toward multifunctional

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.