Reversible polymerization driven by folding

Bisfunctionalized m-phenylene ethynylene imine oligomers were polymerized in the polar solvent acetonitrile, resulting in high-molecular weight poly(m-phenylene ethynylene imine)s. It is hypothesized that this polymerization, which proceeds through the reversible metathesis of imine bonds, is driven by the folding of the long m-phenylene ethynylene imine chains. Upon conducting the polymerization in a series of solvents in which the m-phenylene ethynylene oligomers exhibit different folding stabilities, it was possible to correlate the molecular weight of the resulting poly(m-phenylene ethynylene imine)s with the helical stability of the corresponding oligomers. The polymerization was also demonstrated to be reversible and responsive to solvent and temperature changes.     

Preparation of Y2Ba4Cu7O15-δ Superconductor without High Oxygen Pressure

The synthesis of bulk Y₂Ba₄Cu₇O_15-δ superconductor at atmospheric oxygen pressure via solid state sintering is reported. Temperature ranging from 860 to 890 °C as well as time interval over 2 to 15 days were used to investigate the formation of the Y₂Ba₄Cu₇O_15-δ phase. A time-temperature profile characterizing the conditions for the preparation of Y₂Ba₄Cu₇O_15-δ phase suggests the optimal condition to be sintering at 890 °C for over 10 days. Detailed results of X-ray diffraction, electrical resistivity, iodometric titration and magnetization measurements are described.     

CHARGE TRANSFER ACROSS PIGMENTED BILAYER LIPID MEMBRANE AND ITS INTERFACES

Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg²⁺-porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed.     

Core/shell nanocomposite based on the local polarization and its electrorheological behavior

Aimed at the increase of electrorheological effect, a novel core/shell material was prepared by the combination of mechanochemical activity and sol-gel technique. The structure analyses X-ray diffraction, Fourier transform infrared spectrometry, scanning electron microscopy, and energy-dispersive spectrometry showed that a modified kaolinite/titanium oxide nanocomposite consisted of the mechanochemically activated kaolinite/NaCl complex coated by titanium oxide. A distinct enhancement of the electrorheological activity was found by using such particles dispersed in silicone oil than those of kaolinite or titanium oxide alone under a direct current electric field. Modified kaolinite/titanium oxide electrorheological fluid has a larger dielectric constant enhancement deltaepsilon', and a strong interfacial polarization occurs with a clear dielectric loss peak around 2 kHz. Doping NaCl into the core (kaolinite) by the mechanochemical activation and limiting the transferring of the ions by the shell (titanium oxide) may increase the interfacial polarizability of particles and induce a high electrorheological effect.     

Experimental and computational studies of intracomplex reactions in Mg+(primary, secondary alkylamine) complexes induced by photoexcitation of Mg+

We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

A novel route for waste water treatment: photo-assisted Fenton degradation of dye pollutants accumulated in natural polyelectrolyte microshells

The efficient accumulation of dyes in constructed natural polyelectrolyte microshells under moderate conditions, combined with the photo-assisted Fenton reagent, opens a new route for the effective elimination of dye pollutants from waste water.     

Anomalies in the asymmetric hydroboration of olefins with the 11 adduct of (+)-α-pinene and BH3 · THF

The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC₂BH) and monoisopinocampheylborane (IPCBH₂), both prepared from (+)-α-pinene, were studied. In contrast to IPC₂BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH₂ yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged $\text{1}\text{1}$ adduct from (+)-α-pinene and BH₃ · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged $\text{1}\text{1}$ adducts.     

深圳市1408例儿童发中钙,铁,镁含量调查与分析

用火焰原子吸收法检测了深圳市１４０８例１３岁以下儿童发中钙，铁，镁的元素含量，并探讨了元素含量与年龄，性别的关系，结果显示，性别差异有显著意义，钙，镁含量随年龄增长有相似变化。