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Chuiko Institute of Surface Chemistry

National Academy of Sciences of Ukraine
(official site)

Laboratory of Photonics Oxide Nanosystems

 smirn

 

 

Head of Laboratory

Smirnova Nataliia P.

PhD in Chemistry, Senior Researcher

Telephone: + 380 44 422-96-98

Fax: + 380 44 424-35-67

E-mail: This email address is being protected from spambots. You need JavaScript enabled to view it. ;

 

Laboratory staff is 10 co-workers including 1 DSc and 8 PhDs. From 1986, the Laboratory staff have published 5 chapters in collective books, 250 scientific papers, and obtained 5 patents for inventions; 1 DSc and 15 PhD theses were defended.

 

Directions of investigations

Investigationof UV light interaction with the surface of adsorbents, a transfer of electron, proton or exciting energy between adsorbed organic compounds and the active sites of solids - silica, titania and binar oxide systems, synthesis and properties of nanosized metal particles.

Synthesis and physical-chemical properties studies of mixed oxides and layered double hydroxides; creation of photocatalysts on their base.

Synthesis and studies on the structure, surface chemistry, photoelectrochemical and photocatalytical properties of mesoporous films based on oxides of IV group elements and mixed oxide systems.

Mechanisms of photoinduced processes of electron, proton and energy transfer in semiconductor composites under conditions of redox transformations of organic and inorganic compounds.

Technology development of new nanosized broad-spectrum bactericide materials and conjugated nanobiotechnologycal antitumoral hypotoxical preparations based on silver, gold, copper nanoparticles in the colloids and suspensions of dispersed silica.

Researches of photocatalytic elimination of nitrogen-contained organic pollutants form aqueous solutions (cancerogenic polyacenes, dyes, antibiotics) and gas phase (alcohols, ketones); photoreduction of inorganic toxic ions (Cr(VI), Hg(II), Cu(II)).

Systematic spectral researches into the state of incorporated transition and rare-earth ions in inorganic matrices (quartz and borates) by the steady-state, kinetic photo- and radioluminescence, optical absorption, and ESR techniques.

Potential applications: coatings (photocatalysts, electrochemical sensors, self-cleaning windows, tables, walls etc, defogging mirrors, antireflective and ornamental coatings); optics (information recording devices, matrices for MALDI, substrates for IR-, Raman and Fluorescence spectroscopy, biosensors); healthcare(bactericides, system for diagnostics, antimicrobial, conjugated nanobiotechnologycal antitumoral hypotoxical preparations based on silver, gold, copper nanoparticles).

 

Main results for the recent years

Approach involving a simultaneous reduction of silver nitrate and tetrachlorauratic acid using tryptophan (Trp) as a reducing/stabilizing agent was applied during NP synthesis. The obtained Ag/Au/Trp NPs (5-15 nm sized) were able to form stable aggregates with an average size of 370-450 nm and were potentially less toxic than Ag/Au/SDS in relation to a mouse model system based on clinical biochemical parameters and oxidative damage product estimation. Ag/Au/Trp NPs were shown to exhibit anticancer activity in relation to a Lewis lung carcinoma model.

Colloidal solution of Ag nanoparticles, heterogeneous Ag/SiO2 system and bimetallic Ag/Au nanoparticles produced photochemically in colloidal solutions and within porous silica films and powders in the form of alloy and core/shell showed a high antimicrobial activity against a number of pathogenic microorganisms. 

The highly dispersed Zn-Al mixed oxides have been synthesized by citrate method and by thermal decomposition of Zn-Al layered double hydroxides (LDH) prepared by coprecipitation method. The possibility of its reconstruction in LDH in aqueous suspensions has been studied. There was established that the hydration of oxide systems synthesized by citrate method had caused partial conversion of mixed oxides to the crystalline phase of LDH. In the case of oxides obtained by thermal treatment of Zn-Al LDH, the almost complete regeneration of LDH structure has achieved. The effect of ultrasonic treatment, stirring time and the presence of magnesium oxide in oxide systems on hydration process of Zn-Al mixed oxides has been studied. The crystal structure, morphology, textural properties and ability to absorb light in the ultraviolet range of the mixed oxides and products of their hydration have been studied.

Low-temperature sol-gel methods of synthesis of porous nanosized transparent stable films on the basis of titania and its binary compositions with oxides of silicon, iron, and zirconium have been developed. The methods involve simultaneous hydrolysis of corresponding alkoxides in the presence of template agents (CTAB and triblock copolymer P123).The structure and optical properties of these films were characterized using SEM, AFM, low-angle XRD and UV/Vis spectroscopy, hexane adsorption investigation.

Zr or Si oxides doping on the stage of sol-gel process improves thermal stability, retards sintering of the films and stabilizes the nanocrystalline structure with developed porosity. Catalytic activity of mesoporous TiO2 and TiO2/ZrO2 (5-50% of ZrO2) films in the processes of gaseous ethanol photooxidation growth with increasing of specific surface area and surface acidity of the samples. Enhancing of photocatalytic activity of zirkonia-doped films relatively to pure TiO2 originates from an anodic shift of the valence band edge potential (estimated by direct photoelectrochemical measurements).

Possibility of encapsulation of gold (Au), silver (Ag) and copper (Cu) nanoparticles by amino acid – tryptophane (Trp) in solutions and on the silica surface was proven. Tryptophane executes a double function - effective reducing agent of gold ions and stabilizer of Au nanoparticles. The significant increase in the intensity of the carbonil and amino groups as well as the benzene and pyrrole ring vibrations in the Raman spectra of Trp in the presence of Au NP was observed due to donor-acceptor complex formation.

Study of X-ray luminophors - single crystal and glassy lithium tetraborate (LTB) doped with transition and RE ions: Cu, Ag. Mn, Eu Ce using sets of methods: optical absorption; steady- state and time-resolved photoluminescence (PhL); radioluminescence (RL), termoluminescence (TL) including spectrally-resolved 3-dimentional (TL). Valence and coordination states and hence the luminescence properties of all doped species are determined by morphological structures of solid LTB lattice. A comparative characterization of undoped lithium tetraborate (LTB) and Cu-doped (LTB:Cu) single crystals (tissue-equivalent luminophors) to commercially produced TLD-100 and TLD-700 dosimeters was studied. The results show that LTB:Cu is approximately 50 times more sensitive to gamma-radiation than LTB and 5 times as compared to TLD-100 and TLD-700. At the same time LTB is 5 times more sensitive to thermal neutrons, which suggests the application of paired LTB and LTB:Cu for mixed gamma-neutron field dosimetry.

 

Laboratory staff

Smirnova Nataliia P.PhD, Head of Laboratory,

tel.:+38 (044) 4249465; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Chorna Nataliia O., leading engineer,

tel.:+38 (044) 4229698; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Eremenko Anna M.DSc, Leading Researcher,

tel.:+38 (044) 4229698; e-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.

Khaninа Oksana A., PhD, Junior Researcher,

tel.:+38 (044) 4229698; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Linnik Оksana P., PhD, Senior Researcher,

tel.:+38 (044) 4229698; e-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.

Mukha Iuliia P., PhD, Research Associate,

tel.:+38 (044) 4229698; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Petrik Irina S., PhD, Research Associate,

tel.:+38 (044) 4229698; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Starukh Galyna N., PhD, Senior Researcher,

tel.:+38 (044) 4229698; e-mail  This email address is being protected from spambots. You need JavaScript enabled to view it.

Vityuk Nadiia V., PhD, Research Associate,

tel.:+38 (044) 4229698; e-mail:  This email address is being protected from spambots. You need JavaScript enabled to view it.

Yashan Galyna R., PhD, Junior Researcher,

tel.:+38 (044) 4229698; e-mail: jashan This email address is being protected from spambots. You need JavaScript enabled to view it.

 

Recent publications

1. I.O. Shmarakov, Iu.P. Mukha, V.V. Karavan, O.Yu. Chunikhin, M.M. Marchenko, N.P. Smirnova, A.M. Eremenko. Tryptophan assisted synthesis reduces bimetallic gold/silver nanoparticle cytotoxicity and improves biological activity // Nanobiomedicine – 2014. – V. 1. – P. 01 – 10.

2. N. Ostapenko, Yu. Ostapenko, O. Kerita, D. Peckus, V. Gulbinas, A. Eremenko, N. Smirnova, N. Surovtseva Luminescence features of nanocomposites of silicon-organic polymer/porous SiO2 and TiO2 films // Synthetic Metals – 2014. - V. 187. - P. 86 – 90.

3. G. M. Starukh, O. I. Oranska, S.I. Levytska. Reconstruction of ZnO-contained mixed oxides in layered double hydroxides // Ukr. Chem. J – 2014. – V. 80, N 9. – P. 32–40.

4. A. Naumenko, Iu. Gnatiuk, N. Smirnova, A. Eremenko. Characterization of sol–gel derived TiO2/ZrO2 films and powders by Raman spectroscopy// Thin Solid Films. – 2012 – V. 520, N 14. –- P.4541–4546.

5. O. Linnik, I. Petrik, N. Smirnova, V. Kandyba, O. Korduban, A. Eremenko, G. Socol, N. Stefan, C. Ristoscu, I.N. Mihailescu, C. Sutan, V. Malinovski, V. Djokic, D.Janakovic. TiO2/ZrO2 thin films synthesized by PLD in low pressure N-, C- and/or O-containin ggases: structural, optical and photocatalytic properties // Digest Journal of Nanomaterials and Biostructures. – 2012. – V. 7, N 3. – Р.1343–1352.

6. N.V. Gaponenko, V.S. Kortov, N. P. Smirnova, T.I. Orekhovskaya, I.A. Nikolaenko, V.A. Pustovarov, S.V. Zvonarev, A.I. Slesarev, O.P. Linnik, M.A. Zhukovskii, V.E. Borisenko. Sol-gel derived structures for optical design and photocatalytic application // Microelectronic Engineering. – 2012. –V. 90. – Р.131–137. doi:10.1016 90.

7. A.M. Eremenko, N.P. Smirnova, I.P. Mukha, A.P. Naumenko, N.M. Belyi, S. Hayde. Effect of gold nanoparticles on an aerosil surface on the fluorescence and Raman spectra of adsorbed tryptophan // Theoretical and Experimental Chemistry. – 2012. –V. 48, N 1. – Р.49–55.

8. H.I. Korchak, О.V. Surmasheva, А.І. Міkhienkova, A.M Eremenko, Yu.P. Мukha, N.P. Smirnova. Method of synthesis of nanosized silver solutions // Patent of Ukraine № 67484 from  27.02.2012.

9. H.I. Korchak, О.V. Surmasheva, А.І. Міkhienkova, A.M Eremenko., Yu.P. Мukha, N.P. Smirnova. Antimicrobial composition // Patent of Ukraine № 67536 from 27.02.2012.

10. A. Eremenko, N. Smirnova, Iu. Gnatiuk, O. Linnik, N. Vityuk, Yu. Mukha, A. Korduban. Silver and gold nanoparticles on sol-gel TiO2, ZrO2, SiO2 // Surfaces: Optical Spectra, Photocatalytic Activity, Bactericide Properties / Chapter in Book 3: Composite Materials. – 2011. – P.2–32.

11. Yu. Gnatyuk, N. Smirnova, O. Korduban, A. Eremenko. Effect of zirconium in corporation on the stabilization of TiO2 mesoporous structure. // Sur. Interface Anal. – 2010. – V. 42. – P.1276–1280.

12. Yu. Mukha, А. Eremenko, G. Korchak, А. Michienkova. Physicochemical properties and antibacterial action of stabilized silver and gold nanostructures on the surface of disperse silica // Journal of Water Resources and Purification.– 2010. – V. 2. – P.131– 136.

13. G.V. Krylova, Yu.I. Gnatyuk, N.P. Smirnova, A.M. Eremenko, V.M. Gunko. Ag nanoparticles deposited onto silica, titania and zirconia mesoporous films synthesized by sol-gel template method // J. Sol-Gel Sci. Technol. – 2009. – V 50. – P.216–228.