Chandrabhas Narayana

Solid hydrogen at 342 GPa: no evidence for an alkali metal

Solid hydrogen, an electrical insulator, is predicted to become an alkali metal under extreme compression, although controversy surrounds the pressure required to achieve this. The electrical conductivity of hydrogen as a function of pressure and temperature is of both fundamental and practical interest—metallic hydrogen may be of relevance to planetary interiors, and has been suggested as a potential high-temperature superconductor. Calculations, suggest that depairing (destruction of the molecular bond) should occur around 340 GPa, accompanied by the formation of an alkali metal at this pressure, or at substantially higher pressures,. Here we report that solid hydrogen does not become an alkali metal at pressures of up to 342 ± 10 GPa, achieved using a diamond anvil cell. This pressure (which is almost comparable to that at the centre of the Earth) significantly exceeds those reached in earlier experiments—216 GPa (ref. 6) and 191 GPa (ref. 7)—at which hydrogen was found to be non-metallic. The failure of solid hydrogen to become an alkali metal at the extreme pressures reported here has implications for our current theoretical understanding of the solid-state phase.

Surface Enhanced Raman Spectroscopy of Proteins: Implications for Drug Designing

In this review article we present a general overview of the recent progress in the newly developing area of the study of protein-ligand interaction by surface enhanced Raman spectroscopy (SERS). Since its first observation in 1977, SERS have been fast developing into an analytical tool for trace detection of molecular entities, particularly in the area of bio-molecule sensing and characterization. Also, with the development of the ability to design a variety of plasmonic structures and to be able to control and tune their plasmonic properties, we have been able to use them as SERS substrates for probing complex materials. Here we describe yet another application of SERS, mainly protein-ligand interaction and its future into drug designing. We start with a general description of the SERS phenomenon. Subsequently we discuss the key spectral features of amino acids, peptides and proteins, and their structural aspects that can be elucidated from the SERS spectra. In the final sections we discuss the applicati...

Temperature Induced Structural Transformations and Gas Adsorption in the Zeolitic Imidazolate Framework ZIF-8: A Raman Study

Here we have used Raman spectroscopy to investigate molecular level changes in the zeolitic imidazolate framework ZIF-8 (a prototypical zeolite-like porous metal organic framework) as a function of temperature. Temperature dependent Raman spectra suggest that at low temperature the softening of the C-H stretching frequencies is due to the decrease in steric hindrance between the methyl groups of methyl imidazole. The larger separation between the methyl groups opens the window for increased nitrogen and methane uptake at temperatures below 153 K. The appearance of Raman bands at 2323 cm(-1) and 2904 cm(-1) at or below 153 K in ZIF-8 are characteristic signatures of the adsorbed nitrogen and methane gases respectively. Nanoscale ZIF-8 uptakes more molecules than bulk ZIF-8, and as a result we could provide evidence for encaged CO2 at 203 K yielding its Raman mode at 1379 cm(-1).

Spin-phonon coupling in multiferroic RCrO3 (R-Y, Lu, Gd, Eu, Sm): A Raman study

Raman study on a select few orthochromites, RCrO3 (R = Y, Lu, Gd, Eu and Sm), shows that the phonon behavior at TN in compounds with magnetic R-ion (Gd and Sm) is remarkably different from that of non-magnetic R-ion (Y, Lu and Eu). While anomalies in most of the observed phonon frequencies in all these compounds may result from the distortion of CrO6 octahedra due to size effect and magnetostriction arising from Cr-ordering, the anomalous behavior of their linewidths observed at TN for the compounds with only magnetic R-ion suggests spin-phonon coupling. The presence of spin-phonon coupling and the anomalies in the low-frequency modes related to R-ion motion in orthochromites (R = Gd and Sm) support the suggestion that the coupling between 4f-3d moments play an important role in inducing switchable electric polarization.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

Griffiths phase-like behavior and spin-phonon coupling in double perovskite Tb2NiMnO6

The Griffiths phase-like features and the spin-phonon coupling effects observed in Tb(2)NiMnO(6) are reported. The double perovskite compound crystallizes in monoclinic P2(1)/n space group and exhibits a magnetic phase transition at T(c) similar to 111 K as an abrupt change in magnetization. A negative deviation from ideal Curie-Weiss law exhibited by 1/chi(T) curves and less-than-unity susceptibility exponents from the power-law analysis of inverse susceptibility are reminiscent of Griffiths phase-like features. Arrott plots derived from magnetization isotherms support the inhomogeneous nature of magnetism in this material. The observed effects originate from antiferromagnetic interactions that arise from inherent disorder in the system. Raman scattering experiments display no magnetic-order-induced phonon renormalization below Tc in Tb(2)NiMnO(6), which is different from the results observed in other double perovskites and is correlated to the smaller size of the rare earth. The temperature evolution of full-width-at-half-maximum for the stretching mode at 645 cm(-1) presents an anomaly that coincides with the magnetic transition temperature and signals a close connection between magnetism and lattice in this material

Tunable optical properties of graphene oxide by tailoring the oxygen functionalities using infrared irradiation.

The modification of individual oxygen functional groups and the resultant optical properties of a graphene oxide suspension were investigated using a controlled photothermal reduction by infrared irradiation. The evolution of the structural and optical characteristics of GO suspensions was obtained from Raman spectra, x-ray photoelectron spectroscopy, optical absorption, and steady state and time-resolved photoluminescence spectroscopy. The results suggest the gradual restoration of sp(2) clusters within the sp(3) matrix with an increase of the reduction time and power density. The yellow-red emission (∼610 nm) originated from the defect-assisted localized states in GO due to epoxy/hydroxyl (C-O/-OH) functional groups and that of the blue emission (∼500 nm) was ascribed to the carbonyl (C=O)-assisted localized electronic states. With an increase in the reduction time and IR power density, the intensity of the yellow-red emission was found to decrease, with the blue emission being prominent. These experimental findings open up a new dimension for controlling the optical absorption and emission properties of graphene oxide by tailoring the oxygen functional groups, which may lead to the potential application of graphene-based optoelectronic devices.

Contiguous petal-like carbon nanosheet outgrowths from graphite fibers by plasma CVD.

We report a catalyst-free synthesis of cantilevered carbon nanosheet extensions, or petals, from graphite fibers by microwave plasma CVD. Results reveal that the petals grow from the fiber surface layers while preserving graphitic continuity from fiber to the petals. Subtraction of Raman signatures from pristine and decorated fibers reveals a convolution of two underlying peaks at 2687 and 2727 cm−1 that are consistent with profiles of multilayer graphene flakes between 5 and 25 layers. Such structures offer the possibility of minimizing interfacial losses in transport applications, improved interactions with surrounding matrix materials in composites, and a route toward substrate independence for device applications.

Universal metal-semiconductor hybrid nanostructured SERS substrate for biosensing.

We demonstrate here a novel high surface area GaN nanowall network substrate with plasmonic Ag nanodroplets, that can be employed as a highly sensitive, reproducible, and charge independent SERS substrate. The uniformity of the size and distribution of the Ag droplets and the absence of linker ligands result in large near-field intensity, while the GaN nanowall network morphology provides multiple reflections for signal enhancement. FDTD calculations simulate the observed hot-spot distribution and reiterate the higher performance of this hybrid substrate over conventional ones. Our studies on oppositely charged proteins provide a proof of concept for employing this as a versatile charge independent label free SERS substrate for trace biomolecule detection.

Nanostructured barium titanate prepared through a modified reverse micellar route : Structural distortion and dielectric properties

A modified and convenient route using microemulsions (avoiding Ba-alkoxide) was evolved for the synthesis of uniform and monodisperse nanoparticles of BaTiO3 at low temperature (800 °C). X-ray line broadening and transmission electron microscopy studies show that the particle size varies in the range of 20–25 nm. Evidence for tetragonal distortion was found in these nano-sized (20–25 nm) particles of barium titanate from careful x-ray diffraction studies as well as from Raman spectroscopy. Our study showed that the critical size of the cubic to tetragonal transition in barium titanate may be much lower than suggested theoretically. The grain size showed an increase on sintering of 35 nm at 900 °C to 120 nm at 1100 °C, which was much lower than the grain size obtained at this temperature by the normal solid state route. The dielectric constant depends on sintering temperature and was found to increase from 210 (900 °C sintering) to 520 (1100 °C sintering) at 100 kHz. The dielectric constant was highly stable with temperature as well as frequency.