C-H···π interactions and the nature of the donor carbon atom.

The influence of multiple substituents (F, CH3, NO2, CN, Cl, OH and NH2) on the C-H···π interaction in benzene-ethylene complex was investigated using the estimated CCSD(T) method and complete basis set limit. The results were compared with our earlier reported complexes of benzene-acetylene and benzene-methane, thus completing the sp, sp(2) and sp(3) series of C-H donors. The stabilization energy values for multiple fluoro-substituted benzene-ethylene complexes are found to be very close to those of the multiple fluoro-substituted benzene-methane complexes. Expectedly, the stabilization energies for the multiple methyl-substituted benzene-ethylene complexes lie between those of the multiple methyl-substituted benzene-methane and benzene-acetylene complexes. Energy decomposition analysis using the DFT-SAPT method predicts the dispersion energy to be dominant, similar to the benzene-methane complexes. For the symmetrically disubstituted complexes (-OH, -Cl, -NH2, -CN and -NO2), additional C-H···X interaction was observed, possibly due to the angular orientation of the ethylene molecule. Multidimensional correlation analysis between the electrostatic, dispersion and exchange-repulsion with the C-H···π interaction distance (r), Hammett constant (σ) and the molar refractivity (MR) revealed strong correlation between dispersion energy and the C-H···π interaction distance (r) as well as molar refractivity (MR).

Non-linear optical imaging of atherosclerotic plaques in the context of SIV and HIV infection prominently detects crystalline cholesterol esters.

Chronic HIV infection may exacerbate atherosclerotic vascular disease, which at advanced stages presents as necrotic plaques rich in crystalline cholesterol. Such lesions can catastrophically rupture precipitating myocardial infarct and stroke, now important causes of mortality in those living with HIV. However, in this population little is known about plaque structure relative to crystalline content and its chemical composition. Here, we first interrogated plaque crystal structure and composition in atherosclerotic SIV-infected macaques using non-linear optical microscopy. By stimulated Raman scattering and second harmonic generation approaches both amorphous and crystalline plaque lipid was detected and the crystal spectral profile indicated a cholesterol ester (CE) dominated composition. Versus controls, SIV+ samples had a greater number of cholesterol crystals (CCs), with the difference, in part, accounted for by crystals of a smaller length. Given the ester finding, we profiled HIV+ plaques and also observed a CE crystalline spectral signature. We further profiled plaques from Ldlr-/- mice fed a high fat diet, and likewise, found CE-dominate crystals. Finally, macrophage exposure to CCs or AcLDL induced auto-fluorescent puncta that co-stained with the LC3B autophagy sensor. In aggregate, we show that atheromatous plaques from mice, macaques and humans, display necrotic cores dominated by esterified CCs, and that plaque macrophages may induce autophagic vesicle formation upon encountering CCs. These findings help inform our knowledge of plaque core lipid evolution and how the process may incite systemic inflammation.

All that glitters is not gold: A non-destructive probing of Thanjavur painting by Raman spectroscopy.

In this work, we demonstrate the use of Raman spectroscopy in detecting the presence of gold and semi-precious/precious gemstones in one of the classical paintings of India namely the Thanjavur paintings which have been awarded the Geographical Indication. We find through Raman spectroscopy that there are paintings where fake gold is used in the place of original gold foils. This result has been validated by carrying out the energy dispersive X-ray analysis (EDX) which confirms the Raman spectroscopy findings. We propose Raman spectroscopy as a diagnostic tool for detecting the presence of gold and thereby to frame regulations for the Thanjavur painting market which would be of utmost importance to the artisans as well as its connoisseurs.

Conformation analysis of 1″,4″-Dispirocyclohexane-6,6'-bis(benzothiazoline): Combined IR, Raman, XRD and DFT approach.

The subject of the study is the structure and conformation of 1″,4″-Dispiro-cyclohexane-6,6'-bis(benzothiazoline), a dispiro compound that has a cyclohexyl ring flanked by two benzothiazoline rings on either side. Using single crystal X-ray diffraction measurements, Infra-red absorption, and Raman spectroscopy techniques, it is found that the central cyclohexyl ring assumes the chair conformation and the sulfur, nitrogen atoms in both the benzothiazole rings are in the trans configurations. The experimental findings are further corroborated by geometry optimization and frequency calculations at B3LYP/6-311++G** level of theory using Gaussian 09 suite of program.