Solid-Liquid Phase Transfer Catalytic Method for the Preparation of Acyclic and Cylic and Cyclic Ketene Acetals

Solid-liquid phase transfer catalytic elimination reaction for the preparation of acyclic and cyclic ketene acetals has been developed.     

Metal‐ and solvent‐free,clickable synthesis and postpolymerization functionalization of poly(triazole)s

In this study, a series of linear poly(triazole)s (PTAs) were successfully synthesized by the metal‐ and solvent‐free, thermal click polymerization of diazide and dialkyne (A₂ + B₂) monomers. All click polymerizations proceeded smoothly at 80 °C in an open atmosphere without protection from oxygen and moisture. After being polymerized for 36 h, the crude polymer was further fractionated into three fractions using a multistep precipitation method. By selectively choosing precipitating agents, this process produced poly(triazole) fractions with low polydispersity index (<1.30). The resulting PTAs are soluble in common organic solvents and stable at a temperature up to 320 °C. Furthermore, the methyl benzoate moieties in the main chain can serve as useful building blocks for further postpolymerization functionalization, yielding 1,2,4‐triazole derivatives. This functionalization strategy offers potential for the development of novel triazole‐based materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Exceptional Blueshifted and Enhanced Aggregation‐Induced Emission of Conjugated Asymmetric Triazines and Their Applications in Superamplified Detection of Explosives

A novel conjugated asymmetric donor–acceptor (CADA) strategy for preventing the redshift in photoluminescence, as well as preserving the merits of donor–acceptor architectures, was proposed and demonstrated for two triazine derivatives, which showed highly efficient, narrow, and blueshifted ultraviolet light emission in solid films along with special aggregation‐induced emission behavior. A mechanism of aggregation‐induced locally excited‐state emission by suppressing the twisted intramolecular charge‐transfer emission for the spectacular optoelectronic phenomena of these CADA molecules was suggested on the basis of both experimental measurements and theoretical calculations. By taking advantage of this special CADA architecture, fluorescent probes based on aggregates of conjugated asymmetric triazines in THF/water for the detection of explosives show superamplified detection of picric acid with high quenching constants (>1.0×10⁷ M ^?1) and a low detection limit of 15 ppb.     

1,3-二羟基呫吨酮类化合物的简洁合成及清除亚硝酸根作用研究

以间苯三酚为起始原料,在伊顿试剂的催化作用下,与不同取代水杨酸反应合成1,3-二羟基呫吨酮类化合物3a~3l 12个,收率63%~87%,并探讨了反应机理及结构-反应活性关系.利用紫外分光光度法测定了所合成化合物对亚硝酸盐的清除作用,结果表明,在37℃、pH 3及反应时间为30 min条件下,1,3-呫吨酮类化合物对亚硝酸根均有较好的清除作用,其中化合物3f和3b的清除作用最强,清除率达34%.同时对1,3-二羟基呫吨酮类化合物清除亚硝酸盐的作用机制及构效关系进行了探讨.     

The removal of H2S derived from livestock farm on activated carbon modified by combinatory method of high-pressure hydrothermal method and impregnation method

H₂S is considered as the main gas pollutant from livestock farm and activated carbon (AC) is widely used as adsorbent for H₂S. This paper focuses on the influence of modification conditions and operation conditions on the H₂S adsorption performance on AC samples. The H₂S adsorption performance on modified AC (MAC) samples by single and combinatory method has been investigated. It is concluded that the MAC by combinatory method of high-pressure hydrothermal method followed by alkaline solution impregnation method could promote the H₂S adsorption performance remarkably. The H₂S adsorption performance differs with different operation conditions. Meanwhile the samples of fresh AC and exhausted AC have been characterized using BET, FTIR, TPD and Boehm titration method. The experimental results are confirmed that the characteristics of AC have significant influence on the adsorption ability for H₂S.     

A simple, rapid, and efficient oxidation of oximes to ketones and aldehydes with manganese dioxide catalyzed by kieselguhr under solvent-free conditions

A simple, rapid, and efficient oxidation of oximes to the corresponding ketones and aldehydes with manganese dioxide catalyzed by kieselguhr under solvent-free conditions at room temperature in the yields between 82 and 98 is described. It seems that kieselguhr in the present procedure can highly expedite the reaction rate. By comparing to other methods described previously, the main advantages of this oxidation are that the oxidations are more efficient, the reaction conditions are milder, the reaction times are shorter, and the work-up is easier. Furthermore, the amount of manganese dioxide used in this oxidation is largely decreased.     

Laser-induced circular dichroism by a resonant circularly polarized pump optical field

The paper presents and discusses a generalization of the equations of laser-induced circular dichroism (LICD) derived for linear molecules. LICD for freely rotating molecules by a resonant circularly-polarized pump field is an optical analogue of the Faraday effect in isotropic media. Its fundamental formulae and existent conditions have been deduced using the density matrix theory with a two-level model and time-reversal arguments. The antisymmetric rotational polarizability and LICD of symmetric and asymmetric top molecules are studied concretely using perturbation theory and angular momentum algebra. The order of magnitude of LICD and the physical phenomena closely related with it have been discussed. The results show that the LICD effect is exhibited by all freely rotating molecules and may provide useful information on optical activity and antisymmetric polarizability.