6,7-Dimethyl-5-phenyl-1H-thieno[2,3-e]-[1,4]diazepin-2(3H)-one

In the title molecule, C15H14N2OS, the seven-membered ring adopts a boat conformation. The carbonyl, imine and phenyl groups lie to one side of the molecule, and the thienyl ring and methylene group to the other.

(±)-1-Hydr­oxy-6,6-dimethyl-1H,6H-naphtho[1,2-c]furan-3,9-trione

The title compound, C₁₄H₁₂O₄, crystallizes as discrete mol­ecular species which form hydr­oxy-to-ketone hydrogen-bonded dimers disposed about crystallographic centres of symmetry.

Cation dynamics in dimethyl-pyrrolidinium-based solid-state ion conductors

Dimethyl-pyrrolidinum-based salts have been investigated by means of DSC, conductivity, NMR and Raman spectroscopy. The investigation aims to study the effect of the anion on the behaviour of the salt, in terms of plastic properties as well as rotational degrees of freedom of the cation. The materials range from the non-plastic iodide salt to the highly plastic BF₄ salt, which flows under its own weight at elevated temperatures. The different rotational and translational motions of the cations, and the difference between rotator and plastic phases are discussed.

LiI-doped N,N-Dimethyl-Pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by up to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the ¹H NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. ⁷Li NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.

Zwitterion effect in polyelectrolyte gels based on lithium methacrylate-N,N-dimethyl acrylamide copolymer

Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal.

Lithium doped N,N-dimethyl pyrrolidinium tetrafluoroborate organic ionic plastic crystal electrolytes for solid state lithium batteries

The organic ionic plastic crystal material N,N-dimethyl pyrrolidinium tetrafluoroborate ([C1mpyr][BF4]) has been mixed with LiBF4 from 0 to 8 wt% and shown to exhibit enhanced ionic conductivity, especially in the higher temperature plastic crystal phases (phases II and I). The materials retain their solid state well above 100 °C with the melt not being observed up to 300 °C. Interestingly the conductivity enhancement is highest with the lowest level of LiBF4 addition in phase II, but then the order of enhancement is reversed in phase I. In all cases, a conductivity drop is observed at the II → I phase transition (105 °C) which is associated with increased order in the pure matrix, as previously reported, although the conductivity drop is least for the highest LiBF4 amount (8 wt%). The 8 wt% sample displays different conductivity behaviours compared to the lower LiBF4 concentrations, with a sharp increase above 50 °C, which is apparently not related to the formation of an amorphous phase, based on XRD data up to 120 °C. Symmetric cells, Li/OIPC/Li, were prepared and cycled at 50 °C and showed evidence of significant preconditioning with continued cycling, leading to a lower over-potential and a concomitant decrease in the cell resistivity as measured by EIS. An SEM investigation of the Li/OIPC interfaces before and after cycling suggested significant grain refinement was responsible for the decrease in cell resistance upon cycling, possibly as a result of an increased grain boundary phase.

Synthesis and structure of an intramolecularly coordinated diaryltelluronic acid and its dimethyl ester

The oxidation of the telluroxane cluster (8Me₂NC₁₀H₆Te)₆O₈(OH)₂ (4) or the diaryl ditelluride (8-Me₂NC₁₀H₆Te)(₂) (7) using H₂O₂ provided the diarylditelluronic acid [8-Me₂NC₁₀H₆Te(O)(OH)₂]₂(O) (6), which is the second member of this compound class and the first one to contain an intramolecularly coordinated substituent. Attempts at recrystallizing 6 from Methanol provided the partial ester [8-Me₂NC₁₀H₆Te(O)(OH)(OMe)]₂(O) (8). In addition structural motifs of known diaryltelluronic acids were compared using DFT calculations.

Hydrogen bonding interactions in poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone)/poly(hydroxyether of bisphenol A) triblock copolymer/homopolymer blends and the effect on crystallization, microphase separation and self-assembly

This study investigated the self-assembled microphase separated morphologies that are obtained in bulk, by the complexation of a semicrystalline poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer and a homopolymer, poly(hydroxyether of bisphenol A) (PH) in tetrahydrofuran (THF). In these blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically, the homopolymer interacts with PCL blocks through hydrogen bonding interactions. The crystallization, microphase separation and crystalline structures of a triblock copolymer/homopolymer blends were investigated. The phase behavior of the complexes was investigated using small-angle X-ray scattering and transmission electron microscopy. At low PH concentrations, PCL interacts relatively weakly with PH, whereas in complexes containing more than 50 wt% PH, the PCL block interacts significantly with PH, leading to the formation of composition-dependent nanostructures. SAXS and TEM results indicate that the lamellar morphology of neat PCL-PDMS-PCL triblock copolymer changes into disordered structures at 40-60 wt% PH. Spherical microdomains were obtained in the order of 40-50 nm in complexes with 80 wt% PH. At this concentration, the complexes show a completely homogenous phase of PH/PCL, with phase-separated spherical PDMS domains. The formation of these nanostructures and changes in morphology depends on the strength of hydrogen bonding between PH/PCL blocks and also the phase separated PDMS blocks.

Selective removal of anionic dyes using poly (N, N -dimethyl amino ethylmethacrylate) functionalized graphene oxide

An in situ polymerization strategy was used to functionalize graphene oxide (GO) with poly(N,N-dimethyl amino ethylmethacrylate) (PDMAEMA) for the selective removal of anionic dyes. Various characterization methods demonstrate that PDMAEMA-grafted GO (GO-PDMAEMA) was successfully synthesized, and the high PDMAEMA content of 68.5% in GO-PDMAEMA changed the zeta potential significantly from -36.5 (GO) to 41.5 (GO-PDMAEMA). This change in the charge of GO-PDMAEMA greatly increased the adsorption capacities for anionic dye orange G (OG) compared to the pristine GO. The maximum adsorption capacity for anionic OG dye based on the Langmuir model is 609.8 mg g-1. The adsorption mechanism is believed to be a consecutive process of intra-particle diffusion and surface adsorption, with electrostatic interactions as the key driving force. The GO-PDMAEMA nanocomposite also showed excellent regeneration capacity and selectivity towards the separation of various anionic dyes (i.e. OG, Eosin yellow and Congo red) from an aqueous dye mixture. In conclusion, our method offers a promising strategy for developing new anionic dye adsorbents.

The rapid analysis of heroin drug seizures using micellar electrokinetic chromatography with short-end injection

A simple and rapid method for the analysis of heroin seizures by micellar electrokinetic chromatography with short-end injection is described. Separations were performed using an uncoated fused silica capillary, 50 cm×50 mm I.D.×360 mm O.D. with an effective separation length of 8 cm. The system was run at 25°C with an applied negative voltage of –25 kilovolts. Injection of each sample was for 2 s at –50 mbar. UV detection was employed with the wavelength set at 210 nm. The background electrolyte consisted of 85:15 (water:acetonitrile, v/v) containing final concentrations of 25 mM SDS and 15 mM sodium borate, pH 9.5. Samples and standards were prepared in 0.1% v/v acetic acid and diluted in the run buffer containing 1 mg/ml of N,N-dimethyl-5-methoxytryptamine as an internal standard. Under these conditions a text mixture containing caffeine, paracetamol, morphine, codeine, heroin, and acetylcodeine was resolved within 1.5 min. The method was used to determine the concentration of heroin in heroin seizure samples, and the results were in good agreement with those obtained by a validated gas chromatographic method.

Variation in gametophyte dominance in populations of Chondrus verrucosus (Gigartinaceae, Rhodophyta)

We describe the abundance, including spatial and temporal variability, of phases of the isomorphic Chondrus verrucosus Mikami from Japan. Chondrus verrucosus occurred in a dense (∼90% cover) and temporally stable bed on a small, isolated rocky outcrop (Oyakoiwa) in Shizuoka Prefecture. Small vegetative fronds were always much more abundant than large vegetative and fertile fronds over the spring to late summer periods in 1999 and 2000. Over the same period, fertile carposporophytic fronds were generally more abundant than fertile tetrasporophytic fronds, and fertile male fronds appeared infrequently at low densities. Using the resorcinol-acetal test, we determined the proportion of gametophytes and tetrasporophytes in three populations of C. verrucosus: Oyakoiwa and Noroshi (Shizuoka) in the summers of 1999 and 2000 and Kamehana Point (Miyagi) in autumn 2000. All populations had a significantly higher proportion of gametophytes than tetrasporophytes in both years, although gametophytic proportions were lower at Noroshi (∼70%) than at Oyakoiwa (∼80%) and Kamehana Point (∼97%). However, examination of all isolated individuals sampled on Noroshi showed equal proportions of each phase in 1999, but gametophyte dominance (74%) in 2000. Differences in dispersal and spore production between phases are discussed as mechanisms potentially contributing to variation in gametophyte dominance.