Infrared analysis in the aqueous humor of patients with uveitis: Preliminary results.

Inflammatory processes affecting the uvea result in a temporary o permanent blurred vision and represent an important cause of visual impairment worldwide. It is often hard to make a precise diagnosis which is dependent on the clinical expertise, diagnostic tests, laboratory investigations in blood and sometimes in the aqueous humor (AH). With the aim of obtaining proof of principle Fourier Transformed Infrared (FT-IR) absorbance spectroscopy was applied to study the molecular composition of 72 AH samples collected in 26 patients with uveitis and in 44 controls. The unsupervised exploration of the internal structure of the dataset by principal component analysis reduced hundreds IR variables to those most representative allowing to obtain the predictive model that distinguished the AH spectra of patients with uveitis from controls. The same result was obtained by unsupervised agglomerative cluster analysis. After labeling the spectra with some clinical information it was observed that most severe uveitis with active processes were grouped separately from chronic and relapsing uveitis and controls. The consistence of prediction models is discussed in the light of supporting etiological diagnosis by machine learning processes. In conclusion, proof of principle has been obtained that the IR spectral pattern of AH may reflect particular uveal diseases.

Spectroscopic evidence of the radioresistance of Chroococcidiopsis biosignatures: A combined Raman, FT-IR and THz-TDs spectroscopy study.

In the last decades, Mars has been widely studied with on-site missions and observations, showing a planet that could have hosted life in the past. For this reason, the recent and future space missions on the red planet will search for traces of past and, possibly, present life. As a basis for these missions, Space Agencies, such as the European Space Agency, have conducted many experiments on living organisms, studying their behavior in extraterrestrial conditions, learning to recognize their biosignatures with techniques remotely controllable such as Raman spectroscopy. Among these organisms, the radioresistant cyanobacterium Chroococcidiopsis was irradiated during the STARLIFE campaign with strong radiative insults. In this article we have investigated this cyanobacterium using Raman spectroscopy and extended the characterization of its biosignatures and its response to the radiative stress to the mid- Infrared and Terahertz spectral region using the Fourier Transform InfraRed (FT-IR) and Terahertz Time Domain spectroscopy (THz- TDs), which demonstrates the compatibility and suitability of these techniques for future space missions.

Low energy electrodynamics of CrI3 layered ferromagnet.

We report on the optical properties from terahertz (THz) to Near-Infrared (NIR) of the layered magnetic compound CrI3 at various temperatures, both in the paramagnetic and ferromagnetic phase. In the NIR spectral range, we observe an insulating electronic gap around 1.1 eV which strongly hardens with decreasing temperature. The blue shift observed represents a record in insulating materials and it is a fingerprint of a strong electron-phonon interaction. Moreover, a further gap hardening is observed below the Curie temperature, indicating the establishment of an effective interaction between electrons and magnetic degrees of freedom in the ferromagnetic phase. Similar interactions are confirmed by the disappearance of some phonon modes in the same phase, as expected from a spin-lattice interaction theory. Therefore, the optical properties of CrI3 reveal a complex interaction among electronic, phononic and magnetic degrees of freedom, opening many possibilities for its use in 2-Dimensional heterostructures.

Tracking of the biochemical changes upon pleomorphic adenoma progression using vibrational microspectroscopy.

Head and neck tumors can be very challenging to treat because of the risk of problems or complications after surgery. Therefore, prompt and accurate diagnosis is extremely important to drive appropriate treatment decisions, which may reduce the chance of recurrence. This paper presents the original research exploring the feasibility of Fourier transform infrared (FT-IR) and Raman spectroscopy (RS) methods to investigate biochemical alterations upon the development of the pleomorphic adenoma. Principal component analysis (PCA) was used for a detailed assessment of the observed changes and to determine the spectroscopic basis for salivary gland neoplastic pathogenesis. It is implied that within the healthy margin, as opposed to the tumoral tissue, there are parts that differ significantly in lipid content. This observation shed new light on the crucial role of lipids in tissue physiology and tumorigenesis. Thus, a novel approach that eliminates the influence of lipids on the elucidation of biochemical changes is proposed. The performed analysis suggests that the highly heterogeneous healthy margin contains more unsaturated triacylglycerols, while the tumoral section is rich in proteins. The difference in protein content was also observed for these two tissue types, i.e. the healthy tissue possesses more proteins in the anti-parallel ß-sheet conformation, whereas the tumoral tissue is dominated by proteins rich in unordered random coils. Furthermore, the pathogenic tissue shows a higher content of carbohydrates and reveals noticeable differences in nucleic acid content. Finally, FT-IR and Raman spectroscopy methods were proposed as very promising methods in the discrimination of tumoral and healthy tissues of the salivary gland.

Nanoscale infrared probing of amyloid formation within the pleomorphic adenoma tissue.

BACKGROUND: The process of malignant transformations of many tumour cases is still unclear and more specific experimental approaches are necessary. The detailed identification of the pathological changes may help in the therapy progression through the development of drugs with more selective action. METHODS: In this study, the AFM-IR nanospectroscopy was applied for the first time to the pleomorphic adenoma (TM) and the marginal tissue characterizations. In order to verify the obtained spectral information, conventional FT-IR investigations were also performed. RESULTS: The AFM-IR data (topographies, intensity maps, and spectra) show structural changes observed for the margin and TM samples. Additionally, within the tumour tissue the fibril-like areas, characteristic for amyloid diseases, were distinguished. CONCLUSIONS: The application of AFM-IR allows to determine changes in the protein secondary structures between the fibrils and the regions outside them. It has been proved that, for the former areas, the α-helix/random coil/ ß-sheet components dominate, while for the latter regions the α-helix/random coil indicate the main contribution to the protein composition. GENERAL SIGNIFICANCE: The FT-IR results remain in good agreement with the AFM-IR data recorded for the areas outside the fibrils of the TM. This observation confirms that by means of the conventional FT-IR method the identification of the considered fibrils structure would be impossible. Only application of the AFM-IR nanospectroscopy allow for characterization and visualization of the fibrillization process occurring within the investigated tumour tissue.

Terahertz and mid-infrared plasmons in three-dimensional nanoporous graphene.

Two-dimensional (2D) graphene emerged as an outstanding material for plasmonic and photonic applications due to its charge-density tunability, high electron mobility, optical transparency and mechanical flexibility. Recently, novel fabrication processes have realised a three-dimensional (3D) nanoporous configuration of high-quality monolayer graphene which provides a third dimension to this material. In this work, we investigate the optical behaviour of nanoporous graphene by means of terahertz and infrared spectroscopy. We reveal the presence of intrinsic 2D Dirac plasmons in 3D nanoporous graphene disclosing strong plasmonic absorptions tunable from terahertz to mid-infrared via controllable doping level and porosity. In the far-field the spectral width of these absorptions is large enough to cover most of the mid-Infrared fingerprint region with a single plasmon excitation. The enhanced surface area of nanoporous structures combined with their broad band plasmon absorption could pave the way for novel and competitive nanoporous-graphene based plasmonic-sensors.

Optical and Vibrational Spectra of CsCl-Enriched GeS2-Ga2S3 Glasses.

Optical and FTIR spectroscopy was employed to study the properties of 80GeS2-20Ga2S3-CsCl chalcohalide glasses with CsCl additives in a temperature range of 77-293 K. It is shown that CsCl content results in the shift of fundamental absorption edge in the visible region. Vibrational bands in FTIR spectra of (80GeS2-20Ga2S3)100 - х (СsCl) x (x = 5, 10, and 15) are identified near 2500 cm(-1), 3700 cm(-1),, around 1580 cm(-1), and a feature at 1100 cm(-1). Low energy shifts of vibrational frequencies in glasses with a higher amount of CsCl can be caused by possible thermal expansion of the lattice and nanovoid agglomeration formed by CsCl additives in the inner structure of the Ge-Ga-S glass.

Second-order susceptibility spectra for δ-BiB3O6 polymer nanocomposites deposited on the chalcogenide crystals.

The optimized conditions for the enhancement of the second harmonic generation in the composites of the orthorhombic δ-BiB3O6:Pr(3+) nanoparticles embedded in polyvinyl alcohol films and deposited on the AgGaGe2Se6, AgGaGe2.7Si0.3Se8 (90 mol.% AgGaGe3Se8 - 10 mol.% AgGaSi3Se8), and AgGaGe3Se8:Cu substrates were established. The highest second-order susceptibility was achieved during the Ag-Ga-Ge-Se crystalline substrates photo-illumination by nanosecond laser pulses of about 2900 nm wavelength. The effect was found to be completely reversible after the interruption of the photo-inducing stimulation. Complementary studies of Atomic Force Microscopy, AFM, X-ray Diffraction, XRD, and Fourier-Transform Infrared Spectroscopy, and DFT simulations of spectral dependences of the corresponding second-order nonlinear optical susceptibilities, were performed.

Facing the challenge of biosample imaging by FTIR with a synchrotron radiation source.

Fourier-transform infrared (FTIR) synchrotron radiation (SR) microspectroscopy is a powerful molecular probe of biological samples at cellular resolution (<10 microm). As the brilliance of SR is 100-1000 times higher than that of a conventional Globar source, FTIR microscopes are now available in almost all advanced SR facilities around the world. However, in spite of this superior performance, the expected advances in IR SR microscopy have not yet been realised, particularly with regard to bio-analytical studies of single cells and soft tissues. In recent decades solid-state array detectors have revolutionized the fields of molecular spectroscopy and chemical imaging, and now new IR focal plane array detectors implemented at ultra-bright SR facilities will extend the performance and overcome the existing limitations, possibly allowing IR SR instrumentation to achieve the highest sensitivity and resolution of molecular imaging. The impact of IR imaging on large tissue area and the complexity of the analysis are discussed. In view of the high brilliance of SR sources, a comparison of published microscope images is given. Finally, it is briefly outlined how an optimized combination of IR instrumentation and SR optical systems could reach the expected advantages of a SR-based FTIR imaging system.

Time-resolved infrared spectroscopy as an in situ tool to study the kinetics during self-assembly of mesostructured films.

Rapid scan time-resolved infrared spectroscopy has been used to investigate in situ the kinetics of the chemical processes involved in the formation of self-assembled mesostructured films. The experiments have been done in transmission mode on films cast on a diamond disk using an infrared microscope. Two specific materials have been studied: silica and titania mesoporous films templated by a triblock copolymer surfactant (Pluronic F-127). The time dependence of solvent evaporation and condensation of the chemical species have been clearly observed. Different stages in the film formation have been identified, which support well the general theory of self-assembly. The in situ FTIR spectroscopy using time-resolved rapid scan has proven to be a very effective tool for in situ analysis of film formation from a liquid phase.

Kinetics of polycondensation reactions during self-assembly of mesostructured films studied by in situ infrared spectroscopy.

In situ synchrotron FTIR experiments have been performed during evaporation-induced self-assembly (EISA) of mesoporous films and the role of silica polycondensation in obtaining highly organized mesostructures has been illuminated.

Highly ordered "defect-free" self-assembled hybrid films with a tetragonal mesostructure.

One-pot self-assembled hybrid films were synthesized by the cohydrolysis of methyltriethoxysilane and tetraethoxysilane and deposited via dip-coating. The films show a high "defect-free" mesophase organization that extends throughout the film thickness and for domains of a micrometer scale, as shown by scanning transmission electron microscopy. We have defined these films defect-free to describe the high degree of order that is achieved without defects in the pore organization, such as dislocations of pores or stacking faults. A novel mesophase, which is tetragonal I4/mmm (space group), is observed in the films. This phase evolves but retains the same symmetry throughout a wide range of temperatures of calcination. The thermal stability and the structural changes as a function of the calcination temperature have been studied by small-angle X-ray scattering, scanning transmission electron microscopy, and Fourier transform infrared spectroscopy. In situ Fourier transform infrared spectroscopy employing synchrotron radiation has been used to study the kinetics of film formation during the deposition. The experiments have shown that the slower kinetics of silica species can explain the high degree of organization of the mesostructure.

Optical performances of SINBAD, the synchrotron infrared beamline at DAphiNE.

SINBAD (Synchrotron Infrared Beamline At DAphiNE) is the first Italian synchrotron radiation beamline operating in the infrared range. It collects the radiation emitted by DANE, an electron-positron collider designed to work at 0.51 GeV with a beam current I> 1 A. The actual performances of the beamline, in terms of brilliance gain with respect to blackbodies and polarization properties, are presented and discussed. Finally, the stability of the SINBAD source, a critical issue for Fourier-transform infrared spectroscopy, is discussed.