toward multifunctional
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TOWARD MULTIFUNCTIONAL “CLICKABLE” NANOPARTICLES
Volodymyr Turcheniuk, Aloysius Siriwardena, Vladimir Zaitsev, and Sabine Szunerits
Institute of Electronics, Microelectronics and Nanotechnology, Universite Lille 1, France
Taras Shevchenko University of Kiev, UkrainePontifícia Universidade Católica do Rio de Janeiro
Laboratoire de Glycochimie des Antimicrobiens et des Agroressources, Universite de Picardie, Amiens, France
Professor Vladimir ZaitsevD.Sc., Ph.D., corr. Memb. NAS
Ukraine
Iron oxide magnetic nanoparticles with versatile surface functions based on dopamine anchors
• SiO2,• ZrO2,• TiO2
• SiC,• C• Si
Nanoscale, 2013, 5, 2692 Cited - 22
www.achem.univ.kiev.ua
RESEARCH INTERESTS
1. Chemistry on the interface: immobilised reagent /solution2. Immobilised layer topography and its influence for the material properties3. Immobilised metal complexes composition and stability
Synthesis Application
Surface-modified materials
Investigation
1. Solid-phase analytical reagents2. Test-systems for simple analysis3. Adsorbents for selective pre-concentration4. New chromatographic phases5. Catalytically active materials6. Chemical and biosensors7. Drug delivery systems
Fundamental problems
Structure of Research activity
Groups for application
Group for preparation and characterisation
General scientific directionOrgano-mineral
composites
Silica-based
Analytical application
Oksana Tananaiko,Marina Zuy
Viktoria Khalaf,Olena KonoplytskaLuidmila Kostenko
Application in catalysis
Tatiana Kovalchuk,
Sergey Alekseev,
Vasiliy Gerda,
Silicon-based
Lab-on-chip
S. Alekseev
O. Tananaiko
N. Kobylinskaya
Other inorganic support
Application in Catalysis
Several examples of Organo-mineral composite Materials (OMCM)кислотами, основаниями комплексонами
анионобменниками
OH
N+
OH
N
N+
R
OH
N+
RR
R
OH
P+
Ph Ph
Ph
Si NR2Si SO3H
Si NH
NH2Si
SO3H
Si NH+P
P
O
OHO
OH
OHO
Solid acids and bases
Ion-exchangers
Chelating compounds
Si NN
COOH
COOH
COOH
Si NH
PO3H2
OH
N N
NOH
Si
Si NCO2H
CO2H
www.achem.univ.kiev.ua
CHELATING SILICA-BASED MATERIALS
Si(CH2)3 NCH2PO3H2
CH2PO3H2
Si (CH2)3 NH
O
N
COONa
Si C
O
N
OH
(CH2)3NH
Si (CH2)3 NH PN(C2H5)2
N(C2H5)2
S
Silice greffée HPA Application: catalyse acide
O
EtOH+H+ +-H+
ETBE
SiOH
SiOH
Si
NH2
SiO Si
SiOSi
Si
NH2
SiOH
SiOH
Si
N+
OSi
SiOH
SiOH
Si
N+
SiOH
SiOH
Si
NN
SiOH
SiOH
Si
NN+ +
mono- polycouche
hydrophilique -phobic
H3[PW12O40] H4[SiW12O40] H3[PMo12O40] H4[SiMo12O40]
CH3OH
O
CH3OC2H5
O
CH3OH
OH
-H2O,+H+
-H+
EtOH+
Acétate d'éthyle
SiO2-PE-Eu films
R–SO3−Na+ + Eu(III) → R–SO3−Eu(III) + Na+
Modification of Graphene oxide with polymer
O
O
O O
C
C
O
1. NH2-PEG-NH22. EDC3. Mercaptoethanol
H2N NH2
O
O
COOH
O
C O
OH
O
C O CO
OH
HO
O
OH
O
O
OH
GO-COOH
in H2O
NHO
H2NONH
H2N
OHN
NH2
O
HN
NH2
OHN
NH2
OHN
NH2
GO-PEG
2 h, 45 °C
35 kHz
H2N OO NH2
31
M=1500 Da
Infrared Photothermal Therapy with Water Soluble Reduced Graphene Oxide: Shape, Size and Reduction Degree Effects. Nano LIFE 2015 Vol. 5, No. 1
C1s high resolution XPS spectra
Synthesis of hybrid material through covalent interaction
COOH
COOHCOOH
CTAB
O
O
O O
C
C
OH
NHO
H2NONH
H2N
OHN
NH2
O
HN
NH2
OHN
NH2
OHN
NH2
GO-PEG
+
Carbodiimide
Graphene coated Gold nanorods
0
0.5
1
1.5
2
200 400 600 800 1000 1200
GO-Au hybridrGO-PEGGold NRs
Abs
orba
nce
Wavelength, nm
252 nm
527 nm727 nm
736 nm
shift 9 nm
Material Zeta, mV
Gold NRs -24.5rGO-PEG -26.2
covalent interaction
1.5 nm
1.7 nm
10 nm
Characterization of hybrid material: TEM and HRTEM images
10 nm
Graphene layer
Graphene Layer thickness around 1.7 nm
Part 2.
HRTEM of Gold-Graphene composite
SEM images of Gold-graphene compositePart 2.
Conclusion: we managed to cover Gold Nanorods with layer of reduced Graphene Oxide preserving its stability and solubility in water.
SEM image of Gold Nanorods covered with Graphene. Stability tested after 2 months at 4 °C
Graphene layer protects Gold Nanorods from degradation!!!
SEM image of Gold Nanorods after 2 months at 4 °C
Stability
GO GO-COOH rGO-PEG
Infrared Photothermal Therapy with Water Soluble Reduced Graphene Oxide: Shape, Size and Reduction Degree Effects. Nano LIFE 2015 Vol. 5, No. 1
Remarkable stability at room temperature of GO-PEG within 6 months at room temperature
Photothermal propertios of Gold-Graphene composite.
Infrared Photothermal Therapy with Water Soluble Reduced Graphene Oxide: Shape, Size and Reduction Degree Effects. Nano LIFE 2015 Vol. 5, No. 1
Biomedical applicationAu-Graphene rGO-PEG GO
22°C57°C85 °C
• There was no sign of acute toxicity of rGO–PEG for HeLa and MDA-MB-31 cancer cells over a wide concentration range
Relative cell viabilities of HeLa after irradiation
Infrared Photothermal Therapy with Water Soluble Reduced Graphene Oxide: Shape, Size and Reduction Degree Effects. Nano LIFE 2015 Vol. 5, No. 1
A complete destruction of the tumor cells could be achieved with a laser power of 6 W/cm2 and a concentration of 60 gm L1 of rGO–PEG.
Electrocatalytic sensors
Cobalt phthalocyanine tetracarboxylic acid modified reduced graphene oxide: a sensitive matrix for the electrocatalytic detection of peroxynitrite and hydrogen peroxide. RSC Adv., 2015, 5, 1474
Electrocatalytic response rGO/CoPc–COOH modifedglassy carbon electrodes
Cyclic voltammograms on GCE modified by rGO/CoPc–COOH in the absenceand in the presence of 15 nM peroxynitrite in pH 10, and pH 7.4
Electrochemical Reaction• Co(II)Pc–COOH -> Co(III)Pc–COOH + e• Co(III)Pc–COOH + O=N–O–O- -> Co(II)Pc–COOH–OONO°• Co(II)Pc–COOH–OONO° + e -> Co(III)Pc–COOH + ONO2°• 2 ONO2° -> O2 + NO2
Amperometric determination of PON using glassy carbon electrode modified with rGO/CoPc–COOH
Selectivity
nitrate, nitrite, hydrogen peroxide, dopamine (DA), Ascorbic acid (AA), glucose (Gl) at 1000 times excess
Si N(CH3)3HO3As+ -
N+
NCl-
SD-SiO2
N+
NBF4Si N -
DA-SiO2
SiOO Si
OMeO O
OHCH2 n
CH2 O C8H17
OO Si
OMeO
O
TX-SiO2
Si SO3
NN
NN
+
Ph
PhPh
-
SiO2-SO3Ph3Taz+-
Silica based activated phases!
Fe3O4- based activated phases
Horseradish peroxidase (HRP)
6-(ferrocenyl)-hexanethiol
UV/Vis spectra (left) and calibration curves (right) recorded with subsequently modified MF-MPs:
(A) MF-MP1; C= 20 mg/g
(B) MF-MP2 (0.5 mg mL1) in 2 mL of a solution containing 20-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) (3.6 mM) and H2O2 (50 mM) (black line) and of naked magnetic particles (dotted grey line); C= 14,6 mg/g -> 30 mg/g
(C) MF-MP3 (recorded after 60 min of immersion of 0.2 mg mL1 MF-MP3 in a phenol-sulfuric acid solution).C= 19 mg/g -> 60 mg/g
Toward “Clickable” Diamond Nanoparticles
NH
ND
O
N3
NO2
O
OH
compound (1)
Cu(I)
NH
ND
O
N NNNO2
OH
OH
K2CO3
Br
NO2
O
OH
(1)
Phenylboronic-Acid-Modified Nanoparticles: Potential Antiviral Therapeutics
2-nitrodopamine
Toward Multifunctional “Clickable” Diamond Nanoparticles
Langmuir 2015, 31, 3926−3933
Characterization
Stability
Suspensions of ND−dop−EG+N3 (50 μg/mL) in PBS (pH 7.4, 0.1 M) at different time intervals together with a bar diagram of the change in particle size
4-pentynoic acid
α-D-mannopyranoside (α-mmp),
The use of PWR in combination with an adapted surface-modification strategy results in detection limits of glycans–lecin binding events around 500 pM, comparable to fluorescence based approaches, with the advantage of being label free.
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