Molecular spectroscopy

Group of Molecular Vibrational Spectroscopy – group leader Prof. Valdas Šablinskas

Keywords: FTIR spectroscopy; Raman spectroscopy; low frequency Raman; SERS; matrix isolation; cancer spectral markers; conformational analysis; thin films

Research activities of the group

Modern vibrational spectroscopy is frequently used in many fields of science and industry for qualitative and quantitative analysis of solid, liquid and gaseous substances. Main limiting factors of wider application of the method are (I) limited sensitivity and (II) difficulties with analysis of polymeric and biological substances related to very complex structure of their spectra. We are solving such problems using some smart methods of sampling.

Since modern spectroscopic methods of vibrational spectroscopy are very informative and featuring nondestructivity, potential for express analysis, reasonable price, they are in great demand for various scientific, diagnostic solutions.

For many years our research team is focused on:

• Qualitative and quantitative spectral analysis of gases, solids, solutions and composites
• Raman and mid-infrared chemical imaging of surfaces and films
• Conformational analysis of organic substances
• Qualitative and quantitative spectral analysis of biological crystals and fluids
• Spectroscopic diagnostics of cancer cells)
• Development of methods of SERS spectroscopy for various substances to approach the theoretical sensitivity limit, to reduce chemical interaction between nanoparticles and molecules under study, to functionalize the nanoparticles

Our interest for cooperation

The group offers services related to the research activities of the group.

We are searching for partners in the frame of HORIZON 2020 to apply our methods of Raman and infrared spectroscopy in various fields of photonics, semiconductors and nanoscience.

Together with MDs from Santariskiu klinikos we are involved  in designing of FTIR express analyser of cancerous biological tissue, based on fiber ATR-probe, which can act as smart surgical knife.

Our team

Our group consists from 7 members, including experienced and young scientists. Average age of the group is 33 years. The group has capacity to perform complex spectroscopic analysis of any substance of molecular origin.

Research outcomes

The group on average publishes 8 scientific papers annually. Selected publications from recent years:

1. C. Zimmerer, I. Matulaitienė, G. Niaura, U. Reuter, A. Jankea, A., R. Boldt, V. Šablinskas, G. Steiner, Nondestructive characterization of the polycarbonate - octadecylamine interface by surface enhanced Raman spectroscopy, Polymer Testing, DOI: 10.1016/j.polymertesting, vol. 73, p. 152-158 (2019).
2. V. Vajda, M. Pucetaite, S. McLoughlin, A Engdahl, J. Heimdahl, P. Uvdal, Molecular signatures of fossil leaves provide unexpected new evidence for extinct plant relationships, Nature Ecology and Evolution, doi:10.1038/s41559-017-0224-5 (2017).
3. M. Pucetaite, S. Tamosaityte, R. Galli, V. Sablinskas, G. Steiner, Microstructure of urinary stones as studied by means of multimodal nonlinear optical imaging, Journal of Raman Spectrocopy, (online Early View, DOI: 10.1002/jrs.4985) (2016).
4. G. Steiner, G. Preusse, C. Zimmerer, M. Krautwald-Junghanns, V. Sablinskas, H. Fuhrmann, E. Koch, T. Bartels, Label free molecular sexing of monomorphic birds using infrared spectroscopic imaging, Talanta, 150,155–161 (2016).
5. M. Pucetaite, M. Velicka, J. Pilipavicius, A. Beganskiene, J. Ceponkus, V. Sablinskas,Uric acid detection by means of SERS spectroscopy on dried Ag colloidal drops. Journal of Raman Spectrocopy, vol. 47(6), p. 681-686 (2016).
6. J. Ceponkus, M. Jonusas, C. P. Cotter, M. Pucetaite, V. Aleksa, G. A. Guirgis and V. Sablinskas, Structural studies of 1,1-dimethyl-2-oxy-1-silacyclohexane by means of matrix isolation infrared absorption spectroscopy, The Journal of Physical Chemistry A, 119 (11), 2721–2726 (2015).

Currently the group is involved in 4 years project financed by Lithuanian science council in the frame of National program “Healthy aging”.

We regularly provide spectroscopic services for some high-tech companies, such as SPRANA, ALTECHNA, OPTOLITA and other companies.

Resources

Our research group is equipped with a set of modern spectral instruments, which allow using interaction of light with matter for analysis of substances in wide spectral range from 200 nm to 1 mm. More detailed information can be found at www.spectroversum.ff.vu.lt

Contacts

Prof. Dr. Valdas Sablinskas

Faculty of Physics Vilnius University

E-mail:

Phone: +370 5 223 4596

www.spectroversum.ff.vu.lt

Group of Spectroscopy of Magnetic Resonancies – group leader Prof. Vytautas Balevičius

Keywords: NMR of advanced materials in solid and liquid states; CW-FT EPR spectroscopy

Research group activities: Crystallographic aspects, spin diffusion and spin-clusters size profile determination in nano-structured complex solids applying CP-MAS technique; Structure elucidation of organic compounds applying high resolution 1D/2D NMR techniques; Molecular-ionic processes in ionic liquids and composites forming liquid crystalline iono-gel mesophases; Large-amplitude proton dynamics in hydrogen bonded systems; EPR Studies of defects induced by (I) impurities; (II) by ionizing radiation: (III) free radicals in bio-systems.

Availibility of methods: NMR spectroscopy of solids and liquids: Magic angle spinning (up to 15 kHz) experiments for solid state NMR with 400 MHz wide bore magnets. The probe possesses an X channel which is tunable from 15N to 31P. Wide line NMR experiments – starting from polymers to single crystal studies and metal physics in frequency range 109Ag – 31P; Variable temperature range –150°C to +400°C; Static low temperature wide line NMR applications for 109Ag – 31P; Variable temperature range from room temperature to  8K.

EPR spectroscopy: CW regime: sensitivity: weak pitch international standard 2500:1; absolute 1.2 x 109 spins / G; up to 80 MHz tuning range; FT regime: sensitivity: with 10 μM TEMPOL in toluene in 10 sec 200:1; 2 ns time pulse resolution. Helium Temperature Control System (3.8 - 300 K); Variable Nitrogen Temperature Control System (Temperature range 100 K - 500 K); Programmable one axis goniometer, 1/8 degree resolution.

Team: Prof. Dr. Juras Banys, ; Dr. Arunas Marsalka, ; Dr. Vytautas Klimavicius, ; PhD student Mantas Simenas; PhD student Laurynas Dagys, PhD student Kristina Kristinaityte; Prof. Dr. Vytautas Balevicius, (team leader)

Recent publications:

Balevicius V., Aidas K., Svoboda I., and Fuess H., Hydrogen bonding in pyridine N-oxide/acid systems: proton transfer and fine details revealed by FTIR, NMR and X-ray diffraction. – J. Phys. Chem. A, 2012, v.116, p. 8753-8761;

Klimavicius V., Gdaniec, Z., Kausteklis, J., Aleksa, V., Aidas, K., and Balevicius, V., NMR and Raman Spectroscopy Monitoring of Proton/Deuteron Exchange in Aqueous Solutions of Ionic Liquids Forming Hydrogen Bond: A Role Of Anions, Self-Aggregation, and Mesophase Formation. – J. Phys. Chem. B, 2013, v.117, p. 10211-10220;

Klimavicius V., Kareiva A., and Balevicius V., Solid-State NMR Study of Hydroxyapatite Containing Amorphous Phosphate Phase and Nano-Structured Hydroxyapatite: Cut-Off Averaging of CP MAS Kinetics and Size Profiles of Spin Clusters. - J. Phys. Chem. C, 2014, v.118, p. 28914-28921;

 Klimavicius V., Dagys L., and Balevicius V., Subnanoscale Order and Spin Diffusion in Complex Solids through the Processing of Cross-Polarization Kinetics. - J. Phys. Chem. C, 2016, v.120, p. 3542-3549; Dagys L., Klimavicius V., and Balevicius V., Processing of CP MAS kinetics: Towards NMR crystallography for complex solids. - J. Chem. Phys. 2016, v.145, 114202 (9).

Resources: Bruker AVANCE 400 WB and Bruker AVANCE 400 SB spectrometers. Frequency 400 MHz, 2 superconducting magnets of wide- and standard bore, electronic units for independent (parallel) NMR investigation of solid and liquid state.

Bruker X-Band CW/FT EPR Elexys 580 spectrometer, working in pulse FT and CW regimes.

Contacts:

Group of Multiwave Raman Spectroscopy – group leader Prof. Gediminas Niaura

Keywords: Raman spectroscopy; Resonance; Excitation wavelength; Nanomaterials; Electrified interfaces; Functional materials; Carbon; Solar cells; SERS.

Research group activities:

Research of the group focuses on several themes related to the development of multiwavelength Raman spectroscopy and molecular level analysis of carbon materials, biomolecules, ionic liquids, nanostructures, thin films for Solar elements and studies of the structure of electrochemical interfaces.

The research group closely collaborates with chemists and biochemists from Lithuania, Poland, and Sweden.

Proposals:

Structural characterization of nanomaterials and surfaces.

• • Multiwavelength Raman spectroscopy of carbon materials (graphene, carbon nanotubes, diamond like carbon films, nanostructured graphite);
• • Multiwavelength Raman spectroscopic analysis of components of Solar elements (kesterite, perovskite and others);
• • Multiwavelength Raman and infrared spectroscopic characterization of nanostructured hydroxyapatite;
• • Surface-enhanced Raman spectroscopic characterization of adsorbed molecules at Au, Ag, and Cu electrodes. In situ studies at controlled electrode potential;
• • Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) characterization of interfaces;

Raman spectroscopy of aggregates, conformational and dynamic processes in ionic liquids, characterization of water structures in functional materials.

Multiwavelength Raman spectroscopy provides detailed molecular level characterization of materials and processes. Because of dependence of parameters of Raman bands on excitation wavelength (dispersion effect) for carbon materials, resonance Raman spectra of biomolecules and SERS studies of electrified interfaces, new important knowledge on the structure and function of the molecular systems might be extracted.

Team:

Prof. Dr. Gediminas Niaura, Group leader

Dr. Valdemaras Aleksa, Researcher

Jonas Kausteklis, PhD student

Research outcomes:

Research group published more than 180 publications in international peer-reviewed journals which have been cited by other scientists more than 2000 times. The h index of the group leader is 26.

Main recent publications:

1) J. Kausteklis, V. Aleksa, M.A. Iramain, S.A. Brandan, Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid, Journal of Molecular Structure 1164 (2018) 563-576 (DOI: 10.1016/j.molstruc.2018.03.100).

2) J. Kausteklis, V. Balevičius, V. Aleksa, Two-dimensional Raman spectroscopy of ionogel phase formation in long-chain ionic liquid/water systems, Journal of Raman Spectroscopy 48 (2017) 126-131 (DOI: 10.1002/jrs.4983).

3) A. Jagminas, G. Niaura, R. Žalnėravičius, R. Trusovas, G. Račiukaitis, V. Jasulaitienė, Laser light induced transformation of molybdenum disulfide-based nanoplated arrays, Scientific Reports 6 (2016) Art. Nr. 37514 (DOI: 10.1038/srep37514).

4) J. Čeponkus, V. Šablinskas, V. Aleksa, M. Pucetaitė, R. Platakytė, C.W. Reed, C. Cotter, G. Guirgis, Raman and infrared spectroscopic studies of structure and stability of 1,1,2,2-tetrachloro-1,3-disilacylopentane, Vibrational Spectroscopy 81 (2015) 136-143 (DOI: 10.1016/j.vibspec.2015.11.002).

5) G.A. Guirgis, H.W. Dukes, J.K. Wyatt, C.J. Nielsen, A. Horn, V. Aleksa, P. Klaeboe, Vibrational spectra, quantum chemical calculations and spectral assignments of 1,1-difluoro-1-silacyclohexane, Spectrochimica Acta Part A – Molecular and Biomolecular Spectroscopy 136 (2015) 51-57 (DOI: 10.1016/j.saa.2013.10.058).

Resources:

Several Raman spectrometers provide possibility to record multiwavelength Raman spectra by using excitation radiation from UV (325 nm) to NIR (1064 nm) spectral region. We are able to conduct in-situ spectroelectrochemical Raman studies in moving electrochemical cell at controlled electrode potential by using Ag, Au or Cu electrodes.

Contacts:

Prof. Dr. Gediminas Niaura

Chemical Physics Institute, Faculty of Physics, Vilnius University

E-mail:

Phone: +370 686 45026

Group of Theoretical Molecular Spectroscopy – group leader Dr. Kęstutis Aidas

Our research activities are focused on theoretical modelling of structural, dynamic, spectroscopic and thermochemical properties for complex molecular materials. We use modern computational methods including electronic structure calculations, molecular dynamics simulations and combined QM/MM techniques. We have established strong cooperation with experimental NMR and ESR groups at Vilnius University. We collaborate with theoretical chemistry groups at Univerity of Cagliari (Italy), Stockholm University (Sweden) and Metropolitan Autonomous University (Mexico City, Mexico), http://web.vu.lt/ff/k.aidas/]

Quantum mechanics/molecular dynamics modelling of NMR, ESR and UV/vis absorption spectroscopic properties of complex molecular systems including ordinary liquids and solutions, biological systems, metal-organic frameworks and ionic liquids.

 Quantum chemical modelling of aqueous acidity constants for drug-like compounds.

Lithuanian Science Council grant for research project "Modeling quadrupolar NMR relaxation: development and applications" (dr. K. Aidas, PhD student D. Lengvinaitė), 2017-2020.