Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz-13 MHz) has been used to analyse the frequency, temperature and bias-field dependences of the molecular dynamics of a very high-spontaneous-polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature-dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X-mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*-SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*-SmA phase transition was revealed.     

Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes

Summary The reaction of ()-(tetren)CoOH²⁺ with S₂O ₃ ^2- in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH²⁺,S₂O ₃ ^2- ] formation. Replacement of coordinated OH^- by S₂O ₃ ^2- is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH²⁺ (tetren-H)CoOH ₂ ²⁺ , the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S₂O₃)⁺ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS₂O₃]⁺ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S₂O ₃ ^2- .     

Kinetics and mechanism of the interaction of DL-methionine with cis-diaquaethylenediamine platinum(II) perchlorate in aqueous medium

The kinetics of the interaction of DL-methionine with [Pt(en)(H2O)2]2+ have been studied spectrophotometrically as a function of [Pt(en)(H2O)22+], [DL-methionine], PH and temperature. The reaction proceeds via a rapid outer sphere association followed by two slow consecutive steps having first order dependence on the aqua ion and methionine concentrations. Activation parameters have been evaluated using the Eyring equation. The low H1 (15.6 kJ mol–1) and large negative value of S1 (–230 J K–1 mol–1) as well as H2 (19.5 kJ mol–1) and S2 (–226 J K–1 mol–1) indicate an associative mode of activation for both the aqua ligand substitution processes in the two consecutive steps.     

Characterization of the Reaction of Chloroacetaldehyde with Single and Double Stranded DNA

Chloroacetaldehyde reacts with viral M13mp18 single and double stranded DNA to form the highly fluorescent adducts, etheno-AMP and etheno-CMP.

Absorbance and fluorescence spectroscopy can be used to monitor and characterize these reactions. Both single and double stranded DNA showed increases in the absorbance following reaction with the aldehyde. The fluorescence also increased in these two groups and continued to rise with increasing time of incubation until a point of saturation was reached. The fluorescence of the double stranded moiety was considerably enhanced following reaction with the aldehyde while that of the single stranded population was not, making this method appropriate for the separation of small quantities of the two populations of DNA.     

Three-dimensional bundle-like multiwalled carbon nanotubes composite for supercapacitor electrode application

Bundle-type mutil-walled carbon nanotubes (MWCNTs) composite electrode is the first investigation and publication for the supercapacitor application. According to the thermogravimetric analysis results, as-synthesized BCNTs are considered as the electrode materials for supercapacitors and electrochemical double-layer capacitor in this study. The Brunauer–Emmett–Teller specific surface area of as-prepared bundled carbon nanotubes (BCNTs) is 95.29 m²/g given to a type III isotherm and H3 hysteresis loops. Slow scanning rates promote and enhance to achieve high C_b because of the superior conductivity of CNT bundles and one side close-layered Ni/Mg/Mo alloy inside the BCNT-based electrode and facile electron diffusivity between electrolyte and electrode. The specific capacitance C_s (1,560 F/g) is nearly equal to the maximum specific capacitance, which the BCNT-based composite electrode can actually be able to charge or fill in. The maximum energy density value is 195 Wh/kg with corresponding power density values of 0.21 kW/kg. Furthermore, the active 3D BCNTs material fabricated electrode enhances to contact the electrolyte directly and decreases the ion diffusion limitation. Electrochemical impedance spectroscopy spectrum summarized as the low-frequency area controls by mass transfer limitation, and the high-frequency area dominates by charge transfer of kinetic control. After 2,000 consecutive cyclic voltammetry sacnings and galvanostatic charge-discharge cycles at a current density of 1.67 A/g performs, the specific capacitance retentions of 3D BCNTs electrodes achieved 128.2 and 77.3%, respectively. Three-dimensional BCNT composite electrodes exhibit good conductivity and low charge transfer resistance, which is beneficial to fast charge transfer between the BCNTs electrode materials and electrolytes.     

Effect of spin–orbit coupling on spin transport at graphene/transition metal interface

In spite of large spin coherence length in graphene due to small spin–orbit coupling, the created potential barrier and antiferromagnetic coupling at graphene/transition metal (TM) contacts strongly reduce the spin transport behavior in graphene. Keeping these critical issues in mind in the present work, ferromagnetic (Co, Ni) nanosheets are grown on graphene surface to elucidate the nature of interaction at the graphene/ferromagnetic interface to improve the spin transistor characteristics. Temperature dependent magnetoconductance shows unusual behavior exhibiting giant enhancement in magnetoconductance with increasing temperature. A model based on spin–orbit coupling operated at the graphene/TM interface is proposed to explain this anomalous result. We believe that the device performance can be improved remarkably tuning the spin–orbit coupling at the interface of graphene based spin transistor. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Stereospecific Formal [3+2] Dipolar Cycloaddition of Cyclopropanes with Nitrosoarenes: An Approach to Isoxazolidines

The MgBr₂‐catalyzed formal [3+2] cycloaddition of donor–acceptor activated cyclopropanes with nitrosoarenes offers a novel approach to various structurally diverse isoxazolidines. The reactions, which are experimentally easy to conduct, occur with complete stereospecificity and perfect control of regioselectivity. Product isoxazolidines can be readily transformed into α‐amino lactones by reductive or decarboxylative N? O cleavage and subsequent lactonisation, and the N‐aryl bond cleavage is also possible under oxidative conditions.     

Basic alumina supported one-pot synthesis of structurally diverse pyridine/quinolinine-fused novel diazepanium, diazocanium, imidazodilinium and tetrahydro-pyrimidiniums

Basic alumina supported solvent-free one-pot synthesis of pyridine-fused polycyclic diazepaniums was achieved under microwave irradiation. The process was successfully extended to the synthesis of pyridine-fused bicyclic imidazolidiniums and tetrahydro-pyrimidiniums and also of tri- and tetracyclic diaza-heterocycle-fused quinoliniums. The dual characteristic of basic alumina, a solid support as well as a base, was successfully employed in the current investigation. The method emerged to be an effective route in terms of product yield, reaction time, and ease of purification and most importantly for environment friendly protocols.     

Population Genetic Structure and Marker Trait Associations Using Morphological,Phytochemical and Molecular Parameters in <Emphasis Type="Italic">Habenaria edgeworthii</Emphasis>—a Threatened Medicinal Orchid of West Himalaya,India

Habenaria edgeworthii Hook. f. ex Collett is an important terrestrial orchid used in different Ayurvedic formulations. In the present study, variations among morphological, phytochemical and molecular markers were assessed. A significant difference was observed among populations using morphological traits. Inter-simple sequence repeat (ISSR) data revealed lower genetic diversity at population level (He = 0.207) as compared to species level (He = 0.334). Analysis of molecular variance (AMOVA) indicates 74 % variation among populations and 26 % within population. Tuber extracts showed significantly (p < 0.05) higher total phenolics and flavonoids among the populations. Antioxidant activity determined by 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical scavenging, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging and ferric reducing antioxidant power (FRAP) assays exhibited considerable antioxidant potential. Furthermore, the associations between molecular and morphological and phytochemical attributes were studied using multiple regression analysis (MRA). Several ISSR fragments were associated with some morphological and phytochemical traits. These ISSR fragments can be useful for breeding programme of the species when no other genetic information, such as linkage maps and quantitative trait loci, is available.