v.v. arslanov, m.a.kalinina functional supramolecular systems at interfaces leninskij pr. 31,...
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V.V. Arslanov, M.A.Kalinina
FUNCTIONAL SUPRAMOLECULAR SYSTEMS
AT INTERFACES
Leninskij pr. 31, Moscow, 119991 Russia
Tel.: +7 (095) 955-4489, [email protected]
1. Dynamic properties of organized ultra thin films at liquid and solid surfaces.
2. 2D polymer networks for immobilization of functional molecules and nanoparticles and improvement stability of supramolecular devices.
DD yy nn aa mm ii cc ss
Diffusion-binding Diffusion+Binding Diffusion-Binding+Isolation
Composition tuning
Compression isotherms of ODA monolayer and mixed monolayer of ODA+Ionophore
0
10
20
30
40
50
60
0 20 40 60 80
Surface area,
, mN/m
Е2/molec.
π
octadecylamine+ionophore
octadecylamine
Ca-ionophore (BAPTA)1,2-Bis(2-aminophenoxy)ethane-
N,N,N’N’-tetraacetic acid
“MOLECULAR PUMP” sensing LB membrane for selective calcium determination
Immobilization of non-amphiphilic Ca-ionophore in LB film of mixed monolayers with octadecylamine
Octadecylamine
(ODA)
A2/molec.
Fundamental problem of ISE’s membranes:Only a part of binding agent participates in analyte recognition.
NN
O O
СОО-
СОО- СОО- СОО-
Diffusion+Binding
+
Effect of interfering ions
on the response of 17 layer
BAPTA/ODA LB membrane
QCM responses of a LB film of ODA and Ca-ionophore (BAPTA) to presence of Ca2+ ions in aqueous solution of CaCl2
BaCl2
10-3 M0
300
600
900
1200
-8 -7 -6 -5 -4 -3 -2 -1lg[Ca2+]
ma
ss u
pta
ke
, n
g
1
2
CaCl2/0.1 NaCl
CaCl2
[metal salt],
1.0010-3 M
Mass uptake (m) (ng)
CaCl2 827
BaCl2 58
MgCl2 72
NaCl 24
KCl 8
Response time is Response time is 10 s10 s
pH 7.2pH 7.2
Detection limit is Detection limit is 1010-11-11MM
= 23 mN/m
5 - 5 min
4 - 1.5 min
3 - 40 s
2 - 10 s
= 32 mN/m
1 - 5 min0
200
400
600
800
1000
1200
-8 -6 -4 -2lg [Ca
2+]
Mas
s u
pta
ke,
ng
1
5
43
2
Surface pressure control of
preorganization
Influence exposure time and of deposition surface pressure on a work of sensor.
Mass uptake vs calcium concentration dependencies obtained with 17-layer ODA/BAPTA LB membranes deposited on quartz crystals at surface pressure 32 mN m-1 and 23 mN m-1 and
exposed to CaCl2 solutions
Impedance response for Impedance response for 4 layer4 layer ODA/BAPTA LB ODA/BAPTA LB
membranes before (original film) and after immersion membranes before (original film) and after immersion
into solutions of 10into solutions of 10-8-8 M , 10 M , 10-6-6 M and 10 M and 10-4-4 M of CaCl M of CaCl22
0
10
20
30
40
50
60
70
80
0 50 100 150 200 250
ZRe, kOhm
ZIm
, kO
hm
10-4 M
10-6 M
10-8 M
free film
Time-dependent reflectance changes measured at a fixed angle
of incidence ( = 64°) for 6 layer ODA/BAPTA LB membranes
exposed in calcium chloride solutions.
0 25 50 75 100 125 150 175 200 225 250 275 3004200
4400
4600
4800
10-8 M
10-6 M
10-4 M
10-2 M
Ca2+
refle
cta
nce
, a
rb.
un
its
time, sec
44
44,2
44,4
44,6
44,8
-8 -6 -4 -2lg [Ca2+]
refl
ecta
nce
, a
rb.
un
its
Linear calibration of REF signal vs calcium concentration for 10
sec of measurements
10-810-610-410-1Concentration of Ca2+ ions in solution, M
1:11:31:51:10
The ratio of number of ionophore molecules to number of Ca2+ ions in LB (10 seconds)
Where Ca2+-cations are
settle?
MECHANIZM OF “MOLECULAR PUMP” OPERATION
(LB film of mixed monolayers of Ca-ionophore and ODA)
Са2+
Ca(OH)2
–COO-
C18H37NH3+
- + - + - + - + + + ++ - + - pHh
- + - + - + - + + + + + - + -
Са2+ + 2OH- = Ca(OH)2
1. Specific molecular organization of the film providing both a weak bonding of ions with ionophore and rapid transfer of Ca-ions.
2. Local increase of pH in sites of film with increased content of protonated amine groups. The precipitation of Ca hydroxide is observed in this sites.
Region of local increase
of pH
Optical microscopy images for 17 layer ODA/BAPTA (a, b) and ODA (c) LB Optical microscopy images for 17 layer ODA/BAPTA (a, b) and ODA (c) LB membranes immersed into aqueous solution of 10membranes immersed into aqueous solution of 10-2-2 M CaCl M CaCl
22
50 ma 50 mb
1 mc
1.5 1.5 minmin
10 s10 s
5 min5 minODAODA
ODA/BAPTAODA/BAPTA
N
N N
N
Macrocyclicpolyamine
Conformationalflexibility of the ring
Amphiphiliccompound
dicetyl cyclen(DCC)
Conformational tuning
- powerful method to control the receptor properties of LB membranes
0
10
20
30
40
50
60
50 70 90 110 130 150
Аrea per molecule, square angstroms
,mN/m
Condensedstates
Expanded state NN NN
69,5 0LEp
N
NNN
76,2 0
Ld
80,40
N
NN
N
Lc
0
10
20
30
40
50
60
40 70 100 130 160
Area per molecule (square angstroms)
,mN/ m
pH 3.5pH 5.6
pH 8.5
Surface pressure control Monolayer density
pH-controlMonolayer charge
Control over macrocycle conformationIn Langmuir monolayer
Monolayer is a precursor of solid state ultra thin film (LB film).
Evaluation of functional efficiency as well as adjustment of the molecular composition/conformation arrangement
4.2
pH4.6 4.8
Cu(II)Cu(II)Ni(II)
Ni(II)
Ni(II)
Cu(II)
Cu(II)
Cu(II)
Cu(II)
Cu(II)
Cu(II)Ni(II)
Ni(II)Ni(II)
Ni(II)
Ni(II)
Ni(II)
Ni(II)
Ni(II)
Ni(II)Cu(II)
Cu(II)
Ni(II)
INVERSION OF MACROCYCLE SELECTIVITY IN LANGMUIR MONOLAYER
7 8 9 100
50
100
150
200
250CuK
NiK
NiK
CuK
Intensity,
imp
Energy, keV
NN CuN
NNN N Cu
NNN N Cu
7 8 9 100
20
40
NiK
NiK
CuK
CuK
Intensity,
imp
Energy, keV
NNN Cu
NNN N Cu
NNN N Ni
Intensity,
imp
Energy, keV7 8 9 10
0
50
100
150NiK
CuK
NiK
CuK
)) NiN
NN N Ni
NNN N Ni
NNN N
PLANAR ELEMENT OF CHEMICAL SENSORPLANAR ELEMENT OF CHEMICAL SENSOR
50
100
150
200
250
300
350
400
-8 -7 -6 -5 -4 -3 -2lg [Cu(II)]
f, Hz
DCC LB-film ( 11 layers)
0
80
160
240
320
400
0 2 4n, number of cycles
f, Hz
SENSING UNIT TRANSDUCING PLATFORM PLANAR SENSOR+LB film of DCCQuartz crystal microbalance
calibration
Testing measurements(2 weeks later)
-8
10 mmol CuCl2
0.01 mol CuCl2
0
50
100
150
200
f, Hz
Zn(II)Ni(II)
Cu(II)
Cu(II) Zn(II) Ni(II)
0
50
100
150
200
f, Hz
Cast film of DCC LB film of DCC
Selectivity of DCC in ultra thin films
The interactions of Zn(II)-DCC complex with imide group of the uracil in SAM-supported LB monolayer
Time-dependent changes of resonance angle measured for SAM-supported LB monolayer of Zn(II)-DCC complex exposed to the uracil
or adenine solution.
(inset); the linear calibration of maximal SPR signal on a logarithm of uracil concentration
Zn(II)-DCC complexes preformed in Langmuir monolayer
Zn(II)-DCC complexes formed in LB film(LB of pure DCC + solution of ZnCl2)
adenine
uracil
NN
N NZn+2
H
HH
H
N
NH
O O
Interaction of Zn-DCC with deprotonated imide
moiety
SPR-sensogram
suracil, 10-3 M, pH
7.3
“Switch on” and “switch off” the binding of uracil
The interactions of Zn(II)-DCC complex with dianionic phosphate monoester
SPR kinetic curves of phosphate recognition by SAM-supported LB monolayer of Zn(II)-DCC formed after monolayer transferring on SAM support:
the binding of HPO42- in 10-4 M of Na2HPO4 at pH 7.5
and the curve obtained for 10-4 M NaH2PO4 at pH 6.5
O-PRO
O-
O
Zn2+NN
N N
HH
H H
Zn-DCC as monotopic
receptor for dianionic
phosphate monoester HPO4
2-
H2PO4-
SolventTipToCReorganization
TYPES OF INSTABILITY
STRUCTURAL THERMAL MECHANICAL CHEMICAL
The Enhancement of Nanodevice Stability
Low- molecular weight compounds
ReorganizationToC Tip Solvent
Monolayers of polymeric compounds
(linear, branched, comb-like)
PROBLEMS OF POLYMER APPLICATION• Functionalization• Formation of true monolayer on the water surface• Low level of organization
Polymerization of monomers in monolayers
PROBLEMS Demand of amphiphility Restrictions on reaction conditions
(temperature, water surface) Common system –
photopolymerization of olefins
Functionalized surfaces and ultrathin films of 2D networked polymer Functionalized surfaces and ultrathin films of 2D networked polymer
matrix for immobilization of molecules and nanoparticlesmatrix for immobilization of molecules and nanoparticles
2D hybrid blocks of networked polymer containing molecules or nanoparticles
3D multilayer structure assembled of 2D blocks by LB technique
Reactive surface or 2D block of cross-linked polymer formed by use of monolayer technique
Interlocking of molecules or nanoparticles in matrix of networked polymer
Functional groups of the network
Functional molecules or nanoprticles interlocked in polymer network
Reactive oligomer(s)
Gold nanoparticle
NH
NNN
R
R HDicetylcyclen
M A T E R I A L SM A T E R I A L SM A T E R I A L SM A T E R I A L S
Triethylenetetramine (TETA)
Polyoxometalates: H3[PW12O40]
Epoxy-novolac oligomer (GY-1180)
O
CH2
HC
H2C
O
CH2
O
CH2
HC
H2C
O
CH2
O
CH2
HC
H2C
O
n
NH2-CH2 2 2 2NH2CH 2CH -NH-CH 2-NH-CHCH
CURING AGENTS
Compression isotherms of epoxy
oligomer monolayers on the surface of
water and aqueous H3[PW12O40] solutions
at various exposure times
water
10 min
4 hours
24 hours
H3[PW12O40]
water
10 min
4 hours
24 hours
H3[PW12O40]
H3[PW12O40]
Epoxy oligomer
ECOF2004
Formation of mixed monolayer 2D cross-linking
Н2О
Н2О
Preparation of cross-linked monolayer by use of mixture of oligomer and curing agent
0
5
10
15
20
25
30
0 50 100 150 200 250 300
A, A2/molec.
, mN/m
1 час
4 часа
24 часа
II
I
1 hour
24 hours
4 hours
Compression isotherms of mixed monolayers of
epoxy oligomer and triethylenetetramine on the
surface of water at various exposure times
Curing agent in mixed monolayer (TETA)
Epoxy oligomer in monolayer
TRANSMISSION ELECTRON MICROSCOPY IMADGES OF TWO-DIMENSIONAL EPOXYAMINE POLYMER NETWORKS
Au nanoparticles immobilized in 2D epoxyamine polymer network
One monolayer
Immobilization of gold nanoparticles
Н2О
Н2О
TEM image of one monolayer of epoxyamine cross-linked polymer
deposited onto the TEM grid
One monolayer
AFM-IMAGE OF MIXED MONOLAYER OF TERNARY SYSTEM - EPOXY OLIGOMER/TRIETHYLENETETRAMINE (CURING AGENT)/DICETYLCYCLEN - ON THE
SURFACE OF SILICON
Matrix of cross-linked epoxy-amine
polymer
Phase of amphiphilic
cyclen
Interaction of Cu2+ cations with DCC immobilized into cross-linked polymer matrix
“Complexation-Regeneration” cycles
pH 5.6
pH 2.0
Zn(II)/ DCC/URACIL COMPLEXES IMMOBILIZED IN 2D NETWORKED EPOXYAMINE MATRIX
Zn(II)NH
N
NN
R
R H
N –
NH
OO
Zn(II)-DCC complex/UracilTEM - image
50 nm
One monolayer
X PPP
X P
PO
OH
PO
O
OH
OH
OH
O
O
POO
OHOH NH
NH
O
O
OH
OH
O
POO
OHOH
N
N
N
N
NH2
NN
N NH H
N N
NNN
N NH
H
H
NH
H
CH38
Zn2+Zn2+
4 ClO4-
Zn(II)-BC
Langmuir monolayer
adenosine-5’-phosphate (AMP)
uridine-5’-triphosphate (UTP)
pH 8.5
S S S SSS SS
LB monolayertransferred on SAM
S S S SSS SSS SSS SS S S S S SS SSS S
Active matrices of Zn(II)-BC in nucleotide solution
pH 7.0-7.5
Design active biomimitic surfaces for programmed self-assembling of nucleotides
Molecular recognition in Zn(II)-BC monolayers – water/solid interface
S S S SSS SS
0
30
60
90
120
0 1000 2000 3000 4000 5000F, Hz
Z R
e, O
m
thiol-Zn(II)-BC
thiol-Zn(II)-BC-adenine
thiol-Zn(II)-BC-adenine-uracil
0 50 100 150 200 250 300
3796
3797
3798
3799
3800
3801
3802
0.1 g/l
H2O
min
uracil
Zn(II)-BC
time, min
The dependence of resonance angle of SPR spectra on time for Zn(II)-BC monolayer exposed to uracil solution with concentration of base 0.1gL-1 at pH 7.3; 20˚C.
Bode diagram for Zn(II)-BC monolayer exposed in adenine solution (0.05 gL-1) and in mixed solution of adenine/uracil with concentration of each base 0.05 gL-1. Red/Ox [FeCN6]3-/4-/KCl (0.1N), pH 7.35.
The dependence of resonance angle of SPR spectra on time for Zn(II)-BC monolayer exposed to Na3PO4 solution (10-4M of salt) at pH 7.5; 20˚C.
0 50 100 150 200 2503796
3797
3798
3799
3800
3801
3802
3803
Na3PO
4
Zn(II)-BC
min
time, min
Zn(II)-BC monolayer binds both imide and phosphate groups and can be usedas a sensing unitof chemical sensors
THE BINDING OF COMPLEMENTARY NUCLEOTIDES IS A MULTISTEP PROCESS CONTROLLED BY THE GEOMETRY OF THE ACTIVE MATRIX!!!(the hierarchical self-assembling of functionalized supramolecular systems)
1)The binding of the first nucleotide on one head of Zn(II)-BC
2)The coupling of complementary
nucleotide with a first one nucleotide with a first one
via base pairing and the via base pairing and the
coordination of the terminal coordination of the terminal
phosphate group of phosphate group of
complementary nucleotide complementary nucleotide
to the other head of Zn(II)-to the other head of Zn(II)-
BCBC
3)The binding of the terminal 3)The binding of the terminal
phosphate and phosphate and
decomposition of the coupledecomposition of the couple
4)The binding of the second 4)The binding of the second
complementary nucleotide complementary nucleotide
via specific base pairing via specific base pairing
XP
PP
S S S SSS SSS SSS SS S S S S S
XP
PP
XP
PP
XP
PP
XP
PP
XP
PP
X
PP
PXP
PP
S SSS S
21 34
XP
PP
P P P
S S S SSS SSS SSS SS S S S S S S
XP
PP
XP
PP
XP
PP
3d step UTP2nd step ATP1st step UTP
S
XP
PP
XP
PP
X
XP
PP
SS S S S S S S
XP
PP
S
XP
PP
XP
PP
0 100 200 300 400
3792
3794
3796
3798
3800
3802
UTP
ATP
ATP+UTP
Zn(II)-BC
min
time, min
ONE- AND MULTI-STEP HIERARCHICAL SELF-ASSEMBLING OF FUNCTIONALIZED SUPRAMOLECULAR SYSTEMS
0 50 100 150 200 250 300 3503774
3775
3776
3777
3778
3779
3780
3781
3782
ATP
UTP
UTP
H2O
Zn(II)-BC
min
time, min
ONE-STEPMULTI-STEP
S S S SSS SS
XP
XP
PP
XP
XP
PP
XP
XP2nd step
UMP
1st step ATP
S S S SSS SS
XP
PP
XP
PP
XP
PP
XP
PP X
PP
XP
PP
XP
P3d step2nd step1st step
S S S SSS SS
XP
PP
X P X P
2nd step ATP1st step UMP
Formation of self-organized matrices of non-uniform chemistry and topography by use of complementary
nucleotides with different number of phosphate residues and ”switch off” the process by UMP
0 50 100 150 200 250 300 3503790
3791
3792
3793
3794
3795
3796
min
H2O
UMP
ATP
Zn(II)-BC
time, min
0 100 200 300 400 500
3792
3795
3798
3801
3804
3807
3810
3813
UDP
UTPATP+ADP
H2O
Zn(II)-BC
min
time, min 0 50 100 150 200 250 3003790
3792
3794
3796
3798
H2O
min
ATPUMP
Zn(II)-BC
time, min
?
XP
PP
OUTLOOKSDifferent systems of controllable composition and structure can be produced using two types of complementary nucleotides and only type of matrix by means of complementary self-assembling of nucleotides at physiological pH
different chemical and biosensors and functionalized surfaces for cyclic preparative synthesis ( i.e. regioisomers) and catalysis
S S S S S S S
P
S
PX X
A B
new biocompatible and non-toxic materials through polymerization of complementary matrices
XP
P
XP
PP
XP
PP
XP
PP
XP
P
XP
P
organized arrays of artificial codons
S S S S S S S S
PX
PX
PXG C
A
S
LB patterning via gel stamping
agarose stamp
H2O + KJ
Ag+
Ag+
Ag+
Ag+ Ag+Ag+
Ag+
AA A
Ag+
Ag+
Ag+
Ag+
Ag+
Ag+
Ag+
B B
Ag+ +J-= AgJ
Ag+
AA A
Ag+
Ag+
Ag+
Ag+
Ag+
Ag+
Ag+
B B
AgJ
UV treatment:LB decomposition +Ag reduction
AA AB B
arrays of silver nanoparticlespatterned surface
LB film of Ag(I)-DCC complex
50 m
arrays of silver nanoparticles
silicon surface(stamp’s “photo”)
Optical microscopy images for 17 layerOptical microscopy images for 17 layer