This study aims at exploring the potential of ATR-far-ultraviolet (FUV) spectroscopy in investigating electronic structure and transitions of various kinds of biological molecules. For this purpose, ATR-FUV spectra were measured for several kinds of proteins with the different secondary structures, several kinds of carbohydrates, nucleic acids, and lipids. Band assignments have been made for all kinds of biological molecules investigated based on our previous ATR-FUV studies on n-alkanes, alcohols, esters, and amides. For example, the proteins show a characteristic band near 200 nm due to π-π* transition of amide groups. The position of this band varies a little with the secondary structure of proteins but its intensity changes significantly depending on the secondary structure and solutions. All the carbohydrates studied yielded a band near 170 nm due to n-Rydberg transition of ether. In addition, acetylcarbohydrates give an additional band near 190 nm originating from π-π* transition of amide at 2’ carbon. The present study has demonstrated that ATR-FUV spectroscopy is a new powerful technique in exploring electronic structure and transitions of biological molecules, in general. It is also possible to use ATR-FUV spectroscopy for quantitative and qualitative analysis of biological molecules. Moreover, it is of note that information regarding electronic transitions collected by ATR-FUV spectroscopy is useful for UV resonance Raman (UVRR) spectroscopy studies of biological molecules. A combined ATR-FUV spectroscopy and UVRR spectroscopy method may provide a novel analytical tool for molecular and electronic structure of biological molecules.
SnO2-based glass-ceramics activated by rare earth ions have been extensively investigated because of the need to develop reliable fabrication protocols and clarify some interesting optical, structural, and spectroscopic features of the system. There is one important weakness in glass photonics when the rare earth ions are employed as luminescent sources. This is the low absorption cross section of the electronic states of the rare earth ions. A sensitizer is therefore requested. In the last years, we demonstrated that SiO2-SnO2 glass ceramics, presenting a strong absorption cross section in the UV range due to the SnO2 nanocrystal, are effective rare earth ions sensitizers. Another interesting property of the SiO2-SnO2 system is its photorefractivity. The high photorefractivity of sol-gel-derived SnO2-SiO2 glass-ceramic waveguides has been demonstrated in several papers published by our consortium. It has been shown that the UV irradiation induces refractive index change allowing the direct writing of both channel waveguides and Bragg gratings.
The results presented in this communication not only demonstrate the viability and outstanding properties of the SiO2- SnO2 glass-ceramics for photonic applications but also put the basis for the fabrication of solid state and integrated lasers. The next steps of the research are the fabrication of the channels and mirrors exploiting the photorefractivity as well as to draw glass ceramic fiber, checking the lasing action and corresponding functional characteristics. Finally, it is worth noting that the dynamic of the energy transfer from the nanocrystals to the rare earth ions is still an exciting open question.
UV Resonance Raman (UVRR) scattering offers several advantages with respect to spontaneous Raman one, such as the significant increment of the detection limit and the selectivity needed to incisively monitor specific chromospheres within the sample. Here we present a synchrotron-based Resonance Raman instrument that exploits the wide and continuously tunable UV emission provided by the synchrotron source. As an example, we discuss the solvation dynamics of two model peptides, N-acetyl-leucine-methylamide (NALMA) and N-acetyl-glycine-methylamide (NAGMA), by putting in evidence on the advantages of the use of SR-based UVRR. The experimental results evidence that the fine tuning of the excitation wavelength allows to choose the best working conditions that ensure to reliably detect the spectral changes of the amide signals, as function of concentration and temperature of peptide. The analysis of the spectra provides new insights on the hydrogen-bond interactions at the peptides backbone.
Although Deoxyribonucleic acid (DNA) is considered substantially stable in aqueous solution, slow hydrolysis can damage its double-helix structure and cause denaturation when it is stored for several months. Therefore, the design of aqueous solvents that are able to stabilize and maintain DNA conformation is a challenging issue. Ionic liquids (ILs) appear as ideal water co-solvents for DNA biotechnology due to their unique properties. We have investigated the thermal stability of DNA in 1-butyl-3-methylimidazolium aqueous solutions by synchrotron-based UV Resonance Raman (UVRR) spectroscopy with the aim to clarify the role played by concentration of IL in stabilizing the DNA natural conformation. The synchrotron-based UV source for UVRR measurements allows us to enhance specific vibrational signals associated to nitrogenous bases of DNA, through an appropriate tuning of the excitation wavelength. Such approach permits to probe the rearrangements in the local environment around specific nucleotides as a function of thermal conditions.
Looking at the literature of the last years is evident that glass-based rare-earth-activated optical structures represent the technological pillar of a huge of photonic applications covering Health and Biology, Structural Engineering, Environment Monitoring Systems and Quantum Technologies. Among different glass-based systems, a strategic place is assigned to transparent glass-ceramics, nanocomposite materials, which offer specific characteristics of capital importance in photonics. These two-phase materials are constituted by nanocrystals or nanoparticles dispersed in a glassy matrix. The respective composition and volume fractions of crystalline and amorphous phase determine the properties of the glass-ceramics. The key to make the spectroscopic properties of the glass-ceramics very attractive for photonic applications is to activate the nanocrystals by luminescent species as rare earth ions. From a spectroscopic point of view the more appealing feature of glass-ceramic systems is that the presence of the crystalline environment for the rare earth ions allows high absorption and emission cross sections, reduction of the non-radiative relaxation thanks to the lower phonon cut-off energy and tailoring of the ion-ion interaction by the control of the rare earth ion partition. Although the systems have been investigated since several years, chemical and physical effects, mainly related to the synthesis and to the ions interactions, which are detrimental for the efficiency of active devices, are subject of several scientific and technological investigations. Here we focus on fabrication and assessment of glass-ceramic photonic systems based on rare earth activated SiO2-SnO2 glasses produced by sol-gel route.
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