Pyrochlore “dynamic spin-ice” Pr2Sn2O7 and monoclinic Pr2Ti2O7: A comparative temperature-dependent Raman study

Here we report a temperature-dependent Raman study of the pyrochlore “dynamic spin-ice” compound Pr₂Sn₂O₇ and compare the results with its non-pyrochlore (monoclinic) counterpart Pr₂Ti₂O₇. In addition to phonon modes, we observe two bands associated with electronic Raman scattering involving crystal field transitions in Pr₂Sn₂O₇ at ∼135 and 460 cm⁻¹ which couple strongly to phonons. Anomalous temperature dependence of phonon frequencies that are observed in pyrochlore Pr₂Sn₂O₇ are absent in monoclinic Pr₂Ti₂O₇. This, therefore, confirms that the strong phonon-phonon anharmonic interactions, responsible for the temperature-dependent anomalous behavior of phonons, arise due to the inherent vacant sites in the pyrochlore structure.     

Zirconium complexes to overcome oxygen inhibition in free‐radical photopolymerization of acrylates: Kinetic,mechanism, and depth profiling

The photopolymerization process of acrylate coatings initiated by visible light (λ > 380 nm) and performed in air was studied in the presence of zirconium complexes. Depth profiling experiments were performed using confocal Raman microscopy showing that the conversion, which is low at the surface of the sample, increases with increasing depth and reaches a full conversion close to the substrate. RT‐FTIR spectroscopy corroborates Raman results in evidencing the efficiency of some zirconium compounds to reduce oxygen inhibition. Finally, laser flash photolysis experiments revealed that the beneficial effect in air is attributable to the reaction of the zirconium complex on the peroxyl radicals formed from the reaction of oxygen with radicals. Therefore, the oxygen present in the medium is depleted, allowing a better efficiency of the photopolymerization process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Solid state characterization of an antioxidant alkaloid boldine using vibrational spectroscopy and quantum chemical calculations

Boldo (Peumus boldus Mol.), a Chilean tree traditionally employed in folk medicine and recognized as a herbal remedy in a number of pharmacopoeias, mainly for the treatment of liver ailment, has recently been the subject of increasing attention. Boldine, in particular, the major and most characteristic alkaloid constituent of this plant species, now emerges as its most interesting active principle from the pharmacological viewpoint.In the present work the structural and spectral characteristics of boldine have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by ab initio Hartree-Fock (HF) and density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311G(d,p) basis set. A complete vibrational assignment is provided for the observed Raman and infrared spectra of boldine molecule.     

Quantitative analysis of alcohol-water binary solutions using Raman spectroscopy

Raman spectroscopy was used for rapid and in situ measurements of alcohols in alcohol-water binary systems. An external standard was used to eliminate factors such as laser power or instrumental effects. Band ratios between the Raman bands of the target molecule and that of acetonitrile as external standard were calculated and found to be proportional to the mass fraction of alcohol. Better linearity was achieved as compared with that in the calibration curve obtained by plotting the Raman intensity alone. The equations of the calibration curves were y=0.2747x with R² of 0.9996 and y=0.2189x+1.340×10⁻³ with an R² of 1.000 in methanol-water and in ethanol-water binary systems, with y and x denoting the Raman intensity ratio and the mass fraction of alcohol, respectively.     

Surface-Enhanced Raman Scattering (SERS) of Nitrothiophenol Isomers Chemisorbed on TiO2

Surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculations were used to investigate the nature of the charge-transfer (CT) process between nitrothiophenol (NTP) isomers and the n-type semiconductor, TiO₂. The Raman signals of p-NTP and m-NTP that were chemisorbed onto TiO₂ were significantly enhanced with respect to their corresponding neat compounds. In particular, an enhancement factor (EF) of 10²–10³ was observed for both p-NTP and m-NTP, with m-NTP displaying a larger EF compared to p-NTP. The Raman signal of o-NTP on TiO₂ was not detectable, owing to interference from fluorescence emissions. A molecule-to-TiO₂ charge-transfer mechanism was responsible for the enhanced Raman signals observed in p-NTP and m-NTP. This transfer was due to a strong coupling between the adsorbate and the metal oxide, which led to an optically driven CT transition from the HOMO of NTP into the conduction band of TiO₂. Based on the mesomeric effect, the NO₂ group para to the thiol had a stronger electron-withdrawing ability than the NO₂ group at the meta position. A less-efficient CT transition from p-NTP to TiO₂ in the surface complex resulted in a weaker Raman-signal enhancement for p-NTP compared to m-NTP. The DFT calculation determined that the HOMO and the LUMO of NTP bound to TiO₂ were located entirely on the adsorbate and the semiconductor, respectively, thereby supporting the experimental findings that a molecule-to-TiO₂ mechanism was the driving force behind the observed SERS effect.     

High-pressure Raman study of MgV2O6 synthesized at high pressure and high temperature

A new structural phase of MgV2O6 was obtained by a high-pressure,high-temperature(HPHT) synthesis method.The new phase was investigated by the Rietveld analysis of X-ray powder diffraction data,showing space group Pbcn(No.60) symmetry and a = 13.6113(6) (1 = 0.1 nm),b = 5.5809(1) ,c = 4.8566(3) ,V = 368.93(2) 3(Z = 4).High pressure behavior was studied by Raman spectroscopy at room temperature.Under 22.5 GPa,there was no sign of a structural phase transition in the spectra,demonstrating stability of the HPHT phase up to the highest pressure.     

Anomalous Molecular Phase of Nitrogen: Implications to the Phase Diagram

Despite their simplicity, diatomic molecules of first row elements can exhibit very complex phase diagrams. Determination of the phase diagrams can be further complicated by the existence of hysteretic molecular phases that can be observed over large regions of coexistence. Here we present evidence for a previously unreported molecular phase of nitrogen existing at room temperature at least over the range of 33-74 GPa. Our measurements show that sample history may have a significant impact on the thermodynamic states accessed by the molecular nitrogen solid and, by extension, also on the established phase diagram.     

SERS decoding of micro gold shells moving in microfluidic systems

In this study, in situ surface‐enhanced Raman scattering (SERS) decoding was demonstrated in microfluidic chips using novel thin micro gold shells modified with Raman tags. The micro gold shells were fabricated using electroless gold plating on PMMA beads with diameter of 15 μm. These shells were sophisticatedly optimized to produce the maximum SERS intensity, which minimized the exposure time for quick and safe decoding. The shell surfaces produced well‐defined SERS spectra even at an extremely short exposure time, 1 ms, for a single micro gold shell combined with Raman tags such as 2‐naphthalenethiol and benzenethiol. The consecutive SERS spectra from a variety of combinations of Raman tags were successfully acquired from the micro gold shells moving in 25 μm deep and 75 μm wide channels on a glass microfluidic chip. The proposed functionalized micro gold shells exhibited the potential of an on‐chip microfluidic SERS decoding strategy for micro suspension array.