry


Inorganic ChemistryInternational Journal of


International Journal ofPhotoenergy


Analytical Methods in Chemistry

Journal of

Volume 2013

ISRN Organic Chemistry



Journal of

Spectroscopy

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 946739 23 pageshttpdxdoiorg1011552013946739

Review ArticleImidazole and Triazole Coordination Chemistry forAntifouling Coatings

Markus Andersson Trojer1 Alireza Movahedi1 Hans Blanck2 and Magnus Nydeacuten13

1 Applied Surface Chemistry Department of Chemical and Biological EngineeringChalmers University of Technology 412 96 Goteborg Sweden

2Department of Biological and Environmental Sciences University of Gothenburg 405 30 Goteborg Sweden3 Ian Wark Research Institute University of South Australia Adelaide SA 5001 Australia

Correspondence should be addressed to Markus Andersson Trojer markusanderssonchalmersse

Received 29 April 2013 Accepted 9 July 2013

Academic Editor Suleyman Goksu

Copyright copy 2013 Markus Andersson Trojer et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

Fouling of marine organisms on the hulls of ships is a severe problem for the shipping industry Many antifouling agents are basedon five-membered nitrogen heterocyclic compounds in particular imidazoles and triazoles Moreover imidazole and triazoles arestrong ligands for Cu2+ and Cu+ which are both potent antifouling agents In this review we summarize a decade of work withinour groups concerning imidazole and triazole coordination chemistry for antifouling applications with a particular focus on thevery potent antifouling agent medetomidine The entry starts by providing a detailed theoretical description of the azole-metalcoordination chemistry Some attention will be given to ways to functionalize polymers with azole ligands Then the effect ofmetal coordination in azole-containing polymers with respect to material properties will be discussed Our work concerning thecontrolled release of antifouling agents in particular medetomidine using azole coordination chemistry will be reviewed Finallyan outlookwill be given describing the potential for tailoring the azole ligand chemistry in polymerswith respect toCu2+ adsorptionand Cu2+ rarrCu+ reduction for antifouling coatings without added biocides

1 Introduction

A major problem for the shipping industry is fouling ofmarine organisms such as algae mussels and barnacles onship hulls [1ndash5] As the ship moves through the water thehull is subjected to form drag and skin friction drag Sincefouling increases the surface roughness the skin friction dragis increased which subsequently results in increased fuelconsumption and reduced manoeuvrability [3] Traditionalcountermeasures against marine fouling are coatings con-taining antifouling toxicants that have had severe environ-mental consequences on marine ecosystems The most well-known examples are organometallic paint systems (compris-ing lead arsenic mercury etc) which met the market in theearly 1960s The notorious tributyltin self-polishing coating(TBT-SPC) was developed in the 1970s [1 6] The reason forthe success of the TBT-SPC paints is that the rate of releasecan be controlled on amolecular level Generally these paints

are based on acrylic or methacrylic copolymers The activesubstance (TBT) is covalently attached to the carboxylicgroup of the polymer which is hydrolytically instable inslightly alkaline conditions (as in seawater) [1 4 6] Toxiccopper pigment is also included in the TBT-SPC paintsystems which in combinationwith TBT provides protectionagainst the entire spectrum of fouling organisms since somealgae are tolerant to TBT but not to copper and vice versa[7] As the use of TBT containing paints increased marinelife in the vicinity of harbours and marinas was severelyaffected [8 9] The hazardous nature of TBT for the marineenvironment is ascribed to its weakening of fish immunesystems causing imposex and sterility in female gastropods(at such low concentration as 1 ngL) as well as its bioac-cumulative properties in mammals [1 4 6] Starting withTBT ban for pleasure craft in France 1982 TBT-contain-ing paint systems were successively phased out in the 1990s












Im-EHEC

n

O

N OO

NNH

O

N OO

NNH

n

n

N

N

OO

OO

O

OO

OO

O

OH

NHN

OH

991

OH

HO

n

ma cn

SO OOH

SO OOH

b

ma cn b

4 96

44 56

4 96 PMMA

P(1-VIm)

PVM-4

PVM-44

P4VM-4

PHMI P(E-alt-HMI)

N

HN

Medetomidine

PSEBS

SPSEBS

N

NIm H H

CH3

H

H

Polymers

Biopolymers

Synthetic polymers

O O

nm

NNH

NO O

n

Nm

n

O O

NS

O

Isothiazolinones

H

Cl Cl

HOcthilinone

Fluconazole

OHF

F

N

N N

N

N N

Itraconazole

NNNN

O

NOO

O

Cl

ClN

NN











OIT

DCOIT

N

N

ClClotrimazole


Selectope

Seanine

Me(1)-Im

Me(4)-Im

Imidazole

1-methylimidazole

4-methylimidazole

R2O R2O

R2

R2

R2R2

R3

R3

R1

R1

R1

R1

CH3

C8H17

C8H17

R2 = H CH3

(()

)[ ]

( () )

( () ) ( )

( ) ( ) ( )( ) ( )

( ) ( )[

[ [ [

[ []

] ] ]

] ]






Releasedbiocide


binder


Pigment

Binder


Erodinglayer

Unreactedpaint

Seawater(H2O NaCl)




polymer shell



(a)

(b)















4

2+sdot



4





ℎsymmetry [Zn(Im)

6]2+ (see




ℎ






Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im



N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5



3(imidazole)


1is





3) and













M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy












Im-EHEC

n

O

N OO

NNH

O

N OO

NNH

n

n

N

N

OO

OO

O

OO

OO

O

OH

NHN

OH

991

OH

HO

n

ma cn

SO OOH

SO OOH

b

ma cn b

4 96

44 56

4 96 PMMA

P(1-VIm)

PVM-4

PVM-44

P4VM-4

PHMI P(E-alt-HMI)

N

HN

Medetomidine

PSEBS

SPSEBS

N

NIm H H

CH3

H

H

Polymers

Biopolymers

Synthetic polymers

O O

nm

NNH

NO O

n

Nm

n

O O

NS

O

Isothiazolinones

H

Cl Cl

HOcthilinone

Fluconazole

OHF

F

N

N N

N

N N

Itraconazole

NNNN

O

NOO

O

Cl

ClN

NN











OIT

DCOIT

N

N

ClClotrimazole


Selectope

Seanine

Me(1)-Im

Me(4)-Im

Imidazole

1-methylimidazole

4-methylimidazole

R2O R2O

R2

R2

R2R2

R3

R3

R1

R1

R1

R1

CH3

C8H17

C8H17

R2 = H CH3

(()

)[ ]

( () )

( () ) ( )

( ) ( ) ( )( ) ( )

( ) ( )[

[ [ [

[ []

] ] ]

] ]






Releasedbiocide


binder


Pigment

Binder


Erodinglayer

Unreactedpaint

Seawater(H2O NaCl)




polymer shell



(a)

(b)















4

2+sdot



4





ℎsymmetry [Zn(Im)

6]2+ (see




ℎ






Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im



N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5



3(imidazole)


1is





3) and













M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Releasedbiocide


binder


Pigment

Binder


Erodinglayer

Unreactedpaint

Seawater(H2O NaCl)




polymer shell



(a)

(b)















4

2+sdot



4





ℎsymmetry [Zn(Im)

6]2+ (see




ℎ






Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im



N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5



3(imidazole)


1is





3) and













M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy











4

2+sdot



4





ℎsymmetry [Zn(Im)

6]2+ (see




ℎ






Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im



N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5



3(imidazole)


1is





3) and













M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Seawater (H2ONaCl)


eminus

eminus

Cu2+

Cu2+

Cu+

Cu+

C

SIm Im

NIm Im

Im Im



N

HN

HN

HN

N

N

N

N

1

1

2

2

3

3

4

4

5

51

2

34

51

23

4

5

1

2

34

5

1

2

34

5



3(imidazole)


1is





3) and













M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


M-L 120590-bond





eminus

eminus

eminus

eminus

eminus

eminus


dxy


M-L 120590-bond



Cu2+


Cu2+


z x

y

Cu2+

Cu2+Cu2+

x

y

z



N

N

N

dx2minusy2

dx2minusy2 (Cu2+)


Zn2+Zn2+Cu2+

(a) (b) (c)



6]2+


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

120590

120587


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding

Complex



120590 levels



120590lowast levels

120587lowast levels

E


d120590lowast

d120587lowast

d120587

d120587

d120587

d120587

d120587

d120587

d120587

dxy

dyzdxz

dz2

3d

4p

4s


120590-bonds


120587-bonds

120587lowast

Δ

Δ

Δ

120590

120587






120587-interaction


Metal Ligand

Bond

ing

Non

bond

ing

Ant

ibon

ding


(a) (b)

dyzdxzdxydz2

dz2 dx2minusy2

d120590







O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


O

O

N OO

NNH

O OO

n

HO

O

HNN

O

O

HNN

1 2


HN N

O

N N

O

N N

O

HO EHEC N N

HO

O EHECHN N

HO

O EHEC

3

3

NaH

AcOH O

OO

O

n

HN N

HO

H

H

EHEC=

O

O

N OO

HNNH

N

N

HN

N

O O

1 (HMI)

2

3 4


1 2


3



lowast( )

[]


Ph3CClPh3C

Ph3C

Ph3C

R1 =

R1 =

(CH2)2O CH2CH2

R2 =

R1

R1

R1

R1

R2

R2

R2

R1R2

NH2 NH2

R2 = H CH3

AIBN 1 (DMSO 80∘C) 2 3 4 (THF 70∘C)















N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy











N

NN

N N N

Cu(I)

Ru(II)

N

NN

N

NN

N

NN

R1

R1

R1

R1

R1

R2 R2

R2

R2

R2




4]2+ and PVM-





1-substituted



4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


4000 3000 2000 1500 1000 400

31171506

915

952

3122 1513

915

952

310714971727 665

1145

(a)

(b)

(c)

Tran

smitt

ance

(cmminus1)








119892is




1200 2400 3600Field (G)

Half field signal

4 96

PVM-4

m n

OON

N

44 56PVM-44

m n

OON

N

2400 2600 2800 3000 3200 3400 3600Field (G)

PMMAOOn

Reference

N

N

N

HN

N

HN

(a1)

Inte

nsity

Inte

nsity

(a2)

(a3)

(a4)

(b1)

(b2)

(c1)

(c2)

lowast

lowastlowast

lowast

|A|

g

gperp

CH3

H3C

H2O

lowastlowast

( () )

( () )

( )





100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


100

110

120

130

140

150

160

170

180

Zn(II)Cu(II)

UndopedCalculated


Tg

(∘C)

113116

108 105

175

108

160

140

121127

Polymers










minusprobed






M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


M2+ M2+

M2+

Im

ImIm

Im

Im

Im Im

Im

Im

Im

Im

Im

Im

Im

Im Im Im

Im

Im

ImImIm

ImIm



Polymer backbone

Cu2+ or Zn2+

lowastlowast

N

NOO

915

988

1665

1727

1000 9002000 1600

915952

9881727

1643

(cmminus1)1000 9002000 1600

(cmminus1)

120575(HOH) 120575(Im) 120575(HOH) 120575(Im)

Bridged water







0

0005

001

0015

002

0025

003

0035

004

0 200 400 600 800 1000 1200 1400Time (min)

Visc

(kg

ms)

0

00005

0001

00015

0002

00025

CuCl2

Thic

knes

s (mlowast

106)







Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Rinsing


100

200

300

Δm

(ng

cm2)

minus5 0 5 10 15 20 25 30Time (min)

















0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


0

20

40

60

80

100Ad

sorp

tion

()




(a)

0

20

40

60

80

100

Adso

rptio

n (

)


ZnOTiO2

CuO

Al2O3

SiO2

MgO

(b)

Rele

ase r

ate (

gcm

2)

07

0

14

21

28

35times10minus8

0 5 10 15 20 25 30Time (h)

Varnish 1Varnish 2

(c)






Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy



Im

(1 4)-Im

1-Im 4(5)-Im

MeO-ImMe-Im

CF3-Im CN-Im

F-Im





HN HN HN HNN N N N

CH3HO

O

NH2N


120587-acceptor




Ceminus eminus

eminus











H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


H3C

HN

N

N

N

CH3

2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200Field (G)

2400 2600 2800 3000 3200 3400 3600Field (G)

12

3

4 56

7

8

9

12

34

56

78 9

(a)

(b)

(b1)

mI = +32 mI = +12

mI = +12

mI = +12

mI = +12

mI = +32

mI = +32

mI = +32

mI = minus12

mI = minus12

mI = minus12

mI = minus12









Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy


Zn2+

R1R2

(a)

Zn2+

(b)

Cu2+

(c)



4Cl2] and





2Cl2] despite


2400 2600 2800 3000 3200 3400 3600Field (G)

minus250000

minus200000

minus150000

minus100000

minus50000

50000

100000

150000

Inte

nsity

(au

)

0




Acknowledgments



References























































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy











































































































































































ISRN Chromatography






CatalystsJournal of






Advances in

Physical Chemistry








Journal of

Chemistry







Journal of

Volume 2013




Journal of

Spectroscopy

imidazole and triazole coordination chemistry for antifouling

Documents