Protein crystallography beamline (PX-BL21) at Indus-2 synchrotron.

The protein crystallography beamline (PX-BL21), installed at the 1.5 T bending-magnet port at the Indian synchrotron (Indus-2), is now available to users. The beamline can be used for X-ray diffraction measurements on a single crystal of macromolecules such as proteins, nucleic acids and their complexes. PX-BL21 has a working energy range of 5-20 keV for accessing the absorption edges of heavy elements commonly used for phasing. A double-crystal monochromator [Si(111) and Si(220)] and a pair of rhodium-coated X-ray mirrors are used for beam monochromatization and manipulation, respectively. This beamline is equipped with a single-axis goniometer, Rayonix MX225 CCD detector, fluorescence detector, cryogenic sample cooler and automated sample changer. Additional user facilities include a workstation for on-site data processing and a biochemistry laboratory for sample preparation. In this article the beamline, other facilities and some recent scientific results are briefly described.

A new compact symmetric shear diamond anvil cell for in situ high-pressure-torsion studies.

In situ studies under severe plastic deformation at high pressures, employing shear diamond anvil cells, have recently gained much interest in the high-pressure community owing to their potential applications in material processing methods, mechanochemistry, and geophysics. These studies, combined with multi-scale computational simulations, provide important insights into the transient hierarchical microstructural evolution, structural phase transitions, and orientation relationship between parent and daughter phases and help establish the kinetics of strain-induced phase transitions under severe plastic deformation. The existing SDACs are mostly used in axial x-ray diffraction geometry due to geometrical constraints providing less reliable information about stress states and texture. Their asymmetric design also poses serious limitations to high-pressure shear studies on single crystals. To overcome these limitations, a new compact symmetric shear diamond anvil cell has been designed and developed for in situ high-pressure torsion studies on materials. The symmetric angular opening and short working distance in this new design help obtain a more reliable crystallographic orientation distribution function and lattice strain states up to a large Q range. Here, we present the advantages of the symmetric design with a few demonstrative studies.

High pressure Raman investigation on trans-urocanic acid.

Trans-urocanic acid (t-UCA) is an important epidermal UV protector predominantly found in human skin. Exposure of UV radiation triggers photoisomerization of t-UCA into its other conformer, cis-urocanic acid (cis-UCA), which has been shown to be a mediator of UV-induced immune-suppression leading to skin cancer. In this report, we present the investigation of molecular changes of t-UCA under high pressures by in-situ high pressure Raman spectroscopy. The study indicates onset of ring opening polymerization of t-UCA at pressure above 1.4 GPa. At pressures beyond 5 GPa, a well discernible characteristic vibrational mode (CC stretch) accompanied by several other spectral features such as δ CO2- and δ NH modes of cis-UCA point towards the isomerization of residual t-UCA monomers into cis-UCA. The content of cis-UCA gradually increased with increase in pressure. On release to ambient conditions, the spectrum of the quenched sample showed Raman modes of polymer and cis-UCA indicating that the changes are irreversible.

Spectroscopic studies of temperature induced phase transitions in metal-organic complex trans-PtCl2(PEt3)2.

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 4.2 K in a wide spectral range. The studies suggest drastic orientational changes of different moieties around 180 K and 130 K in the ligand groups attached to the central Pt atom. This is accompanied by a systematic strengthening of C-H⋯Cl hydrogen bonds in the 180-130 K temperature range. A discontinuous change in intensity, peak variations of modes and emergence of new modes across 180 K and 130 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.

Pressure-induced structural phase transformations in silicon nanowires.

High-pressure structural behavior of silicon nanowires is investigated up to approximately 22 GPa using angle dispersive X-ray diffraction measurements. Silicon nanowires transform from the cubic to the beta-tin phase at 7.5-10.5 GPa, to the Imma phase at approximately 14 GPa, and to the primitive hexagonal structure at approximately 16.2 GPa. On complete release of pressure, it transforms to the metastable R8 phase. The observed sequence of phase transitions is the same as that of bulk silicon. Though the X-ray diffraction experiments do not reveal any size effect, the pressure dependence of Raman modes shows that the behavior of nanowires is in between that of the bulk crystal and porous Si.

Structural phase transitions in trigonal Selenium induce the formation of a disordered phase.

Arguments based on the Mermin-Wagner theorem suggest that the quasi-1D trigonal phase of Se should be unstable against long wavelength perturbations. Consisting of parallel Se-Se chains, this essentially fragile solid undergoes a partial transition to a monoclinic structure (consisting of 8-membered rings) at low temperatures (≈50 K), and to a distorted trigonal phase at moderate pressures (≈3GPa). Experimental investigations on sub-millimeter-sized single crystals provide clear evidence that these transitions occur via a novel and counter-intuitive route. This involves the reversible formation of an intermediate, disordered structure that appears as a minority phase with increasing pressure as well as with decreasing temperature. The formation of the disordered state is indicated by: (a) a 'Boson-peak' that appears at low temperatures in the specific heat and resonance Raman data, and (b) a decrease in the intensity of Raman lines over a relatively narrow pressure range. We complement the experimental results with a phenomenological model that illustrates how a first order structural transition may lead to disorder. Interestingly, nanocrystals of trigonal Se do not undergo any structural transition in the parameter space studied; neither do they exhibit signs of disorder, further underlining the role of disorder in this type of structural transition.

High pressure iso-structural phase transition in BiMn2O5.

The high pressure behavior of multiferroic BiMn2O5 has been investigated using powder x-ray diffraction and Raman scattering techniques as well as density functional theory based first principles calculations. Our investigations show a reversible iso-structural phase transition in BiMn2O5 above 10 GPa. The compressibility along the c axis, i.e. along the edge-shared distorted Mn(4+) octahedral chains, has been found to be significantly reduced above this phase transition, suggesting a dominant role of the relatively rigid Mn-O framework in the high pressure phase rather than that of the coordination sphere around the Bi atom. Bader charge analysis of the charge densities obtained from first principles calculations shows partial atomic charge redistribution among Bi(3+) and Mn(3+) atoms across the phase transition which could be the probable cause of this phase transition.

Pressure induced structural phase transition in triglycine sulfate and triglycine selenate.

To elucidate the cause of destruction of ferroelectricity with pressure in triglycine sulfate and triglycine selenate, we have investigated these compounds with the help of Raman measurements as well as first principles total energy and structural optimization calculations. Our results show that, beyond the critical pressures, the loss of ferroelectricity in these compounds is due to the conformational change in one of the three glycine ions of these crystals. Our studies suggest that pressure induced phase transition might be of displacive nature unlike the temperature induced ferroelectric phase transition in these crystals which is known to be of order-disorder type.