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Tuning of molecular and electronic properties of Pt(II)-organic complexes have a profound effect on their applications in the fields of technology, pharmaceuticals and crystal engineering. Here, we present combined infrared and Raman spectroscopic investigations on trans-PtCl2(PEt3)2 systematically carried out at various temperatures from 300 to 4.2â¯K in a wide spectral range. The studies suggest drastic orientational changes of different moieties around 180â¯K and 130â¯K in the ligand groups attached to the central Pt atom. This is accompanied by a systematic strengthening of C-Hâ¯Cl hydrogen bonds in the 180-130â¯K temperature range. A discontinuous change in intensity, peak variations of modes and emergence of new modes across 180â¯K and 130â¯K in the lattice region are suggestive of a possible structural phase transition. It is interesting to note that the spectral signatures of the low temperature phase are different from those reported recently for the high pressure phase in this compound. These studies will be useful in better understanding the physico-chemical properties of metal-organic complexes in order to exploit their applications in various bio-chemical and technological fields.
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High pressure (up to â¼2.2 GPa) Raman scattering studies were performed in carbon tetrachloride (CCl4) under static and dynamic compressions using diamond anvil cell (DAC) and laser-driven shock methods, respectively, and their results are compared. The laser-driven shock experiments were conducted in a glass-confined target geometry. The symmetric stretching mode ν1, symmetric bending mode ν2, and asymmetric bending mode ν4 blueshifts with pressure. Mode Gruneisen parameters were obtained for the above Raman modes. Time-resolved Raman spectroscopic (TRRS) studies were performed under laser-driven shock compression at different delay times. Shock velocity deduced from the intensity ratios of Raman signal scattered from unshocked and shocked regions of symmetric stretching mode is in agreement with the one obtained from one-dimensional hydrodynamic simulations.
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Hydrogen bonding is essential for the stability of amino acids. A change in the geometry and conformation of hydrogen bonds in such molecular systems, for example, under varying thermodynamic conditions of temperature/pressure, may lead to subtle or drastic phase transitions. We demonstrate here the mechanism of temperature-induced phase transitions in the polycrystalline solid sample of l-leucine [(CH3)2-C(4)H-C(3)H2-C(2)H(C(1)OO-)(NH3+)], an "essential" amino acid, using in situ Fourier transform infrared spectroscopy in the temperature range 300-4.3 K. Unambiguous spectral signatures of preferred microstructural changes have been reported, which are linked to phase transitions at â¼150 and â¼240 K. The transition at 150 K is found to be associated with a sudden change in reorientation dynamics of the torsional vibrations of the (C3C4) group. In contrast, the transition at 240 K is associated with the conformational distortions in the NH3 group, which causes strengthening of the hydrogen bonds in the ac-plane forming two-dimensional sheets, well separated from each other in the b-direction. These findings pave the way toward settling the long-standing debate on the temperature-induced behavior of l-leucine as well as harnessing its physicochemical properties.
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Glycine, the most fundamental amino acid, albeit studied for many decades, has kept researchers captivated with interesting structural variations relevant to important biological, astrophysical and technological applications. We report here a noticeable effect of deuteration on the three dimensional hydrogen bonding network of α-glycine using low temperature infrared absorption studies in a wide spectral range, corroborated with Raman scattering studies. These systematic studies in the range 300-4.2â¯K have demonstrated a relatively compact assembly of glycine molecules in the three dimensional bilayered structure of hydrogenated glycine (gly-h) at low temperatures. This is inferred from a remarkable temperature effect in the weak intra-bilayer hydrogen bond ~ along the b-axis, which strengthens upon cooling. A pronounced increase in the intensity of NH3 torsional and NH stretching modes has been observed. This is accompanied with a large rate of stiffening and softening respectively of these modes upon cooling and a change in slope across 210â¯K and 80â¯K. In contrast, the D---O hydrogen bond lengths in fully deuterated isotope (gly-d), as estimated using empirical correlation, show that the weak intra-bilayer hydrogen bond is not strengthened upon cooling down to 180â¯K, whereas the stronger intra-layer hydrogen bonds in the ac-plane become further strong. The ND3 torsional vibrations show no temperature effect. This implies a relatively stable two dimensional layered structure formed by strongly hydrogen bonded glycine sheets in the ac-plane. Below 180â¯K, similar qualitative trends have been obtained for the hydrogen bond lengths in the two isotopes. In addition, temperature induced variation of the characteristic "indicator" band of zwitterionic gly-h and gly-d has also been reported.
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Spray drying had been used to synthesize silica-carbon black nanocomposite micrometric granules with a uniform distribution of the two components. This was achieved by hindering the preferential diffusion of hydrophobic carbon and hydrophilic silica particles in the water droplets during evaporative assembly by introducing gum arabic as a stabilizing agent and network former. Both positive and negatively charged silica nanoparticles were used to check the stability of the sol and its effect on the morphology of the spray dried granules. X-ray and neutron scattering, complemented with electron microscopy, were used to investigate the correlation and distribution of the nanoparticles within the granules. Porous silica granules, having surface area of 157â¯m2/g, were obtained after removal of carbon black by calcination. An environment-friendly solar absorbing coating had been prepared using as synthesized granules.
Assuntos
Carbono/química , Goma Arábica/química , Nanocompostos/química , Nanopartículas/química , Dióxido de Silício/química , Dessecação , Difusão , Interações Hidrofóbicas e Hidrofílicas , Nanocompostos/ultraestrutura , Nanopartículas/ultraestrutura , Tamanho da Partícula , Porosidade , Eletricidade EstáticaRESUMO
The hydrogen bonded dimeric structure of the model amide based molecular crystal acrylamide has been investigated under pressure using micro-spectroscopy, employing synchrotron infrared radiation up to 24GPa at room temperature. The high pressure spectra indicate systematic evolution of new features above 4GPa, which have been identified to be due to the emergence of a polymeric phase. The polymerization gets completed up to 16.8GPa and the observed changes are found to be irreversible upon the release of pressure. The behavior of NH stretching modes indicate that the uniform inter- and intra-dimeric interactions, rather than depicting a drastic reconstruction across the phase transition, show subtle modifications and become diverse in the high pressure polymeric phase.
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Oxalic acid dihydrate, an important molecular solid in crystal chemistry, ecology and physiology, has been studied for nearly 100 years now. The most debated issues regarding its proton dynamics have arisen due to an unusually short hydrogen bond between the acid and water molecules. Using combined in situ spectroscopic studies and first-principles simulations at high pressures, we show that the structural modification associated with this hydrogen bond is much more significant than ever assumed. Initially, under pressure, proton migration takes place along this strong hydrogen bond at a very low pressure of 2 GPa. This results in the protonation of water with systematic formation of dianionic oxalate and hydronium ion motifs, thus reversing the hydrogen bond hierarchy in the high pressure phase II. The resulting hydrogen bond between a hydronium ion and a carboxylic group shows remarkable strengthening under pressure, even in the pure ionic phase III. The loss of cooperativity of hydrogen bonds leads to another phase transition at â¼ 9 GPa through reorientation of other hydrogen bonds. The high pressure phase IV is stabilized by a strong hydrogen bond between the dominant CO2 and H2O groups of oxalate and hydronium ions, respectively. These findings suggest that oxalate systems may provide useful insights into proton transfer reactions and assembly of simple molecules under extreme conditions.
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The study of hydrogen bonds near symmetrization limit at high pressures is of importance to understand proton dynamics in complex bio-geological processes. We report here the evidence of hydrogen bond symmetrization in the simplest amino acid-carboxylic acid complex, glycinium oxalate, at moderate pressures of 8 GPa using in-situ infrared and Raman spectroscopic investigations combined with first-principles simulations. The dynamic proton sharing between semioxalate units results in covalent-like infinite oxalate chains. At pressures above 12 GPa, the glycine units systematically reorient with pressure to form hydrogen-bonded supramolecular assemblies held together by these chains.
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(p-Chloroanilinium)2CuCl4(C2H14Cl6CuN2) is from an important family of organic-inorganic layered hybrid compounds which can be a possible candidate for multiferroicity. In situ high pressure FTIR, Raman and resistivity measurements on this compound indicate the weakening of Jahn-Teller distortion and the consequent removal of puckering of the CuCl6(4-) octahedra within the layer. These effects trigger insulator to semiconductor phase transition along with a change in the sample colour from yellow to dark red. This article explains the crucial role of the anisotropic volume reduction of the CuCl6(4-) octahedron (caused due to the quenching of Jahn-Teller distortion) in the observed insulator to semiconductor phase transition.
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For the first time, the emission spectrum of A(3)Pi(0)-X(1)Sigma(+) band system of InCl molecule has been recorded on BOMEM DA8 Fourier transform spectrometer at an apodized resolution of 0.025 cm(-1). The rotational structure of 1-0, 2-1, 0-0, 0-1, 1-2, 0-2, and 1-3 bands belonging to the A(3)Pi(0)-X(1)Sigma(+) transition of In(35)Cl has been analyzed and accurate equilibrium rotational constants of the A(3)Pi(0) state obtained. It has also been possible to unambiguously assign rotational lines of 1-0, 0-0, and 0-1 bands belonging to In(37)Cl isotopomer. No perturbations have been observed contrary to what has been reported by some of the earlier workers. Copyright 2001 Academic Press.