1. TOWARD MULTIFUNCTIONAL
“CLICKABLE” NANOPARTICLES
Volodymyr Turcheniuk, Aloysius Siriwardena,
Vladimir Zaitsev, and Sabine Szunerits
Institute of Electronics, Microelectronics and Nanotechnology,
Université Lille 1, France
Taras Shevchenko University of Kiev, Ukraine
Pontifícia Universidade Católica do Rio de Janeiro
Laboratoire de Glycochimie des Antimicrobiens et des
Agroressources, Université de Picardie, Amiens, France

2. Professor Vladimir Zaitsev
D.Sc., Ph.D., corr. Memb. NAS Ukraine

3. Iron oxide magnetic nanoparticles with
versatile surface functions based on
dopamine anchors
• SiO2,
• ZrO2,
• TiO2
• SiC,
• C
• Si
Nanoscale, 2013, 5, 2692 Cited - 22

4. www.achem.univ.kiev.ua
RESEARCH INTERESTS
1. Chemistry on the interface: immobilised reagent /solution
2. Immobilised layer topography and its influence for the material properties
3. Immobilised metal complexes composition and stability
Synthesis Application
Surface-modified
materials
Investigation
1. Solid-phase analytical reagents
2. Test-systems for simple analysis
3. Adsorbents for selective pre-concentration
4. New chromatographic phases
5. Catalytically active materials
6. Chemical and biosensors
7. Drug delivery systems
Fundamental problems

5. Structure of Research activity
Groups for application
Group for preparation and
characterisation
General scientific direction
Organo-
mineral
composites
Silica-
based
Analytical
application
Oksana Tananaiko,
Marina Zuy
Viktoria Khalaf,
Olena Konoplytska
Luidmila 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

6.  Several examples of Organo-mineral composite Materials (OMCM)
кислотами, основаниями комплексонами
анионобменниками
OH
N
+
OH
N
N
+
R
OH
N
+
R
R
R
OH
P
+
Ph
Ph
Ph
Si NR2
Si SO3
H
Si N
H
NH2
Si
SO3H
Si NH+
P
P
O
OH
O
OH
OH
O
Solid acids and bases
Ion-exchangers
Chelating compounds
Si N
N
COOH
COOH
COOH
Si N
H
PO3H2
OH
N N
NOH
Si
Si N
CO2
H
CO2
H

7. www.achem.univ.kiev.ua
CHELATING SILICA-BASED MATERIALS
Si(CH2)3 N
CH2PO3H2
CH2PO3H2
Si C
O
N
OH
(CH2)3NH
Si (CH2)3 NH P
N(C2H5)2
N(C2H5)2
S

8. Silice greffée HPA Application: catalyse acide
O
EtOH+H+
+
-H+
ETBE
Si
OH
Si
OH
Si
NH2
Si
O
Si
Si
O
Si
Si
NH2
Si
OH
Si
OH
Si
N
+
O
Si
Si
OH
Si
OH
Si
N
+
Si
OH
Si
OH
Si
N
N
Si
OH
Si
OH
Si
N
N+ +
mono- polycouche
hydrophilique -phobic
H3[PW12O40]
H4[SiW12O40]
H3[PMo12O40]
H4[SiMo12O40]
CH3
OH
O
CH3
OC2H5
O
CH3
OH
OH
-H2O,
+H+
-H+
EtOH
+
Acétate d'éthyle

9. SiO2-PE-Eu films
R–SO3−Na+ + Eu(III) → R–SO3−Eu(III) + Na+

10. 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

11. COOH
COOH
COOH
CTAB
+
Carbodiimide
Graphene coated
Gold nanorods
0
0.5
1
1.5
2
200 400 600 800 1000 1200
GO-Au hybrid
rGO-PEG
Gold NRs
Absorbance
Wavelength, nm
252 nm
527 nm
727 nm
736 nm
shift 9 nm
Material Zeta, mV
Gold NRs -24.5
rGO-PEG -26.2

12. 1.5 nm
1.7 nm
10 nm
10 nm
Graphene Layer
thickness around 1.7 nm
Part 2.

13. 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

14. 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

15. 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 application
Au-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

16. 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.

17. 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

18. Electrocatalytic response rGO/CoPc–COOH modifed
glassy carbon electrodes
Cyclic voltammograms on GCE modified by rGO/CoPc–COOH in the absence
and in the presence of 15 nM peroxynitrite in pH 10, and pH 7.4

19. 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

20. Amperometric determination of PON using
glassy carbon electrode modified with
rGO/CoPc–COOH

21. Selectivity
nitrate, nitrite, hydrogen peroxide, dopamine (DA), Ascorbic acid (AA), glucose (Gl)
at 1000 times excess

22. Si N(CH3
)3
HO3
As
+ -
N
+
NCl
-
SD-SiO2
N
+
NBF4
Si N -
DA-SiO2
Si
O
O
Si
OMe
O O
OH
CH2 nCH2 O C8
H17
O
O
Si
OMe
O
O
TX-SiO2
Si SO3
N
N
N
N
+
Ph
Ph
Ph
-
SiO2-SO3Ph3Taz+
-
Silica based activated phases!

23. Fe3O4- based activated phases

24. Horseradish
peroxidase (HRP)
6-(ferrocenyl)-hexanethiol

25. 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

26. Toward “Clickable” Diamond Nanoparticles
NH
ND
O
N3
NO2
O
OH
compound (1)
Cu(I)
NH
ND
O
N N
N
NO2
OH
OH
K2CO3
Br
NO2
O
OH
(1)

27. Phenylboronic-Acid-Modified Nanoparticles:
Potential Antiviral Therapeutics
2-nitrodopamine

30. Toward Multifunctional “Clickable”
Diamond Nanoparticles
Langmuir 2015, 31, 3926−3933

31. Characterization

32. 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

34. 4-pentynoic acid

35. α-D-mannopyranoside (α-mmp),

36. 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.