Faculty of Chemistry

• Department of Analytical and Environmental Chemistry
• Department of Applied Chemistry
• Department of Inorganic Chemistry
• Department of Organic Chemistry
• Department of Physical Chemistry
• Department of Polymer Chemistry

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RESEARCH AREAS

Synthesis and Investigation of Novel Materials and Nanostructures, Development of Analysis Methods

DOCTORAL DISSERTATIONS MAINTAINED IN 2014

J. Rukšnaitė. Surface plasmon resonance and electrochemical imunosensors for human growth hormone and antibodies against human growth hormone detection.
J. Voronovič. Gold nanoparticles and π-π conjugated polymer polypyrrole for glucose biosensors design.
A. Stanulis. Synthesis and characterization of multifunctional tin based compounds.
J. Trinkunaitė-Felsen. Investigation of calcium hydroxyapatite synthesized using natural precursors.
A. Sabaliauskienė. Synthesis, investigation and possible applications of selected phophates and silicates.
R. Skaudžius. Synthesis and investigation of co-substituted yttrium aluminium and yttrium gallium garnets.
I. Balevičiūtė. Spectroscopic ellipsometry of multilayer nanostructures used in biosensors applications.
V. Krikštolaitytė. Design and characterisation of the electrodes of enzymatic biofuel cells.

MAIN CONFERENCES ORGANIZED IN 2014

International conference Nanochemistry and Nanomaterials (2014).
International conference on organic synthesis Balticum Organicum Syntheticum 2014. 

DEPARTMENT OF ANALYTICAL AND ENVIRONMENTAL CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. 219 3117, 219 3114; fax 233 0987
E-mail:

Head - Prof. Dr. Stasys Tautkus

STAFF

Professors:  Habil. Dr. A.Padarauskas, Dr. A. Ramanavičienė, Dr. S. Tautkus, Dr. V. Vičkačkaitė, Habil. Dr. E. Juzeliūnas (part-time).
Associate professors: Dr. A. Kaušaitė-Minkštimienė, Dr. A. Katelnikovas, Dr. E. Naujalis (part-time).
Lecturers: Dr. V. Olšauskaitė.
Doctoral students: I. Baškirova, N. Karlonas, A. Linkevičiūtė, A. Makaravičiūtė, V. Mažeiko, A. Popov, V. Poškus, E. Raudonytė-Svirbutavičienė, M. Skruodienė, V. Šmitienė,   L. Taujenis,  A. Žarkov.

RESEARCH INTERESTS

Development of UPLC-MS techniques for the characterization and determination of organic and bioorganic compounds
Novel microextraction techniques for gas chromatographic analysis
Development of biosensors and immunosensors
Determination of trace elements using atomic absorption spectrometric, spectrophotometric and kinetic methods
Photochemical synthesis of metal oxide particles
Up-conversion phosphors for bio-imaging
Rare earth and transition metal doped phosphors

RESEARCH PROJECTS CARRIED OUT IN 2014

Projects Supported by University Budget

Ultra-High Pressure Liquid Chromatography-Mass Spectrometry for the Investigation of Organic and Bioorganic Compounds. Prof. A. Padarauskas.

High-performance liquid chromatography on a glycopeptide antibiotic teicoplanin based chiral stationary phase coupled with tandem mass spectrometry was developed for fast and reliable enantioseparation of protein amino acids. The effect of the mobile phase parameters (type and content of organic modifier, pH) and the column temperature on the enantioselectivity was investigated. Developed technique was applied for the monitoring of amino acids in commercial fertilizers.

The performance of ultra-high pressure liquid chromatography coupled with tandem mass spectrometry in hydrophilic interaction and reversed phase separation modes was evaluated and compared for the separation ascorbic and dehydroascorbic acids.

Main publications:

Taujenis, L., Olšauskaitė, V., Padarauskas, A. 2014. Enantioselective determination of protein amino acids in fertilizers by liquid chromatography-tandem mass spectrometry on chiral teicoplanin stationary phase.Journal of Agricultural and Food Chemistry, vol. 62, 11099–11108.

Application of Nano- and Microparticles for the Biologically Active Materials Immobilisation and Biosensors Design. Prof. A. Ramanavičienė, Dr. A. Kaušaitė-Minkštimienė.

A biosensor based on glucose oxidase immobilized on gold nanoparticles electrochemically predeposited on the surface of graphite rod electrode was developed. Main analytical characteristics of this biosensor were determined and compared with those determined using a biosensor setup without gold nanoparticles. Analytical signal registered using electrode modified with gold nanoparticles was 2.08 times higher in comparison to electrode without nanoparticles.

Main publications:

German, N., Ramanavicius, A., Ramanaviciene, A. 2014. Electrochemical deposition of gold nanoparticles on graphite rod for glucose biosensing. Sensors and Actuators B: Chemical, vol. 203, 25–34.

The ‘green’, environmentally friendly enzymatic reaction-based synthesis of conducting polymer polythiophene was investigated. Glucose oxidase was shown as an effective catalyst, which, in the presence of glucose, produces hydrogen peroxide suitable for the oxidative polymerization of polythiophene under ambient conditions at neutral pH. It was shown that enzymatic polymerization of polythiophene could be applied in adjustment and/or tuning of K_M^(app.)and other kinetic parameters of glucose oxidase-based electrodes used in biosensor design.

Main publications:

Krikstolaityte, V., Kuliesius, J., Ramanaviciene, A., Mikoliunaite, L., Kausaite-Minkstimiene, A., Oztekin, Y., Ramanavicius, A. 2014. Enzymatic polymerization of polythiophene by immobilized glucose oxidase. Polymers, vol. 55, 1631–1620.

The glucose sensitive electrodes were fabricated by immobilization of glucose oxidase on carbon nanotubes and/or 1,10-phenanthroline-5,6-dione modified graphite rod electrodes. The obtained results indicate that 1,10-phenanthroline-5,6-dione plays an important role in the facilitation of electron transfer between the active site of enzyme and electrode. In addition, carbon nanotubes used in the biosensor design increased the sensitivity of the amperometric signal.

Main publications:

Zor, E., Oztekin, Y., Ramanaviciene, A., Anusevicius, Z., Bingol, H., Barkauskas, J., Ersoz, M., Ramanavicius, A. 2014. Amperometric glucose biosensor based on glucose oxidase, 1,10-phenanthroline-5,6-dione and carbon nanotubes. Journal of the Electrochemical Society, 161(13)H3064–H3069.

Gas Chromatography. Prof. V. Vičkačkaitė.

Dispersive liquid-liquid microextraction in combination with an in situ derivatization was suggested for methyltin compounds sampling and preconcentration from water solutions. Derivatization conditions were optimized and sodium tetraethylborate was selected as a derivatization reagent at pH 3. The effects of extraction and disperser solvents type, volume and extraction time on the extraction efficiency were investigated. 1,2-dichlorobenzene was selected as an extraction solvent and ethanol was selected as a disperser solvent. Gas chromatographic-mass spectrometric conditions for the determination of extracted analytes were optimized. The analytical characteristics of the prepared technique were determined. This work demonstrated that dispersive liquid-liquid microextraction coupled to gas chromatographic-mass spectrometric determination can be an adequate method for the speciation analysis of methyltin compounds in aqueous solutions. The proposed technique is fast, reliable and environment-friendly as it consumes only 20 μL of the extraction solvent.     

Main publications:

Smitiene, V., Semasko, I., Vickackaite, V. 2014. Speciation of methyltins by dispersive liquid-liquid microextraction and gas chromatography with mass spectrometry. Journal of Separation Science, vol. 37, 1989–1995.

Investigation of Instrumental Methods of Analysis of Environmental, Industrial, Biological and Cultural Heritage Objects. Prof. S. Tautkus.

The influence of different parameters on the absorbance of magnesium was described in this work. Acetylene and air pressure, influence of hydrochloric, sulfuric and nitric acids on the analytical signal were investigated. The linear concentration range of magnesium was 0.05–0.5 µg/ml. The detection limit of magnesium was found to be 0.02 µg/ml. Also the selectivity of magnesium determination was investigated. According to the interfering effect the examined metal ions are ordered as: Mn>Ca>Pb>Al, Bi, Cu, K, Na, Sr, Ba, Fe, Ni, Zn, Co, Cd and Cr.

The methodology for determination of magnesium in coffe and mushrooms by flame atomic absorption spectrometry after extraction by a microwave system has been suggested. The obtained results demonstrated that the suggested methodology has a good reproducibility (S_r in the range from 1.0 to 3.8%) and high precision (recovery in the range from 95 to 103%).                 

Rare Earth and Transition Metal Doped Phosphors. Assoc. Prof. A. Katelnikovas.

The synthesis of novel rare earth and transition metal ions doped phosphors and investigation of their optical properties are performed under this project. In 2014 several silicate and molybdate/tungstate inorganic materials doped with Ce³⁺, Eu³⁺, Sm³⁺ and Eu³⁺, Sm³⁺, Pr³⁺ ions, respectively, were prepared and their optical properties explored. In relation with this project an article in Optical Materials (vol. 37, p. 204–210) has been published.

National Research Projects

Research Council of Lithuania. Application of Micromembrane Devices for the Registration of Specific Antigen-Antibody Interaction (No. MIP-059/2012). Prof. A. Ramanavičienė. 2013–2014.

High frequency (40 MHz, silicon nitride surface) and low frequency (7 MHz, gold coated surface) capacitive micromachined ultrasound transducers (CMUT) modified with antigen were tested for the gravimetric detection of specific antibody. The formation of immune complexes on the surface of CMUTs was determined via resonance frequency and electromechanical resistance readings. Finite element analysis reveals that the loading of the low frequency sensors is several times larger than that on high frequency sensors. However, high frequency sensors have better mass sensitivity.

Main publications:

Virzonis, D., Vanagas, G., Ramanaviciene, A., Makaraviciute, A., Barauskas, D., Ramanavicius, A., Wen, W., Kodzius, R. 2014. Resonant gravimetric immunosensing based on a capacitive micromachined ultrasound transducers. Microchimica Acta, vol. 181, 1749–1757.

Makaraviciute, A., Ruzgas, T., Ramanavicius, A., Ramanaviciene, A. 2014. QCM-D study of reduced antibody fragments immobilized on planar gold and gold nanoparticle modified sensor surfaces. Key Engineering Material, vol.605, 340–343. 

Makaraviciute, A., Virzonis, D., Vanagas, G., Barauskas, D., Ramanaviciene, A., Ramanavicius, A. 2014. An immunosensing system for antibody detection based on CMUT resonance sensor. Sensor Letters doi:10.1166/sl.2014.3397.

European Community’s Social Foundation through the Project LAMETECH MOKSLAS under Grant Agreement no.VP1-3.1-SMM-08-K-01-004/KS-120000-1756.

Antibodies were chemically reduced to “half” antibody fragments and employed as recognition ligands on planar gold and gold nanoparticle modified surfaces of a quartz crystal microbalance with dissipation sensor. Antigen interaction with antibody fragments was investigated and compared with non-specific interaction by employing ΔD/Δf plots.

A solid phase extraction procedure for determination of zaleplon and zopiclone in low-volume human haemolysed blood using fast gas chromatography with negative-ion chemical ionization mass spectrometry has been developed and validated.

Main publications:

Makaraviciute, A., Ruzgas, T., Ramanavicius, A., Ramanaviciene, A. 2014. Antibody fragment immobilization on planar gold and gold nanoparticle modified quartz crystal microbalance with dissipation sensor surfaces for immunosensor applications. Analytical Methods, vol. 6 (7), 2134–2140. 

Karlonas, N., Ramanavicius, A.,Ramanaviciene, A. 2014. Development of a solid phase extraction for determination of zaleplon and zopiclone in haemolysed blood using fast gas chromatography with negative-ion chemical ionization mass spectrometry. Journal of Separation Science, vol. 37, 551–557.

Research Council of Lithuania. Perennial Legumes – A Value-Added Food Supplement and A Source of Functional Ingredients (SVE-14012 ). Prof. A. Padarauskas. 2014–2015.

The flavonoid compositions and concentrations in the different parts (leaf, flower and stem) of red clover cultivars were studied using ultra-high pressure liquid chromatography coupled with a diode array and a mass spectrometric detector. Biochanin A and formononetin were the predominant flavonoids in all cultivars.

Research Council of Lithuania. Study of Optical Properties And Biocompatibility of Na(Y/Gd)F₄ Nanoparticles (MIP-030/2014). Prof. G. Streckytė. 2014–2016.

In 2014 the study was focused on the investigation of various conditions for measuring up-conversion emission, kinetics and quantum yields. The obtained results will give significant improvement in up-conversion emission spectra quality and more precise determination of quantum yields.

Dr. Bronislovas Lubys Support and Charity Foundation. Design of Photochemical Reactor and Photochemical synthesis of Nanoparticles of Metal Compounds. Prof. A. Katelnikovas. 2014–2015.

The reactor suitable for photochemical synthesis of nanoparticles of metal compounds was designed and manufactured. Various synthesis conditions for CeO₂ nanoparticle formation were investigated. It was found that indium amalgam discharge lamp heats the reaction mixture to temperatures up to 70 °C, therefore, the solution for better controlling the reaction mixture temperature needs to be found. The CeO₂ nanoparticles were successfully prepared; however, the yield is quite low at the moment.

International Research Projects

Research Council of Lithuania. Lithuania-Belarus Bilateral Cooperation in Science and Technology Program Improved Glucose Biosensors Based on Immobilized Nanobiocomposites. (No. TAP LB 09/2013). Assoc. Prof. A. Kaušaitė-Minkštimienė. 2013–2014.

Several mediators were investigated in order to evaluate their ability to act as electron carriers between the redox-active centre of glucose oxidase and graphite rod electrode surface, and to compare their influence in the designed of amperometric glucose biosensor. The highest amperometric signals were observed using tetrathiafulvalene and tetrathiafulvalene-tetracyanoquinodimethane complex. The impact of amount of immobilized GOx, an optimal pH region for operation, stability and reproducibility of the analytic signal of designed biosensor using these mediators were investigated and discussed.

Main publications:

Kausaite-Minkstimiene, A., Mazeiko, V., Ramanaviciene, A., Oztekin, Y., Solak, A.O., Ramanavicius, A. 2014. Evaluation of some redox mediators in the design of amperometric glucose biosensors. Electroanalysi, vol. 26, 1528–1535.

Contractual Research

CC Fermentas, part of Thermo Fisher Scientific (Lithuania)
CC Elme metalas (Lithuania)

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

Centre for Physical Sciences and Technology (Lithuania)
CC Fermentas, part of Thermo Fisher Scientific (Lithuania)
Kaunas University of Technology (Lithuania)
State Research Institute Centre for Innovative Medicine (Lithuania)
Malmo University (Sweeden) 

OTHER SCIENTIFIC ACTIVITIES

Prof. A. Padarauskas –

• editorial board member of the journal Chemija.

DEPARTMENT OF APPLIED CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. 219 3176, fax 233 0987
E-mail:

Head - Prof. Dr. Rimantas Raudonis

STAFF

Professors: Habil. Dr. V. Daujotis, Dr. R. Raudonis, Dr. J. Senvaitienė (part-time), Dr. V. Kairys (part-time).
Associate professors: Dr. E. Garškaitė, Dr. R. Vaitkus (part-time), Dr. S. Šakirzanovas, Dr. A. Žalga.
Lecturers: Dr. Kiuberis, Dr. D. Ragauskienė (part-time), Dr. Ž. Stankevičiūtė, Dr. R. Voronovič (part time).
Research fellows: Dr. E. Garškaitė (part-time), Dr. S. Šakirzanovas (part-time).
Doctoral students: Y. Barushka, G. Braziulis, S. Kareiva, E. Kielė, J. Raudonienė, D. Sakalauskas, A. Zolumskis, D. Baziulytė, A. Pulmanas, P. Ušinskas.

RESEARCH INTERESTS

Nanoparticle synthesis and film deposition for biomaterials, water cleaning, antifouling surfaces, optoelectronics.
Interfacial liquid properties and development of techniques for their measurements
Solid state materials. Synthesis and characterization of different molybdates
Application of polymers for cultural heritage conservation

RESEARCH PROJECTS CARRIED OUT IN 2014

Projects Supported by University Budget 

Synthesis and Investigation of Novel Materials and Nanostructures, Development of Analysis Methods

Electrochemical Adsorption. Prof. V. Daujotis. 2011–2015.

The measured potential dependences of the velocity of the flow of aqueous solutions past the gold coated spheres correlate with our earlier reported potential dependences of drag force on these spheres. Flow velocity maxima (~0.05% of average velocity) are observed near the potentials of drag force minima. Small increase of velocity is not in contradiction with earlier found rather significant change of drag force the sphere.  It is reasonable to conclude that the increase of flow velocity is most pronounced within the thin solution layer at the sphere surface. This local increase of velocity should be much higher than the measured average velocity of the flow through the tube. Our earlier reported decrease in interfacial viscosity during positive potential scan, which has been calculated from measured drag force via empirical relationship between drag force coefficient and dynamic viscosity, should be considered as to some extent overestimated.  The used relationship does not account for interdependence of frictional and pressure drags. However, it is not possible to correct interfacial viscosity calculations as there is no quantitative theory for sphere drag in turbulent flow. For this reason, the decrease of interfacial viscosity by ~0.5 % at minimum, obtained by using piezoelectric resonator method, should be considered as more reliable. Our results show that the changes of interfacial layer properties, induced by applied potential, extend beyond the interface and can result in the bulk effects such as the change of wall-bounded flow velocity.

Main publication: 

Plaušinaitis, D., Pulmanas, A., Kubilius, V., Raudonis, R., Daujotis, V. 2014. Properties of an interfacial solution layer at gold electrode surface in perchlorate and chloride solutions: piezoelectric resonator and dragforce study. Electrochimica Acta, vol. 121, 278–284.

Upconverting Nanoparticle Synthesis.  Assoc. Prof. S. Sakirzanovas. 2013–2016.

Dr. Bronislovas Lubys Support and Charity Foundation. Project Construction of Supercritical Dryer and Synthesis of Aerogel Materials. 2014.

The main purpose is design and construction of fully automated reactor for supecrytical drying of materials. The major specification for prototype unit: working pressure up to 150 bar, temperature up to 400 °C, programmable control of pressure reduction. The main goal was successfully implemented; 800 ml volume unit was tested to withstand 200 bar at 450 °C. Main parameters are digitally controlled and system logged all sensor data during run. Project is extended to elaborate the procedures for silica aerogel synthesis directly from alcohol medium.

Project funded byResearch Council of Lithuania Study of Optical Properties and Biocompatibility Oo Na(Gd/Y)F4 Nanoparticles. 2014–2016.

Fluoride based nanoparticles exhibit higher upconversion efficiency compared to oxide materials. Reliable and repeatable fluoride nanoparticle synthesis procedure was prepared. By trifluoroacetate salt thermal decomposition method particle size is controllable in the range of 12 to 60 nm. Scanning electron microscope images show highly monodisperse samples. In order to simplify synthesis procedure and make it more environmentally friendly the starting materials were changed to chloride salts. Essentially method remains the same; however the emission of very corrosive hydrofluoric acid is omitted; the improvement benefit is cheaper starting materials and usage of common laboratory glassware. It is expected that lanthanide doped sodium gadolinium fluoride nanoparticles will be suitable for multimodal imaging of biomaterials, upconversion phenomena adaptation for cell structure studies while gadolinium can act as contrast agent in MRI imaging.

Materials Synthesis and Their Film Deposition with Applications for Renewable Energy Technologies. Assoc. Prof. E. Garskaite.

Research description:synthesis of Cu₂O, Ag₃PO₄ and biomaterials (hydroxyapaptite), SnO₂ nanostructuring.SnO₂ nanostructures were made by combining a sol-gel and hard templating method. Prepared nanostructures were investigated with FE-SEM, XRD and HRTEM. Cu2O films were deposited by modified Fehling reaction

Participation at the international conference Advanced Materials and Technologies, 2014, August 27–31, Posters “Hydrogen production through splitting of water: deposition of Cu₂O microspheres and crystals on FTO/ITO glass” and “Templated SnO₂ nanostructures produced by sol-gel method”.

Investigation of the Comoposition of Historical Sealing-wax in Manuscripts Collection and Assessment of the Restoration Compounds. Dr. D. Ragauskiene.

This study was focused on the composition of seals in manuscripts dated from 16th to 19 th century and collected in Wroblewski Library of the Lithuanian Academy of Sciences. Binding medium of the seals was identified using ATR-FTIR spectroscopy. Elemental composition was investigated by SEM-EDX analysis in order to detect pigments and fillers. Besides soft wax seals hard sealing-wax from shellac-colphony-Venice turpentine compounds were found as well as semi-soft seals from wax and resins mixtures, even flour wafer or starch paste seals. The restoration compounds were prepared by the recipes of the historical sealing-wax using shellac, Venice turpentine, colophony, paraffin, dammar and beeswax. Standard materials and models of the seals were tested under two kinds of accelerated ageing conditions: cycling of relative humidity/temperature and photochemical ageing under UVA irradiation. After accelerated ageing the changes in the samples were evaluated using ATR-FTIR spectroscopy and evaluating compressive tests. The restoration compounds were made from paraffin-dammar and beeswax-paraffin (in various ratios) with fillers, such as kaolin, chalk, and without them. It was discovered that restoration compounds from paraffin-dammar were more ageing-resistant under UV irradiation than analogue compounds from beeswax-dammar mixture.

Investigation of Bookbindings and the Components of The Books Printed in 17^th Century Lithuania. Dr. D. Ragauskiene.

The purpose of this study was threefold: to select methods of analysis in order to identify classes of tannins (hydrolisable and condensed) in new-made and historical vegetable-tanned leather; to identify main components of the books printed and bound in 17^th century Lithuania; to confirm binding period and territory of the selected books. Several methods were used:microchemical and SEM-EDX analysis, ATR-FTIR and Raman spectroscopy, TGA, optical microscopy and pH measurements. It was found that both microchemical analysis and ATR-FTIR spectroscopy allow identifying the classes of vegetable tannins. Classes of tannins were clarified in selected plants: galottannin found in the leaf of sumac, ellagitannin found in gallonuts of oak tree and condensed tannin found in the seeds of grapes and mimosa tree. Vegetable tanning was detected in bookbinding of six books; classes of tannins were identified as well. Galottannins were discovered in three books, ellagitannins found in two books and condensed tannin was detected in one book. Deterioration of three parchment bookbinding were influenced by calcium sulphate converted from calcium carbonate and both easily distinguished by Raman spectroscopy method.

Project supported by the Ministry of Culture The Individual Plan of Museum for Preventive Conservation. Dr. D. Ragauskiene.

Project partner: Department of Museology, Faculty of Communication, Vilnius University (Assoc. Prof. Dr. Arūnas Puškorius)

Selected museums implemented the monitoring of microclimate conditions: mainly temperature and relative humidity. The group of experts assessed obtained results, determined illuminance and UV irradiation, sources of air pollutants and effects on museum objects, pest management and control strategies, detected suitable and harmful materials for storage and exhibition.

Reports were completed for Birštonas, Kaišiadorys, Molėtai Museums and Open Air Museum of Lithuania.

Synthesis of Calcium Phosphates by Sol-gel Method. Z. Stankeviciute.

Synthesis of calcium phosphate powders and coatings on titanium, silica and fused silica substrates performed applying sol-gel method.

Main publications:

Trinkūnaitė, J., Stankevičiūtė, Ž., Yang Jen-Chang, C-K.Yang Thomas,  Beganskienė, A., Kareiva, A. 2014. Calcium hydroxyapatite/whitlockite obtained from dairy products: Simple, environmentally benign and green preparation technology. Ceramics International, vol. 40, iss. 8, part B, 12717–13722.

Malakauskaite, M., Stankevičiūtė, Ž., Beganskienė, A., Kareiva, A. 2014. Sol-gel synthesis of calcium hydroxyapatite thin films on quartz substrate using dip-coating and spin-coating techniques. Journal of Sol-gel Science and Technology, vol. 71, iss. 3, p. 437–446.

Gross, K. A.,Kalnina, D., Stankeviciute, Z., Nikolajeva, V. 2014. Charge state of silver halide colloids determines the antibacterial activity in amorphous calcium phosphate. Key Engineering Materials, vol. 587, p. 74–79.

National Research Projects

Project of the Research Council of Lithuania Encouragement of Students’ Scientific Activities “Mixed metal oxide garnet synthesis and investigation”

Project of the Research Council of Lithuania Encouragement of Students’ Scientific Activities “Hydrothermal synthesis of inorganic materials and their characterization”

Project of the Research Council of Lithuania Encouragement of Students’ Scientific Activities “Linas Sinkevicius „Ag₃PO₄ coatings and analysis - hydrogen production via water splitting” 

Project of the Research Council of Lithuania Encouragement of Students’ Scientific Activities “Synthesis and characterization of rare-earth metal molybdates”

Project of the Research Council of Lithuania Encouragement of Students’ Scientific Activities “Synthesis of new materials for SOFC applications”.

Contractual Research

Synthesis and Characterization of Alkaline Earth Metal Molybdates (contribution: LamaTech project). Dr. A. Zalga.

Main publications:

Stankeviciute, R., Zalga, A. 2014. Sol-gel synthesis, crystal structure, surface morphology and optical properties of Eu₂O₃ doped La₂Mo₃O₁₂ ceramic. Journal of Thermal Analysis and Calorimetry, vol. 118, 925–935.

Braziulis, G., Janulevicius, G., Stankeviciute, R., Zalga, A. 2014. Aqueous sol-gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors, Journal of Thermal Analysis and Calorimetry, vol. 118, 613–621.

Braziulis, G., Stankeviciute, R., Zalga, A. 2014. Sol-gel derived europium doped CaMoO₄:Eu³⁺ with complex microstructural and optical properties. Medžiagotyra, vol. 20, 90–96.

National Grant of the Research Council of Lithuania Development of YSZ and GDC Thin Films on Silicon, Silica and Corundum Substrates (contribution: Technological Processes of Membranes production for Micro-Solid Oxide Fuel Cells (MIKROKOKE-2). 

Main publications:

Zalga, A., Kareiva, A., Zarkov, A., Tautkus, S., Abakeviciene, B. 2014. UV-Vis spectroscopical investigations of the YSZ thin films on corundum, silicon and silica substrates. Chemija, vol. 25, 29–33.

Characterization of SnO₂ Nanostructures (contribution: COST Project, Action MP1202 “Rational design of hybrid organic-inorganic interfaces: the next step towards advanced functional materials”; STSM at the Imperial College London, UK). Dr. E. Garskaite.

Biomaterials (Hydroxyapatite) Synthesis and Characterization (contribution: LaMaTech project). Dr. E. Garskaite.

Main publications:

Garskaite, E., Gross, K. A., Sung-Wei Yang, Thomas Chung-Kuang Yang, Jen-Chang Yang, Kareiva, A. 2014. Effect of processing conditions on crystallinity and structure of carbonated calcium hydroxyapatite (CHAp). CrystEngComm, vol. 16, 3950. 

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

Telemark University College, Porsgrunn (Norway)
Leibniz Institute of Photonic Technology (IPHT), Jena (Germany)
National Cancer Institute, Vilnius (Lithuania)

DEPARTMENT OF INORGANIC CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. 219 3110, fax 233 0987
E-mail:

Head – Prof. Habil. Dr. Aivaras Kareiva

STAFF 

Professors: Habil. Dr. A. Abrutis, Habil. Dr. J. Barkauskas, Habil. Dr. A. Beganskienė, Habil. Dr. R. Juškėnas (part-time), Habil. Dr. A. Kareiva, Dr. A. Selskis (part-time).
Associate professors: Dr. D. Jasaitis, Dr. V. Kubilius, Dr. V. Plaušinaitienė.
Lecturers: Dr. I. Grigoravičiūtė-Puronienė (part-time), Dr. R. Skaudžius, J. Pilipavičius (part-time).
Research fellows: Dr. I. Bogdanovičienė, Dr. Z. Šaltytė, Dr. A. Stanulis.
Doctoral students: A. Jankevičiūtė, J. Trinkunaite Felsen, O. Darčanova, J. Pilipavičius, S. Butkutė, M. Liubinienė, M. Malakauskaitė, M. Misevičius, A. Ežerskytė-Misevičienė, A. Laurikėnas, O. Opuchovič, D. Sokol, J. Gaidukevič, E. Gražėnaitė, V. Jonauskė, L. Pavasarytė. 

RESEARCH INTERESTS

Developments of metal-organic chemical vapour deposition technique for oxide films. 
Dielectric, ferroelectric and piezoelectric materials
Magnetic and magnetoresistant materials
Transparent conducting oxides
Conservation of cultural heritage

Synthesis of metal, semiconductors and upconversion nanoparticles

New materials for conservation and preservation of cultural heritage
Synthesis and characterization of graphene and other nano-structured carbonaceous materials
Synthesis of graphene membranes
Synthesis and applications of silica nano-particles
Synthesis and characterization of inorganic-organic hybrid materials
Sol-gel synthesis and investigations of advanced nano-materials (bioceramic, optical materials)
Surfaces and interfaces 

RESEARCH PROJECTS CARRIED OUT IN 2014

Projects Supported by University Budget

New Functional Materials and Chemical Compounds: Synthesis, Self-Order and Investigation of Properties 

1. Synthesis of Functional Oxide Films and Heteroepitaxial Structures by MOCVD (Metalorganic Chemical Vapour Deposition).  Prof. A. Abrutis. 2011–2020.
2. Synthesis and Characterization of Polycrystalline and Amorphous Materials.  Prof. A. Beganskienė,Prof. A. Kareiva and Prof. J. Barkauskas. 2011–2020.

Synthesis of graphite oxide using different oxidizing agents, preparation of graphite oxide membranes on polymer, glass and metal substrates, graphene membranes on polymer, glass and metal substrates were performed as well as examination of graphite oxide and graphene membranes. Transfer of graphene membranes and coatings. Films of magnetoresistant, piezoelectric, ferroelectric and high-k dielectric materials were deposited by metal-organic chemical vapour deposition (MOCVD) technique and their properties were studied. Effect of deposition conditions on the stoichiometry and structural properties of films was investigated. Deposition and annealing conditions for crystalline high-k dielectric films were established and deposited films were tested in metal-insulator-metal capacitors. Investigations have been focused on the synthesis and characterization of the novel upconversion nanoparticles. Alakline earth metal compounds and nano-derivatives were prepared by using co-precipitation or sol-gel synthesis methods. It was demostrated that nanoparticles prepared by sol-gel method were nano size and penetrated into the cellulose fibers and then attach to them. New sol-gel methods for the preparation of calcium phosphate/hydroxyapatite thin films on different substrates using dip- and spin-coating techniques have been developed. An amorphous CHAp was prepared by the modified sol-gel processing route. New ceramic pigments have been synthesized using an environmentally benign aqueous sol-gel chemistry technique.

Main publications:

Klimavicius, V., Kareiva, A., Balevicius, V. 2014. Solid-state NMR study of hydroxyapatite containing amorphous phosphate phase and nanostructured hydroxyapatite: Cut-off averaging of CP-MAS kinetics and size profiles of spin clusters. J. Phys. Chem. C., vol.118, 28914−28921.

Gražėnaitė, E., Kiuberis, J., Beganskienė, A., Senvaitienė, J., Kareiva, A. 2014. XRD and FTIR characterisation of historical green pigments and their lead-based glazes. Chemija, vol.25, 199–205. 

Projects, Programmes, Issues Supported by Research Council of Lithuania

Transparent Conducting Oxide Films for Applications in UV and IR Optoelectronics (No. MIP-023/2013).Prof. A. Abrutis. 2013–2015.

Technological Processes of Membranes Production for Micro-Solid Oxide Fuel Cells(MIKROKOKE-2). National Grant of Research Council of Lithuania. Prof. A. Kareiva.2012–2014.

European Social Fund under National Integrated Programme Biotechnology and Biopharmacy (BIOTEFA). National Research Project. Funding Agency - MITA (VP1-3.1-SMM- 08-K01-005). Prof. J. Barkauskas. 2012–2015.

Sol-Gel Synthesis, Characterization and Application in Modern Technologies of Hybrid Organic-Inorganic Nanomaterials. National Grant of Research Council of Lithuania for Posdoctoral studies. (SF-PD-2012-12-31-0397). Prof. A. Kareiva.2013–2014.

Preparation and Characterization of New Nanocoatings of Calcium Hydroxyapatite for Medical and Biotechnological Application. National Grant of Research Council of Lithuania for Posdoctoral studies. (SF-PD-2012-01-16-0294). Prof. A. Kareiva.2013–2014.

Main publications:

Trinkunaite-Felsen, J., Stankeviciute, Z. , J. C. Yang, Thomas C. K. Yang, Beganskiene, A., Kareiva, A. 2014. Calcium hydroxyapatite/whitlockite obtained from dairy products: simple, environmentally benign and green preparation technology. Ceram. Int., vol. 40, 12717–12722.

Malakauskaite-Petruleviciene, M., Stankeviciute, Z., Beganskiene, A., Kareiva, A.  2014. Sol-gel synthesis of calcium hydroxyapatite thin films on quartz substrate using dip-coating and spin-coating techniques. J. Sol-Gel Sci. Technol, vol. 71, 437–446.

Prichodko, A., Jonauske, V., Cepenko, M., Beganskiene, A., Kareiva, A. 2014.  Sol-gel derived two-dimensional nanostructures of calcium phosphates. Adv. Sci. Technol, vol. 91, 13–18.

International Science Programmes and Projects

European Network on Smart Inorganic Polymers. COST action CM1302. Prof. J. Barkauskas. 2013–2015. 

Rational Design of Hybrid Organic-inorganic Interfaces: the Next Step towards Advanced Functional Materials. COST Project (Action MP1202). Prof. A. Kareiva.2012–2016.

Main publications:

Misevicius, M., Kilmanas, M., Culunlu, S., Sakirzanovas, S., Morkan, A. U., Beganskiene, A., Kareiva, A. 2014. On the sol–gel fabrication and characterization of undoped and cerium-doped Sr₄Al₁₄O₂₅. J. All. Compd., vol. 614, 44–48.

Kiele, E., Lukseniene, J., Griguceviciene, A., Selskis, A., Senvaitiene, J., Ramanauskas, R., Raudonis, R., Kareiva, A. 2014. Methyl–modified hybrid organic-inorganic coatings for the conservation of copper.  J. Cult. Herit., vol.15, 242–249.

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

IHP GmbH, Frankfurt am Oder (Germany)
University Henri Poincare, Institut Jean Lamour, Vandœuvre-lès-Nancy (France)
Department of Inorganic Chemistry, Masaryk University, Brno (Czech Republic)
Department of Analytical and Inorganic Chemistry, Tallinn University of Technology (Estonia)
Department of Inorganic Chemistry, University of Tubingen (Germany)
Department of Inorganic Chemistry, Charles University of Prague (Czech Republic)

OTHER SCIENTIFIC ACTIVITIES

Prof. A. Kareiva –

• member of Lithuanian Academy of Sciences;
• editorial board member of the Chemine Technologija (Chemical Technology);
• deputy editor of the journal Chemija (Chemistry);
• member of Council of Alytus College;
• Chairman of Chemistry Section of Lithuanian Academy of Sciences;
• deputy Chairman of the Department of Mathematics, Physics and Chemistry of Lithuanian Academy of Sciences;
• scientific council member of the Centre for Physical Sciences and Technology.
• Honorary Professor of the International Chair at National Taipei University of Technology, Taiwan (2012–2014). 

DEPARTMENT OF ORGANIC CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. +370 5 219 3197, fax 233 0987
E-mail:

Head - Prof. Habil. Dr. Sigitas Tumkevičius

STAFF

Professors: Habil. Dr. E. Butkus (part-time), Dr. I. Čikotienė (part-time), Habil. Dr. S. Tumkevičius. 
Professor Emeritus: Habil. Dr. P. Vainilavičius.
Associate professors: Dr. A. Brukštus, Dr. M. M. Burbulienė (part-time), Dr. I. Čikotienė (part-time), Dr. V. Jakubkienė (part-time), Dr. V. Masevičius, Dr. E. Orentas (part-time), Dr. S. Stončius (part-time), Dr. A. Žilinskas.
Lecturer: Dr. J. Dodonova.
Research fellows: Dr. M. M. Burbulienė (part-time), Dr. V. Jakubkienė (part-time).
Doctoral students: J. Bucevičius, T. Javorskis, I. Karpavičienė, K. Karpavičius, D. Račkauskaitė, R. Rimkus,

RESEARCH INTERESTS

Enantioselective synthesis of polycyclic molecules
Organocatalysts for asymmetric synthesis
Metal-catalyzed organic reactions
Self-assembly of organic molecules
Heterocyclic chemistry
Synthesis of supramolecular structures based on chiral bicyclic frameworks fused with heteroaromatic fragments
Design, synthesis and transformations of novel nitrogen, oxygen and/or sulphur heterocycles, their functional derivatives and structural analogs of natural compounds
Chiroptical properties
Light-emitting organic materials
Charge-transporting organic materials
Biological activity of organic compounds
Crystal engineering
X-ray diffraction
NMR, FTIR, Raman, UV, CD spectroscopy of organic compounds
Quantum chemical methods

RESEARCH PROJECTS CARRIED OUT IN 2013

Projects Supported by University Budget

Synthesis of Functional Heteroaromatic Materials and Investigation of their Optical and Biological Properties. Prof. S.Tumkevičius. 2014–2020.

A highly effective methods for the synthesis of 2,4,7-trisubstituted pyrrolo[2,3-d]pyrimidines by a combination of nucleophilic substitution, Pd(0) catalyzed Suzuki and N-arylation reactions were developed. Pd(II) catalyzed C-H alkenylation of pyrrolo[2,3-d]pyrimidine was investigated. A series of benzenesulfonamide derivatives, bearing benzimidazole moieties, were designed and synthesized. Some of these compounds exhibited nanomolar affinities and selectivity toward the CA isozymes tested. 

Main publications:

Zubrienė, A., Čapkauskaitė, E., Gylytė, J., Kišonaitė, M., Tumkevičius, S., Matulis, D. 2014. Benzenesulfonamides with benzimidazole moieties as inhibitors of carbonic anhydrases I, II, VII, XII and XIII. J. Enz. Inhib. Med. Chem., vol. 29, no. 1, 124–131.

National Research Projects

Projects, Programmes, Issues Supported by the Research Council of Lithuania:

Novel Functional Pyrrolopyrimidines: Synthesis and Photophysical Properties. Project No. MIP-027/2013. Prof. S. Tumkevicius. 2013–2015.

A series of new 4,4-dialkyl- and 4,4-diaryl-4H-indeno[1,2-b]thiophenes and their 2-bromo derivatives were synthesized and characterized. The developed methods were shown to be efficient for the preparation of the title compounds in a multigram scale. An efficient regioselective Pd-catalyzed direct arylation of 2,4-diaryl-7-methylpyrrolo[2,3-d]pyrimidines with aryl bromides has been developed. The procedure tolerates many functional groups and allows to generate a wide library of novel pyrrolo[2,3-d]pyrimidine derivatives.

Main publications:

Dodonova, J., Tumkevicius, S. 2014. An access to 6-arylpyrrolo[2,3-d]pyrimidines via palladium-catalyzed direct C-H arylation reaction. RSC Adv., vol.4, 35966–35974.

Bucevicius, J., Adomenas, P., Tumkevicius, S. 2014. Synthesis of novel 4,4-dialkyl- and 4,4-diarylindeno[1,2-b]-thiophenes and their 2-bromo derivatives. Chem. Heterocycl. Comp., vol. 50(10), 1413–1420.

Synthesis of Chiral Synthons and Application in Supramolecular Chemistry and Organocatalysis.Global Grant Project No. VP1-3.1-šmm-07-k-01-030. Research Leader: Dr. S. Stončius. 2011–2015.

The chiroptical properties of enantiomerically pure bicyclo[3.3.1]nona-2,6-diene-2,6-dicarbonitrile, and related acids were studied and evidence for transannular through-space interaction and non-exciton-type coupling between the two unsaturated moieties was obtained by circular dichroism spectroscopy and DFT calculations. A method for the synthesis of chiral C₂-symmetric pyridine and 2,2’-bipyridine N-oxide derivatives, a potential Lewis-basic organocatalysts, from enantiomerically pure bicyclo[3.3.1]nonane-2,6-dione has been developed.

Main publications:

Bagdžiūnas, G., Butkus, E., Stončius, S. 2014. Homoconjugation vs. Exciton Coupling in Chiral α,β-Unsaturated Bicyclo[3.3.1]nonane Dinitrile and Carboxylic Acids. Molecules, vol. 19, 9893–9906.

Two Channel Photosystem Based on Tubular Supramolecular Polymer. Global Grant Project No. VP1-3.1-ŠMM-07-K-03-007. Research Leader Dr. E. Orentas. 2013–2015.

New type of supramolecular polymers based on the aggregation of hydrogen bonded cyclic tetramers was developed and characterized. The supramolecular monomer possesing electron rich indole moeity was shown to be essential to guide the aggregation process via unconventional tautomeric form of ureidopyrimidinone. The results obtained indicated that the polymerization process is induced by C₇₀ molecule templation. The inclusion polymers having very good electron conducting guest fullerenes will be used for the construction of organic solar cell.

Main publications:

Butkus, E. 2014. The Favorskii Rearrangement (extend to rings). In Gary A. Molander and Paul Knochel (eds.), Comprehensive Organic Synthesis, 2nd Edition, vol 3, 853–886.

Kažemėkaitė, M., Talaikytė, Z., Butkus, E., Razumas, V. 2014. Synthesis and enzymatic resolution of methyl ferrocenylpentanoate using Thermomyces lanuginosus lipase for construction of ferrocene alkyl thiols. Chemija, 219–224.

An Integrated Discovery of Novel Anti-Cancer Compounds: from Fundamental Researches to Purposeful Modeling and Synthesis. Global Grant Project Nr. VP1-3.1-ŠMM-07-K-01-002. Dr. I. Čikotienė. 2011–2015.

The Kabachnik-Fields reactions of various carbocyclic or heterocyclic acetylenic aldehydes together with subsequent Lewis acid catalyzed cyclizations have been studied. It was found that 5-exo-dig versus 6-endo-dig cyclization mode strongly depends on the structure of starting materials. An electrophile-induced rearrangement of propargylic esters were shown to proceed either via classical alkyne-carbonyl metathesis route or via nucleophilic addition-rearrangement cascade. The products of these reactions can be Morita-Baylis-Hillman adducts (MBHA) or thermodynamically more stable (E)- and (Z)-α,β-unsaturated ketones.

Main publications:

Bukšnaitienė, R., Urbanaitė, A., Čikotienė, I. 2014. Formation of condensed 1H-pyrrol-2-ylphosphonates and 1,2-dihydropyridin-2-ylphosphonates via the Kabachnik-fields reaction of acetylenic aldehydes and subsequent 5-Exo-dig or 6-Endo-dig cyclizations. J. Org. Chem., vol. 79, 6532–6553.

Trujillo, C., Sánchez-Sanz, G., Karpavičienė, I., Jahn, U., Čikotienė, I., Rulíšek, L. 2014. Divergent pathways and competitive mechanisms of metathesis reactions between 3-arylprop-2-inyl esters and aldehydes: an experimental and theoretical study. Chem. Eur. J., vol. 20, (33), 10360–10370.

Čikotienė, I. 2014. Rearrangements of propargylic esters can be induced by some electrophiles. Org. Lett., vol. 16, 2260–2263.

Research Council of Lithuania. Design of Perspective Materials for Application as Semiconductors and in Nano-Technologies and their Characterization by Methods of Steady State and Ultrafast Spectroscopy in a Wide Spectral Range. (No. VP1-3.1-ŠMM-08-K-01-004/KS-120000-1756). Research leader of the Project group: Prof. S. Tumkevičius. 2012–2014.

 

Optical properties of novel 4,7-diaryl- and 2,4,7-triarylpyrrolo[2,3-d]pyrimidines were assessed by performing absorption and fluorescence spectroscopy, fluorescence quantum yields and lifetimes measurements. Influence of structure peculiarities and solvent polarity on the photoluminescence properties of the synthesized compounds was studied. Most of the studied compounds showed positive solvatofluorochromism.

International Research Projects

Bilateral cooperation in scientific research and experimental development in Lithuanian and French integrated action program “Gilibert” project Cyclodextrins – Supramolecular Organocatalysts for the Synthesis of Substituted Pyrrolo and Pyrazolopyrimidines by Multicomponent Reactions. Project no. TAP LZ 08/2013. Research Leader: Prof. S. Tumkevicius. 2013–2014.

A new and efficient catalytic protocol has been developed to synthesize N-substituted pyrrole derivatives in high yield by Paal-Knorr condensation using RAME--CD as catalyst. The method is versatile and can be applied to a range of ketones, including hindered ketones. The mild reaction conditions allow unsymmetrical bis-pyrrole derivatives to be synthesized. Novel Pd(II) complexes coordinated by N,N-bidentate ligands derived from cyclodextrins have been synthesized by copper-catalyzed azide alkyne 1,3-cycloaddition reaction.

Main publications:

Menuel, S., Rousseau, J., Rousseau, C., Vaiciunaite, E., Dodonova, J., Tumkevicius, S., Monflier, E. 2014.  Access to Pyrrole in Water by Methylated Cyclodextrins Assistance. Eur. J. Org. Chem., 4356–4361.
Potier, J., Menuel, S., Rousseau, J., Tumkevicius, S., Hapiot, F., Monflier, E. 2014.  Multifunctional cyclodextrin-based N,N-bidentate ligands for aqueous Heck arylation. Applied Catalysis A: General, vol.479, 1–8.

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

Centre for Physical Sciences and Technology (Lithuania)
Lund University (Sweden)
La Laguna University (Spain)
Jyvaskyla University (Finland)
D’Artois University (France)

OTHER SCIENTIFIC ACTIVITIES

Prof. E. Butkus –

• organic chemistry section editor of the international journal Central European Journal of Chemistryhttp://chemistry.cesj.com;
• editorial board member of the journal Chemija (Chemistry), http://www.lmaleidykla.lt/publ/0235-7216/2013/3/TitulinisRedkolegija.pdf;
• member of the EU program committee of the FP7 Ideas program;
• member of the Lithuanian Academy of Sciences;
• member of the organising committee of the international conference onorganic synthesis Balticum Organicum Syntheticum 2014.

Prof. S. Tumkevičius –

• editorial board member of the journal Chemija (Chemistry),http://www.lmaleidykla.lt/publ/0235-7216/2013/3/TitulinisRedkolegija.pdf;
• editorial board member of the international journal Chemistry of Heterocyclic Compounds, http://www.springer.com/chemistry/organic+chemistry/journal/10593?detailsPage=editorialBoard .

DEPARTMENT OF PHYSICAL CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. 233 7517, 219 3114, fax 233 0987
E-mail:

Head - Prof. Habil. Dr. Arūnas Ramanavičius

STAFF

Professors: Habil. Dr. A. Ramanavičius, Dr. H. Cesiulis, Habil. Dr. A. Malinauskas (part-time), Habil. Dr. R. Ramanauskas (part-time).
Associate professors: Dr. A. Valiunienė, Dr. D. Plausinaitis, Dr. R. Valiūnas (part-time).
Lecturers: Dr. Z. Margaian, Dr. I. Balevičiūtė.
Doctoral students: E. Vernickaitė, L. Mikoliunaitė, L. Pukaitė, L. Dedelaitė, I. Vilkončienė, U. Bubnienė, A. Alubeckas.

RESEARCH INTERESTS

Biosensors
Biofuel cells
Bioelectrochemistry
Electrooxidation of cyanides
Investigation of the electrodeposition and properties of obtained tungsten- and molybdenum-containing alloys
Electrochemical treatment of titanium, tungsten
Photoelectrochemistry
Scanning electrochemical microscopy
Ellipsometry
Surface plasmon resonance

RESEARCH PROJECTS CARRIED OUT IN 2014

Projects Supported by University Budget

New Functional Materials and Chemical Compounds: Synthesis, Self-Order and Investigation of Properties.

Development of Electroanalytical Systems. Prof. A. Ramanavičius. 2011–2015.

Oortho-quinoidal compounds, 1,10-phenanthroline-5,6-dione (PD) and 9,10-phenanthrenequinone (PQ), were examined as electron transfer mediators suitable for amperometric glucose biosensors. The dependences of the electrochemical responses of PD- and PQ-based amperometric glucose biosensors on varied concentrations of glucose were investigated under aerobic and anaerobic conditions. The PD-modified graphite rod (GR) electrode revealed a current response seven times higher than that of the PQ-modified GR electrode. The reactivity indices of orthoquinoidals assessed by means of B3LYP functional method applying 6-311G(D) basis set showed that the electronaccepting potency for PD was markedly higher as compared with that of PQ. Compared to PQ, considerably higher reactivity of PD has been defined in the reactions with NADP+-ferredoxin reductase (FNR, EC 1.18.1.2) as a model singleelectron transfer FAD-dependent enzyme, which provided an additional evidence for PD as a more efficient mediator compared to PQ. This study illustrates that PD can be applied as a redox mediator for glucose oxidase and it could be more suitable for a reagent-less biosensor design than PQ.

Main publications:

Krikstolaityte, V., Barrantes, A., Ramanavicius, A., Arnebrant, T., Shleev, S., Ruzgas, T. 2014. Bioelectrocatalytic reduction of oxygen at gold nanoparticles modified with laccase Bioelectrochemistry. Bioelectrochemistry,vol.  95, 1–6.

Zor, E., Oztekin, Y., Mikoliunaite, L., Voronovic,  J., Ramanaviciene, A., Anusevicius,  Z., Bingol, H., Ramanavicius, A. 2014. 1,10-Phenanthroline-5,6-dione and 9,10-phenanthrenequinone as redox mediators for amperometric glucose biosensors. Journal of Solid State Electrochemistry, vol. 18, 1529–1536.

Abou Chaaya, A., Viter, R., Baleviciute, I., Bechelany, M., Ramanavicius, A., Gertnere, Z., Erts, D., Smyntyna, V., Miele, P. 2014. Tuning Optical Properties of Al2O3/ZnO Nanolaminates Synthesized by Atomic Layer Deposition. Journal of Physical Chemistry C, vol. 118, 3811−3819.

Investigation of the Interfacial Processes. Prof. H. Cesiulis. 2011–2015.

Piezoelectric resonator and drag force measurements show a decrease of interfacial viscosity of perchlorate and chloride aqueous solutions during polarization of gold electrode towards potential of zero charge. Though more noisy, drag force measurements have the advantage over piezoelectric technique as the former is insensitive to potential dependent adsorption, which causes distortion of data on liquid properties obtained from piezoelectric resonator measurements at more positive potentials.

In order to be applied in flip-chip technology, barrier layers should be void-free and uniformly deposited on the entire area of a die to ensure high reliability and high performance of wafer bump-solder interface. To meet these requirements, a set of potentiostatic and galvanostatic electrodeposition was carried out from a citrate electrolyte, at pH 5 and at room temperature. The tests done confirm that void-free Co-W bumps with a uniform tungsten content along the bump can be obtained by potentiostatic and galvanostatic electrodeposition.

On the mechanically polished semi-bright Ti substrates the continuous TiO2 films are formed, whereas ordered nanoporosity is formed on the mirror-like surface of Ti substrate at temperatures of 10-20 degrees C in the H3PO4 electrolyte with NH4F. The photocurrents and photopotentials are affected by the amount of fluorine in the electrolyte and consequently in the deposit.

Main publications:

Tsyntsaru, N., Kaziukaitis, G., Yang, C., Cesiulis, H., Philipsen, H. G. G., Lelis, M., Celis, J.-P. 2014. Co-W nanocrystalline electrodeposits as barrier for interconnects. J Solid State Electrochem, vol. 18, 3057–3064.

Plausinaitis, D., Pulmanas, A., Kubilius, V., Raudonis, R., Daujotis, V. 2014. Properties of an interfacial solution layer at gold electrode surface in perchlorate and chloride solutions: piezoelectric resonator and drag force study. Electrochimica Acta, vol. 121, 278–284

Cesiulis, H., Maliar, T., Tsyntsaru, N., Wenger, F., Ponthiaux, P., Podlaha, E. 2014. Anodic titanium oxide films: photoelectrochemical and tribocorrosion behaviour. Journal of Nanoelectronics and Optoelectronics, vol. 9, 1–6.

National Research Projects 

European Social Fund Agency Materials for High Technologies (in corpore with the Department of Organic Chemistry and Department of Polymer Chemistry). 2011–2014.

The ordered nanoporous arrays on Ti are formed on the extremely smooth surface, therefore convenient electrochemical polishing procedure of Ti was created. The photoelectrochemic al properties of oxidized Ti were studied. Nanoporous arrays and micro-templated were filled up electrochemically by Co-W alloys and composition of Cu/Co-W/Sn. Electrical properties of electroformed devices were determined.

Main publications:

Tsyntsaru, N., Cesiulis, H., Pellicer, E., Celis, J.-P., Sort, J. 2013. Structural, magnetic, and mechanical properties of electrodeposited cobalt-tungsten alloys: intrinsic and extrinsic interdependencies. Electrochim. Acta, vol. 104, 94–103.

Tsyntsaru, N., Kaziukaitis, G., Yang, C., Cesiulis, H., Philipsen, H. G. G., Lelis, M., Celis, J.-P. 2014. Co-W nanocrystalline electrodeposits as barrier for interconnects. J Solid State Electrochem., vol. 18, 3057–3064. doi:10.1007/s10008-014-2488-x.

Lithuanian Research Council: Electrochemical Nanomaterials for Energy Conversion and Catalysis. 2014–2016.

Tungsten anodization and photoelectrochemical properties of obtained layers were investigated. Rich in molybdenuym and tungsten alloys with Ni, Co and Fe were electrodeposited and electrocatalytic properties were investigated.

Lithuanian Research Council: Colaboration Program Lithuania – Belarus: Development of Enzymatic Biosensors (TAP LB 09/2013). 2013–2014.

Main publications:

Ramanavicius, A., Voronovic, J., Semashko, T., Mikhailova, R., Kausaite-Minkstimiene, A., Ramanaviciene,  A. 2014. Comparison of glucose oxidases from Penicillium adametzii, Penicillium funiculosum and Aspergillus Niger in the design of amperometric glucose biosensors. Analytical Sciences, vol. 30, 1143–1149. 

Ramanavicius, A., Kausaite-Minkstimiene, A.,Morkvenaite-Vilkonciene, I., Genys, P., Mikhailova, R., Semashko, T., Voronovic, J., Ramanaviciene, A. 2015. Biofuel cell based on glucose oxidase from Penicillium funiculosum 46.1 and horseradish peroxidase. Chemical Engineering Journal, vol. 264, 165–173.

Semashko, T., Mikhailova, R., Ramanaviciene, A., Ramanavicius, A. 2013. Specificity of glucose oxidase from Penicillium funiculosum 46.1 towards some redox mediators. Applied Biochemistry and Biotechnology, vol.171, 1739–1749. 

International Research Projects

COST action CM1101: Colloidal Aspects of Nanoscience for Innovative Processes and Materials.

This Action will combine coherently the outstanding European expertise in this field, including: theoretical modelling and experimental formation of functional and patterned interfaces; self-assembly of molecules and colloidal particles; synthesis and up-scaling of novel nano-colloidal and bio-colloidal materials; the kinetic and catalytic aspects of these novel materials; and their applications in chemical, pharmaceutical and food industries, as well as in nano-devices such as sensors, assays, photonics and bio-fuel cells. This includes many of the Grand Challenges in energy, health and environmental protection. The Action will provide a platform for coordination of national programs and will stimulate academia-industry cooperation.

Main publications:

Ramanavicius, A., Genys, P., Oztekin, Y., Ramanaviciene, A. 2014. Evaluation of the redox mediating properties of 1,10-phenanthroline-5,6-dione for glucose oxidase modified graphite electrodes. Journal of the Electrochemical Society, vol. 161, B31–B33.

Ramanavicius, A., Oztekin, Y., Ramanaviciene, A. 2014. Electrochemical formation of polypyrrole-based layer for immunosensor design. Sensors and Actuators B-Chemical, vol.197, 237–243.

Çiftçi, H., Oztekin, Y., Tamer, U., Ramanavicine, A., Ramanavicius, A. 2014. Development of poly(3-aminophenylboronic acid) modified graphite rod electrode suitable for fluoride determination. Talanta, vol. 126, 202–207.

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

Katholieke University Leuven (Belgium)
Northeastern University Boston (US)
Institute of Applied Physics of NAS (Moldova)Hasselt University (Belgium)
Selcuk University, Konya (Turkey)
Odessa National I.I. Mechnikov University, Odesa (Ukraine).

DEPARTMENT OF POLYMER CHEMISTRY

24 Naugarduko, LT-03225 Vilnius
Tel. 219 3113, 219 3227, fax 233 0987
E-mail:

Head - Prof. Dr. Ričardas Makuška

STAFF

Professors: Dr. R. Makuška, Dr. S. Budrienė.
Associate professors: Dr. A. Vareikis, Dr. K. Radzevičius (part-time)
Lecturer: Dr. T. Kochanė.
Research fellows: Dr. V. Pamedytytė, Dr. T. Krivorotova, Č. Višnevskij (part-time)
Doctoral students: A. Bočkuvienė, J. Jonikaitė-Švėgždienė, G. Čiuta, S. Mačiulytė, V. Klimkevičius.

RESEARCH INTERESTS

Synthesis and modification of polymers
Living radical polymerization
Polyelectrolytes from natural and synthetic building blocks
Amphiphilic and charge-carrying brush polymers
Cationic polymers for gene transfection
Polymeric carriers for bioactive compounds
Immobilization of biocatalysts onto polymeric carriers
Encapsulation of hydrophilic and lipophilic materials within polymeric shells

RESEARCH PROJECTS CARRIED OUT IN 2014

Projects Supported by University Budget

Synthesis and Study of Hydrophilic Polymers for Bio- and Nanotechnologies. Prof. R. Makuška. 2011–2015.

A series of cationic random and diblock brush copolymers were synthesized by RAFT and used for stabilization of titania dispersions at neutral and alkaline conditions. Association of anionic surfactants with physisorbed branched brush layers was studied and evaluated. Encapsulation of water soluble substances has been studied under appropriate reaction conditions. Poly(urethane-urea) capsules with encapsulated water soluble enzyme were studied as enzyme delivery systems.

Main publications:

Liu, X., Dedinaite, A., Nylander, T., Dabkowska, A. P., Skoda, M., Makuska, R., Claesson, P. M. 2015. Association of anionic surfactant and physisorbed branched brush layers probed by neutron and optical reflectometry. Journal of Colloid and Interface Science, vol. 440, 245–252.

Klimkevičius, V., Graule, T., Makuška, R. 2014. Cationic random and diblock brush copolymers for stabilization of nanoceramic suspensions. Proceedings of the International Conference Chemistry and Chemical Technology. Kaunas, Technologija, 238–240.

National Research Projects

Research Council of Lithuania. Polymeric Anionic Bottle-Brush Structures as Mimics for Biolubricants (No MIP-051/2012). Prof. R. Makuška. 2012–2014.

Anionic molecular brushes bearing side chains of poly((meth)acrylic acid) or poly(2-acrylamido-2-methyl-N-propansulphonic acid) were synthesized by the methods of ATRP and RAFT. Multiblock polymeric structures containing anionic brush fragments were synthesized by several methods, including the use of RAFT CTA with multiple trithiocarbonate groups, or “one pot” RAFT polymerization. Ionization, changes in size, glass transition and thermal stability of the anionic brush polymers was studied.

Main publications:

Krivorotova, T., Jonikaite-Svegzdiene, J., Radzevicius, P., Makuska, R. 2014. Synthesis by RAFT polymerization and properties of anionic cylindrical molecular brushes bearing poly(acrylic acid) side chains. Reactive & Functional Polymers, vol. 76, 32–40.

Visnevskij, C., Ciuta, G., Ketleriute, S., Savickaite, M., Makuska, R. 2014. ISARA ATRP of methacrylic acid neutralized by simple amines yielding linear polymers and anionic molecular brushes. European Polymer Journal, vol. 55, 66–75.

Research Council of Lithuania. Investigation of Encapsulation of Bacteriocins as Biopreservatives (No SVE-03/2014, project partner, executing institution VGTU). Prof. S. Budrienė. 2014–2015.

Nisin-pectin nanoparticles were prepared by ionic complexation method. Nisin loading efficiency using pectin with different degree of esterification at various values of pH was investigated. Nisin-pectin nanoparticles were studied by DLS, DSC and SEM.

European Social Fund under National Integrated Programme “Biotechnology and Biopharmacy”. Grant VP1-3.1-SMM-08-K01-005. Synthesis and Investigation of the Possibility of Applying of Organic and Inorganic Carriers and Matrices for Suitable Selected Biocatalyzators. Prof. S. Budrienė. 2012–2015.

Modified poly(urethane-urea) microparticles were synthesized from poly(vinyl alcohol), isophorone diisocyanate, various diamines and glutaraldehyde. The microparticles were characterized by chemical analytical methods, infrared spectrometry, thermal analysis, surface area and pore volume analysis. Polymeric carriers were used for immobilization of enzymes.

Main publications:

Barkauskas, J., Dakševič, J., Budrienė, S., Razumienė, J., Šakinytė, I. 2014. Adhesion of graphene oxide on a transparent PET substrate: a study focused on the optimization process. Journal of Adhesion Science and Technology, vol. 28, 2016–2031.

Mačiulytė, S., Kučinskaitė, J., Kochanė, T., Budrienė, S. 2014. Synthesis and characterization of poly(urethane-urea) microcapsules using interfacial polyaddition reaction. Proceedings of the International Conference Chemistry and Chemical Technology. Kaunas, Technologija, 249–252. 

MAIN R&D&I (RESEARCH, DEVELOPMENT AND INNOVATION) PARTNERS

Thermo Fisher Scientific Baltics (Lithuania)
Institute of Biochemistry, Vilnius University (Lithuania)
Royal Institute of Technology (Sweden)
Swiss Federal Laboratories for Material Science and Technology (Switzerland) 

OTHER SCIENTIFIC ACTIVITIES

Prof. R. Makuška – 

• member of the Lithuanian Academy of Sciences;
• scientific committee member of the international conference Baltic Polymer Symposium 2014;
• editorial board member of the journal Chemija (Chemistry).