Light-induced effects in glycine aqueous solution studied by Fourier transform infrared-emission spectroscopy and ultraviolet-visible spectroscopy.

Although amino acids are insensitive to visible light, as is generally accepted, we show that particular light-matter interaction can break this obviousness. Using sensitive (FT-IR)-technique in a combination of a broadband visible light source, we registered emission spectra of glycine in the range 2500-500 cm-1. Sensitivity of the infrared emission spectrum to the exciting power -induced changes in the glycine structure was demonstrated experimentally.Vibrational spectra of glycine displayed the prominent spectral features of CH2, COO-, COOH, NH+3 groups in the "fingerprint region". Simultaneous appearance of ionised COO- and unionised COOH forms of glycine in solution at neutral pH clearly indicated that visible light induces the partial protonation of COO- groups; if so, visible light irradiation should lead to occurrence of dimers or dimeric hydrogen - bonded structures. Spectroscopic and microscopic evidence of visible light-mediated formation of aggregates and nucleus in aqueous solution was presented.Electronic absorption/emission spectra of glycine in aqueous solution were primarily characterized in the near ultraviolet-visible region (240-600 nm). Negligible absorption near 270 nm was observed for a 1.0 M solution and dramatically enhanced with its "aging". Moreover, an extension of the absorption edge into the region above 400 nm could be seen. Due to the visible light irradiation, we observed modification of electronic structure or occurrence of additional species causing changes in absorption of glycine amino acid. For "aged" solution, it was shown that excitation spectra corresponding to the different emission wavelengths were entirely different, at that each excitation-spectral band had a characteristic emission band.Communicated by Ramaswamy H. Sarma.

On the effects of high temperature and high pressure on the hydrogen solubility in rhenium.

In situ x-ray diffraction experiments on rhenium hydride compressed up to 46 GPa reveal a hydrogen solubility (x) significantly larger than the previously assumed saturation limit of x ~ 0.38(4). In the layered anti-CdI(2)-type structure of rhenium hydride, the hydrogen solubility was found to increase to x ~ 0.5 at 15 GPa over time. When heated to temperatures above 420 K at pressures above 23 GPa, rhenium hydride undergoes an isomorphous phase transition into the NiAs-type structure accompanied by an increase in hydrogen solubility to x ~ 0.85. The formation of fully stoichiometric rhenium hydride is discussed.

High-pressure synthesis, amorphization, and decomposition of silane.

By compressing elemental silicon and hydrogen in a diamond anvil cell, we have synthesized polymeric silicon tetrahydride (SiH(4)) at 124 GPa and 300 K. In situ synchrotron x-ray diffraction reveals that the compound forms the insulating I4(1)/a structure previously proposed from ab initio calculations for the high-pressure phase of silane. From a series of high-pressure experiments at room and low temperature on silane itself, we find that its tetrahedral molecules break up, while silane undergoes pressure-induced amorphization at pressures above 60 GPa, recrystallizing at 90 GPa into the polymeric crystal structures.

Structural transition in compressed amorphous sulfur.

Properties of amorphous sulfur (a-S) were investigated by synchrotron x-ray diffraction up to 100 GPa between 40 and 175 K. Measurements of the structure factor yielded the radial distribution function and the densities of two amorphous forms. a-S undergoes a structural transition above 65 GPa, accompanied by density discontinuity of 7%. These results indicate the amorphous-amorphous transition, from a low-density to a high-density form, and open up the possibility for the direct measurements of density of liquid-amorphous materials at extreme conditions.

Vibrational dynamics and stability of the high-pressure chain and ring phases in S and Se.

The high-pressure phases of group-VI elements sulfur and selenium in their spiral chain and ring structures are examined by in situ Raman and x-ray diffraction techniques combined with first principles electronic structure calculations. The S-II, S-III, Se-I, and Se-VII having spiral chain structures and S-VI with a molecular six-member ring structure are studied in a wide P-T range. The square spiral chain structure of S-III and Se-VII is characterized by seven Raman modes that harden with increasing pressure. The calculations reproduce the observed frequencies and allow the authors to make the mode assignment. The "p-S" and "hplt" phases of sulfur reported by previous Raman studies are identified as S-II and S-III with the triangular and square spiral chain structures, respectively. The phase relations obtained by the x-ray and Raman measurements show that the high-pressure high-temperature phases of sulfur, observed by x-ray, can be induced by laser illumination at room temperature.

Melting of dense sodium.

High-pressure high-temperature synchrotron diffraction measurements reveal a maximum on the melting curve of Na in the bcc phase at approximately 31 GPa and 1000 K and a steep decrease in melting temperature in its fcc phase. The results extend the melting curve by an order of magnitude up to 130 GPa. Above 103 GPa, Na crystallizes in a sequence of phases with complex structures with unusually low melting temperatures, reaching 300 K at 118 GPa, and an increased melting temperature is observed with further increases in pressure.

Novel chain structures in group VI elements.

Recent developments in high-pressure methods and advances in X-ray crystallography have led to a new level of understanding of phase diagrams and structures of materials under pressure. Recently discovered phenomena such as complex phases of alkali metals, incommensurate host-guest structures, and incommensurately modulated structures have rendered obsolete our conventional wisdom about the range of structures possible in the elements. Using new in situ diffraction techniques, we have resolved the long-standing problem of the phase-transition sequence of sulphur in its non-metallic state. We demonstrate that it is very different from that previously proposed, with only two phases stable between 1.5 GPa and 83 GPa (the pressure of metallization), and temperatures from 300 K to 1,100 K. The phases have a triangular chain and a squared chain structure. The same squared chain structure is found in the heavier group VI element selenium.

Crystal structure of a high-pressure/high-temperature phase of alumina by in situ X-ray diffraction.

Alumina (alpha-Al(2)O(3)) has been widely used as a pressure calibrant in static high-pressure experiments and as a window material in dynamic shock-wave experiments; it is also a model material in ceramic science. So understanding its high-pressure stability and physical properties is crucial for interpreting such experimental data, and for testing theoretical calculations. Here we report an in situ X-ray diffraction study of alumina (doped with Cr(3+)) up to 136 GPa and 2,350 K. We observe a phase transformation that occurs above 96 GPa and at high temperatures. Rietveld full-profile refinements show that the high-pressure phase has the Rh(2)O(3) (II) (Pbcn) structure, consistent with theoretical predictions. This phase is structurally related to corundum, but the AlO(6) polyhedra are highly distorted, with the interatomic bond lengths ranging from 1.690 to 1.847 A at 113 GPa. Ruby luminescence spectra from Cr(3+) impurities within the quenched samples under ambient conditions show significant red shifts and broadening, consistent with the different local environments of chromium atoms in the high-pressure structure inferred from diffraction. Our results suggest that the ruby pressure scale needs to be re-examined in the high-pressure phase, and that shock-wave experiments using sapphire windows need to be re-evaluated.

A new synthetic all-D-peptide with high bacterial and low mammalian cytotoxicity.

Using the synthetic alpha-helical peptide ((RLA)(2)R)(2) as a model the effect of net charge, helicity, and epimeric nature of the peptide on bactericidal potency has been examined. Both the nature and the extent of the net charge were shown to be relatively important for antibacterial activity. The loss of the structured character of the peptide resulted in reducing the activity. The all-D-peptide appeared to be a remarkably strong bacteriostatic agent with MIC <1 microM against Escherichia coli. The peptide was neither hemolytic nor cytotoxic, which in conjunction with data on its stability to enzymatic degradation makes this peptide very attractive in terms of designing new bactericidal agents on the basis of (D)((RLA)(2)R)(2).