Probing Electronic Symmetry Reduction during Charge Migration via Time-Resolved X-Ray Diffraction

The present work focuses on probing ultrafast charge migration after symmetry-breaking excitation using ultrashort laser pulses. LiCN is chosen as prototypical system because it can be oriented in the laboratory frame and it possesses optically-accessible charge transfer states at low energies. The charge migration is simulated within the hybrid time-dependent density functional theory/configuration interaction framework. Time-resolved electronic current densities and simulated time-resolved x-ray diffraction signals are used to unravel the mechanism of charge migration. Our simulations demonstrate that specific choices of laser polarization lead to a control over the symmetry of the induced charge migration. Moreover, time-resolved x-ray diffraction signals are shown to encode transient symmetry reduction at intermediate times.     

EPR and optical absorption studies on Cr3+ ions doped in KZnClSO4 x 3H2O single crystals

EPR and optical absorption spectra of Cr3+ ions doped in KZnClSO4 x 3H2O single crystals have been studied at room temperature. The EPR spectrum exhibits a group of three fine structure transitions characteristic of Cr3+ ions. From the observed EPR spectra, the spin-Hamiltonian parameters have been determined. The optical absorption spectrum exhibits two broad bands characteristic of Cr3+ ions in an octahedral symmetry. From the observed band positions, the crystal field parameters have been evaluated.     

Composition of a monoterpenoid-rich essential oil from the rhizome of Zingiber officinale from north western Himalayas

The chemical composition of the essential oil from the rhizome of ginger (Zingiber officinale Roscoe), collected from Nahan, Himachal Pradesh, India, was determined by gas chromatography and GC-MS. Fifty-one compounds, representing 95.1% of the oil, were identified. The oil was characterized by relatively large amounts of the monoterpenoids 1,8-cineole (10.9%), linalool (4.8%), borneol (5.6%), alpha-terpineol (3.6%), neral (8.1%), geraniol (14.5%), geranial (9.5%), trans-dimethoxy citral (5.0%) and geranyl acetate (6.3%). Five compounds, namely trans-linalool oxide, trans-linalool oxide acetate, (Z)-dimethoxycitral, (E)-dimethoxy citral and epi-zingiberenol are reported for the first time in oil of ginger.     

Assembly of a dinuclear silver complex containing an Ag2S2 motif from a phosphorus-supported trishydrazone ligand. P=S→Ag(I) coordination

The reaction of the phosphorus trihydrazide, (S)P[N(Me)-NH(2)](3) (1) with quinoline-2-carboxaldehyde (C(9)H(6)N-2-CHO) in a 1:3 ratio afforded a trishydrazone, (S)P[N(Me)-N=CH-2-C(9)H(6)N](3) (2). Crystals of 2 were grown in three different solvent media affording an unsolvated (2, monoclinic, P2(1)/n) and two solvated (2·3H(2)O, trigonal, R3 and 2·2CH(3)OH, triclinic, P ?1) crystal forms. Each of these, while possessing an essentially similar molecular structure, adopt different crystal packing giving rise to supramolecular structures mediated by a variety of weak interactions: O-H-N, O-H-O, C-H-N, C-H-O, C-H-S, C-H-π, π-π, N-π and S-π. The reaction of 2 with Ag(ClO(4))(2)·6H(2)O in methanol afforded a dinuclear cationic cage [Ag{(S)P[N(Me)-N=CH-2-C(9)H(6)N](3)}·ClO(4)](2) (3). The molecular structure of 3 reveals a dimeric structure consisting of two Ag(I) ions that are held together by two ligands. Only two arms of the tris hydrazone ligand are involved in coordination while an unprecedented P=S→Ag(I) coordination is seen. This results in the formation of an Ag(2)S(2) dimer that is encapsulated by two trishydrazone ligands. Both compounds 2 and 3 are photoluminescent.     

Interactive effects of ultraviolet-B radiation and temperature on cotton physiology, growth, development and hyperspectral reflectance

Current conditions of 2-11 kJ m(-2) day(-1) of UV-B radiation and temperatures of >30 degrees C during flowering in cotton cultivated regions are projected to increase in the future. A controlled environment study was conducted in sunlit growth chambers to determine the effects of UV-B radiation and temperature on physiology, growth, development and leaf hyperspectral reflectance of cotton. Plants were grown in the growth chambers at three day/night temperatures (24/16 degrees C, 30/22 degrees C and 36/28 degrees C) and three levels of UV-B radiation (0, 7 and 14 kJ m(-2) day(-1)) at each temperature from emergence to 79 days under optimum nutrient and water conditions. Increases in main stem node number and the node of first fruiting branch and decrease in duration to first flower bud (square) and flower were recorded with increase in temperature. Main effects of temperature and UV-B radiation were significant for net photosynthetic rates, stomatal conductance, total chlorophyll and carotenoid concentrations of uppermost, fully expanded leaves during squaring and flowering. A significant interaction between temperature and UV-B radiation was detected for total biomass and its components. The UV-B radiation of 7 kJ m(-2) day(-1) reduced boll yield by 68% and 97% at 30/22 degrees C and 36/28 degrees C, respectively, compared with yield at 0 kJ m(-2) day(-1) and 30/22 degrees C. No bolls were produced in the three temperature treatments under 14 kJ m(-2) day(-1) UV-B radiation. The first-order interactions between temperature, UV-B radiation and leaf age were significant for leaf reflectance. This study suggests a growth- and process-related temperature dependence of sensitivity to UV-B radiation.     

Synthesis, characterization and radiolytic properties of bis(oxalato)borate containing ionic liquids

Previously unreported bis(oxalato)borate (BOB) ionic liquids (ILs) containing imidazolium, pyridinium, and pyrrolidinium cations were prepared from the corresponding halide salts by reaction with sodium bis(oxalato)borate (NaBOB), and their properties are reported. Pulse radiolysis experiments revealed that the BOB anion scavenges solvated electrons with rate constants of 3×10⁸ M⁻¹ s⁻¹ in the ionic liquid C₄mpyrr NTf₂ and 2.8×10⁷ M⁻¹ s⁻¹ in water. This reactivity indicates that BOB ILs may be too sensitive to be used as neat solvents for nuclear separations processes in high radiation fields but may still be useful for preventing criticality while processing relatively “cold” fissile actinides.     

Nanocrystalline NaNbO3 and NaTaO3: Rietveld studies,Raman spectroscopy and dielectric properties

Nanocrystalline NaNbO₃ and NaTaO₃ have been synthesized by the reverse micellar technique for the first time. The particle size of NaNbO₃ was found to be 18 nm while that of NaTaO₃ was found to be 40 nm (much smaller size than most of the earlier reports on NaTaO₃). Rietveld refinement of X-ray diffraction data and Raman spectroscopy confirm that the nanoparticles of NaNbO₃ and NaTaO₃ have orthorhombically distorted structures with Pmc2₁ and Pbnm space groups, respectively. The dielectric constant at 25 °C of NaNbO₃ and NaTaO₃ was found to be 209 and 147 at 1 kHz, respectively. The antiferroelectric transition in NaNbO₃ shifts to lower temperature (325 °C) in the nanocrystalline solid.     

Stereoselective total synthesis of (+)-anamarine via cross-metathesis protocol

A convergent stereoselective total synthesis of (+)-anamarine via cross-metathesis (CM) protocol starting from 2-butyn-1,4-diol and vinyl lactone is reported. Other key features of the strategy include the use of Sharpless asymmetric epoxidation, Sharpless dihydroxylation, and Red-Al reduction.     

Volatile oil composition of Pogostemon heyneanus and comparison of its composition with patchouli oil

The volatile oil of the leaves of Pogostemon heyneanus Benth. (Lamiaceae) was analyzed by GC and GC-MS. Twenty-six components representing 96.0% of the oil were identified. The major components of the oil were acetophenone (51.0%), beta-pinene (5.3%), (E)-nerolidol (5.4%), and patchouli alcohol (14.0%). Comparison of the compositions of the oils of P. heyneanus and P. cablin (Blanco) Benth. (Patchouli oil) showed wide variation between them. Though 13 sesquiterpenes and oxygenated sesquiterpenes were detected in both oils, their concentrations in the oils differed widely. Acetophenone, benzoyl acetone and (E)-nerolidol present in the oil of P. heyneanus were not detected in patchouli oil.     

Development and validation of a highly sensitive LC‐MS/MS‐ESI method for the determination of bicalutamide in mouse plasma: application to a pharmacokinetic study

A highly sensitive, rapid assay method has been developed and validated for the estimation of bicalutamide in mouse plasma using liquid chromatography coupled to tandem mass spectrometry with electrospray ionization in the negative‐ion mode. The assay procedure involves extraction of bicalutamide and tolbutamide (internal standard, IS) from mouse plasma with a simple protein precipitation method. Chromatographic separation was achieved using an isocratic mobile phase (0.2% formic acid:acetonitrile, 35:65, v/v) at a flow rate of 0.5 mL/min on an Atlantis dC₁₈ column (maintained at 40 ± 1°C) with a total run time of 3.0 min. The MS/MS ion transitions monitored were m/z 428.9 → 254.7 for bicalutamide and m/z 269.0 → 169.6 for IS. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. The lower limit of quantitation achieved was 1.04 ng/mL and the linearity range extended from 1.04 to 1877 ng/mL. The intra‐ and inter‐day precisions were in the ranges of 0.49–4.68 and 2.62–4.15, respectively. Copyright © 2012 John Wiley & Sons, Ltd.