Single-Crystal EPR Identification of a Low Hyperfine Value and Interstitial Position of Copper Impurity in Diaquabis[malonato(1-)-κ2O,O′] Zinc(II)

Electron paramagnetic resonance studies have been carried out at 300 K on the Cu(II)-doped [Zn(C₃H₂O₄)₂(H₂O)₂] system in single-crystal and powder forms in order to rationalize the low parallel ⁶³Cu hyperfine value. Angular variation of the hyperfine resonances in the three orthogonal planes shows the presence of only one magnetic site with g and A values equal to g _zz = 2.455, g _yy = 2.121, g _xx = 2.105 and A _zz = 160.9 · 10⁻⁴ cm⁻¹, A _yy = 12.5 · 10⁻⁴ cm⁻¹, A _xx = 7.35 · 10⁻⁴ cm⁻¹. The crystal structure of the host lattice is isostructural with the corresponding cobalt complex and contains two molecules per unit cell. The low magnitude of A _zz value for the complex is rationalized in terms of an admixture of the ground state with the excited state and delocalization of the unpaired spin density onto the ligands. In addition, the highest hyperfine value obtained from the single-crystal data (160.9 · 10⁻⁴ cm⁻¹) is considerably larger than that obtained from the powder spectrum (138 · 10⁻⁴ cm⁻¹). Authors' address: P. Sambasiva Rao, Department of Chemistry, Pondicherry University, Pondicherry 605014, India     

Possible Influence of Layer Deformation and Chiral Segregation on Dielectric Modes in the Dark Conglomerate Liquid Crystal

Dielectric spectroscopy is used to investigate the structure, molecular dynamics, and relaxation phenomena in electric‐field‐induced switchable dark conglomerate (DC) phases in a bent‐core liquid crystal. The DC phases are obtained by applying a high‐frequency ac electric field in the B_1rev phase or by cooling under a dc or an ac field from the isotropic phase. Although the DC phases exhibit good electro‐optic switching properties, the dielectric parameters are different from those observed in typical lamellar SmCP phases and similar to those obtained in a non‐switchable DC phase. We therefore propose that the dielectric response and reduced intensity of the relaxation modes may be a general feature in DC phases and may owe its origin to the deformed layer structure in which certain molecular motions are impeded. Further, we find that in the field‐induced DC phases derived from the isotropic phase, the dielectric modes are affected by chiral segregation promoted by the applied field.     

Fast,Direct, Low‐Cost Route to Scalable,Conductive, and Multipurpose Poly(3,4‐ethylenedixoythiophene)‐Coated Plastic Electrodes

Poly(3,4‐ethylenedioxythiophene) (PEDOT) films are deposited, using an electroless method, onto flexible plastic poly(ethylene terephthalate) (PET) substrates of approximately 20×6 cm². The sheet resistance of a PEDOT–PET film is approximately 600 Ω per square, and the nanoscale conductivity is 0.103 S cm^?1. A plastic electrochromic PEDOT–Prussian blue device is constructed. The device undergoes a color change of pale blue to deep violet–blue reversibly over 1000 cycles, thus demonstrating its use as a light‐modulating smart window. The PEDOT–PET film is also used in a quantum dot solar cell, and the resulting photoelectrochemical performance and work function indicate that it is also promising for photovoltaic cells. The high homogeneity of the PEDOT deposit on PET, the optimal balance between conductivity and optical transparency, and the demonstration of its use in an electro‐optical device and a solar cell, offer the opportunity to use this electrode material in a variety of low‐cost optoelectronic devices.     

Density functional theory investigations on sulfur ylide promoted cyclopropanation reactions: insights on mechanism and diastereoselection issues

The mechanism and diastereoselectivity of synthetically useful sulfur ylide promoted cyclopropanation reactions have been studied using the density functional theory method. Addition of different substituted ylides (Me2S+CH-R) to enone ((E)-pent-3-en-2-one, MeHC=CH-COMe) has been investigated. The nature of the substituent on the ylidic carbon brings about subtle changes in the reaction profile. The stabilized (R=COMe) and semistabilized (R=Ph) ylides follow a cisoid addition mode, leading to 1,2-trans and 1,2-cis cyclopropanes, respectively, via syn and anti betaine intermediates. The simplest and highly reactive model ylide (R=H) prefers a transoid addition mode. Diastereoselectivity is controlled by the barrier for cisoid-transoid rotation in the case of stabilized ylides, whereas the initial electrophilic addition is found to be the diastereoselectivity-determining step for semistabilized ylides. High selectivity toward trans cyclopropanes with stabilized ylides are predicted on the basis of the relative activation energies of diastereomeric torsional transition states. The energy differences between these transition states could be rationalized with the help of weak intramolecular as well as other stereoelectronic interactions.     

Growth of P-Chloroacetanilide Crystals by Gel Aided Solution Technique and Their Characterisation

Single crystals of P-chloroacetanilide which exhibit non-linear optical properties have been grown by solution-gel technique for the first time. Studies on the crystal nucleation have been carried out. The grown crystals are characterised by IR, XRD, and optical microscopy.     

Kinetics and mechanism of the oxidation of some thioacids by benzyltrimethylammonium dichloroiodate

The oxidation of thioglycolic, thiolactic, and thiomalic acids by benzyltrimethylammonium dichloroiodate (BTMAIC) to the corresponding disulfide dimer, is first-order with respect to each the thioacid and BTMAIC. The rates of oxidation were determined at different temperatures and the activation parameters were evaluated. The reaction failed to induce polymerization of acrylonitrile. The reaction rate increases with the increase in the concentration of zinc chloride. Addition of benzyltrimethylammonium chloride enhances the reaction rate. Suitable mechanism has been proposed. © 1996 John Wiley & Sons, Inc.     

An insight into the interactions between LiN(CF3SO2)2 - γBL/DMF — PMMA by FTIR spectroscopy

FTIR spectroscopic analysis has been carried out for liquid electrolytes containing lithium —(trifluormethanesulfonimide or imide) salt as the ion source, a binary solvent composed of γBL and DMF and gel electrolytes containing PMMA. These studies illustrate that for all electrolytes, the cation (Li⁺) — solvent interaction is predominant and occurs through the carbonyl oxygen and the electron rich nitrogen atom of the solvating medium i.e., the binary solvent. Ionic conductivity trends upon varying lithium imide concentration, exhibit a single maximum in both liquid and gel polymeric electrolytes. The conductivity at 25 °C (σ₂₅) decline at high salt concentrations attributable to ion aggregation or cation-anion association, has been explained on the basis of detailed spectral analysis. Addition of PMMA as a gelatinizing agent to liquid electrolytes does not affect the conduction mechanism drastically, which is evident from conductivity measurements and is supplemented by spectral studies.     

The AQUA-MER databases and aqueous speciation server: A web resource for multiscale modeling of mercury speciation

To assess the chemical reactivity, toxicity, and mobility of pollutants in the environment, knowledge of their species distributions is critical. Because their direct measurement is often infeasible, speciation modeling is widely adopted. Mercury (Hg) is a representative pollutant for which study of its speciation benefits from modeling. However, Hg speciation modeling is often hindered by a lack of reliable thermodynamic constants. Although computational chemistry (e.g., density functional theory [DFT]) can generate these constants, methods for directly coupling DFT and speciation modeling are not available. Here, we combine computational chemistry and continuum-scale modeling with curated online databases to ameliorate the problem of unreliable inputs to Hg speciation modeling. Our AQUA-MER databases and web server ( https://aquamer.ornl.gov ) provides direct speciation results by combining web-based interfaces to a speciation calculator, databases of thermodynamic constants, and a computational chemistry toolkit to estimate missing constants. Although Hg is presented as a concrete use case, AQUA-MER can also be readily applied to other elements. © 2019 Wiley Periodicals, Inc.     

Enhancing the Aspirin Loading and Release Efficiency of Silver Oxide Nanoparticles Using Oleic Acid-based Bio-Surfactant from Enteromorpha intestinalis

This study is an attempt to improve the loading and release potential of silver oxide nanoparticles (AgO NPs) using Oleic acid based bio-surfactant isolated from Enteromorpha instestinalis. The isolated Oleic acid based bio-surfactant was characterized using GC–MS, NMR, and HPLC. The AgO NPs were then surface-functionalized with the bio-surfactant and analyzed using XRD, HR-TEM/SAED, DLS, UV–Vis, and FTIR spectroscopy to evaluate the loading of aspirin and functional groups responsible for loading. The model drug Aspirin that has depreciated bio-availability due to poor solubility was used to test the drug carrier efficiency of the AgO NPs after the surface-functionalization. The loading of aspirin was increased by up to 80% in bio-surfactants than PEG-coated NPs (72%) at a 1:1 ratio (Aspirin/NP). The drug release profile of aspirin was evaluated by dialysis at different acidic conditions (pH 1.2, 6.8, and 7.4) and the active release of aspirin was observed in pH 6.8 and bio-surfactant produced better release than PEG and commercial tablet in all the pH conditions. To identify the mechanism of release from the carrier, the release kinetics was studied using zero-order, first-order, Higuchi's, and Korsmeyer Peppas equations and found that the release was time-dependent and non-fickian.