Thin-film polymerization and characterization of Sumitomo's Sumikasuper®-type liquid crystalline polymers

Using the thin film polymerization approach, we have studied the texture evolution when synthesizing a novel liquid crystalline polymer (LCP) system based on Sumikasuper^® LCPs. The main monomers used were p-acetoxybenzoic acid (ABA), 4,4′-biphenol (BP), isophthalic acid (IA), phthalic acid (PA) and terephthalic acid (TA). Polarizing optical microscopy (POM), FTIR, X-ray diffraction (XRD) and atomic force microscopy (AFM) were employed to study the thin film polymerization process and characterize the products. The generation and evolution of liquid crystal phases were monitored; the results revealed that there exists a composition range for the monomers to react and form liquid crystal materials. The critical temperature for LC formation in ABA/BP/IA system decreased with increasing ABA content. FTIR results confirmed the formation of polymers. AFM investigation suggested a similar process of morphological change to that observed using POM. An increasing surface roughness of the thin films with the progress of polymerization was also obtained from AFM analysis. A nematic LC texture of the polymer system was suggested by XRD examination. Results obtained by replacing BP with acetylated BP, and by conducting polymerization using two-monomer systems, suggest that BP units are included in polymers obtained by the thin film polymerization method.     

Anionic Conduction in Blends of Poly(Pyridinium Ethyl Methacrylate Perchloride) and Poly[Oligo(Oxyethylene) Methacrylate-Co-Acrylamide]

Abstract

Blends of poly(pyridinium ethyl methacrylate perchloride) and poly[oligo(oxyethylene) methacrylate-co-acrylamide] were prepared, and the ionic conductivity and mobility of the blends were investigated. Results indicate that both the transference of perchlorate anion and the dissociation of the polymeric salt in the comblike polyether obey the thermoactivation mechanism, and that the perchlorate anion in the blends is free.     

Relationship Between the Polymer Structures and Destabilization of Polymer‐Containing Water‐in‐Oil Emulsions

The viscous properties, scanning electronic microscopy (SEM), and water/oil interfacial tension (IFT) of partially hydrolyzed polyacryamide (HPAM) and hydrophobically associating hydrolyzed polyacryamides modified with N‐dodecylacrylamide were studied with the objective of investigating the influence on destabilization of emulsions. As expected, the copolymers exhibit significant viscosity enhancing capacity and three‐dimensional network structures due to intermolecular hydrophobic associations, and also present high interfacial activities as the IFT decrease with increasing polymer concentration. As a result, the existences of copolymers increased both the viscosity of emulsions and the intensity of interfacial film, in which case slow down the diffusion of demulsifier molecules and enhance the stability of emulsions, finally, the separation of water from oil becomes more difficult.     

CALCULATION OF CONFORMATIONAL ENTROPY AND FREE ENERGY OF POLYSILANE CHAIN

The conformational entropy S and free energy F were calculated by exact enumeration of polysilane chain up to 23segments with excluded volume (EV) and long-range van der Waals (VW) interaction. A nonlinear relation between S_(EV+VW)and chain length n was found though S_(EV) was found to vary linearly with n. We found that the second-order transitiontemperature of polysilane chain with VW interaction increases with the increase of chain length, while that of polysilanechain without VW interaction is chain length independent Moreover, the free energies F_(EV+VW) and FEv are both linearlyrelated with n, and F_(EV+VW) 相似文献   

Flow-injection chemical vapor-generating procedure for the determination of Au by atomic absorption spectrometry

Volatile Au species in an acidified medium were generated at room temperature by reduction with NaBH4 in acidified aqueous medium using a flow-injection chemical vapor-generation atomic absorption spectrometric (FI-CVG-AAS) system in the presence of micro amounts of sodium diethyldithiocarbamate (DDTC). Precision of 2.0% RSD (n = 11, 2.0 mg L(-1) level) was obtained at a sample throughput of 180 h(-1). A detection limit of 24 ng mL(-1) (3sigma) was obtained with 300 microL sample solution. The method was used for the determination of gold in ore sample digests, and the results obtained agreed well with those obtained by flame AAS.     

Highly Enantioselective Iridium‐Catalyzed Hydrogenation of α,β‐Unsaturated Esters

α,β‐Unsaturated esters have been employed as substrates in iridium‐catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic‐ and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural products and pharmaceuticals.     

Elucidation of the Active Conformation of Vancomycin Dimers with Antibacterial Activity against Vancomycin‐Resistant Bacteria

Covalently linked vancomycin dimers have attracted a great deal of attention among researchers because of their enhanced antibacterial activity against vancomycin‐resistant strains. However, the lack of a clear insight into the mechanisms of action of these dimers hampers rational optimization of their antibacterial potency. Here, we describe the synthesis and antibacterial activity of novel vancomycin dimers with a constrained molecular conformation achieved by two tethers between vancomycin units. Conformational restriction is a useful strategy for studying the relationship between the molecular topology and biological activity of compounds. In this study, two vancomycin units were linked at three distinct positions of the glycopeptide (vancosamine residue (V), C terminus (C), and N terminus (N)) to form two types of novel vancomycin cyclic dimers. Active NC‐VV‐linked dimers with a stable conformation as indicated by molecular mechanics calculations selectively suppressed the peptidoglycan polymerization reaction of vancomycin‐resistant Staphylococcus aureus in vitro. In addition, double‐disk diffusion tests indicated that the antibacterial activity of these dimers against vancomycin‐resistant enterococci might arise from the inhibition of enzymes responsible for peptidoglycan polymerization. These findings provide a new insight into the biological targets of vancomycin dimers and the conformational requirements for efficient antibacterial activity against vancomycin‐resistant strains.     

Synthesis of Chiral Benzimidazoles as Acylating Agents for Kinetic Resolution of Racemic α‐Amino Esters

A series of novel chiral 1‐benzoyl‐2‐(α‐N‐substituted aminoethyl)benzimidazoles are synthesized with the improved method in high yields (72–84%) and developed as nonenzymatic acylating agents for kinetic resolution of racemic α‐amino esters. The process exhibits high enantioselectivity (ee up to 94%) for α‐amino esters under mild reaction conditions.     

Synthesis of mesoporous NiO nanosheet and its application on mercury (II) sensor

NiO nanosheets with uniformly distributed mesoporosity were successfully synthesized on a large scale by calcination of β-Ni(OH)₂ nanosheet precursor, which was simply prepared using 1,6-hexanediamine-assisted solution approach. The as-prepared mesoporous NiO nanosheets have been introduced for the first time for the sensing of mercury ions, which were found to be useful for selective electrochemical detection of Hg²⁺ with a linear range of 0.8 to 500?μM in pH?6.0 phosphate-buffered solutions, providing us another opportunity for exploring new electrochemical application of NiO nanomaterials.     

Graphene–Au composite sensor for electrochemical detection of para-nitrophenol

A novel electrochemical sensor for para-nitrophenol (p-NP) was constructed with graphene–Au composite containing 10 % Au (G–Au 10 %). In the composite, Au nanoparticles with the size of ca. 11 nm were regularly scattered on graphene sheet without aggregation, which offers dramatically higher electrocatalytic activity on the redox of K₃[Fe(CN)₆]/K₄[Fe(CN)₆] couple than sole Au nanoparticles. Compared to sole Au nanoparticles, the G–Au 10 % also exhibited dramatically improved electrocatalytic activity on the reduction of p-NP. Amperometric detection of p-NP at G–Au 10 % modified electrode displayed a wide linear range of 0.47–10.75 mM with detection limit of 0.47 μM and a high sensitivity of 52.85 μA/mM. Considering the thrifty in utilization of noble Au, the G–Au 10 % can be successfully applied as a low-cost and powerful sensing material for trace detection of p-NP.