A General, Highly Efficient Ullmann C-O Coupling Reaction under Microwave Irradiation and the Effects of Water

A general, rapid and highly efficient method for the synthesis of diaryl ethers under the assistance of microwave irradiation was described. A series of diaryl ethers were prepared by direct coupling of phenols and aryl halides in good to excellent yields in anhydrous DMF or NMP at 150 ℃ within 20 rain. The presence of water was found to have a significant impact on the Ullmann C-O coupling reaction between aryl halides and phenols under microwave irradiation.     

Microwave-promoted cross-coupling of acid chlorides with arylboronic acids: a convenient method for preparing aromatic ketones

Simple catalytic systems for cross-coupling reactions of acyl chlorides with arylboronic acids under microwave conditions were tested. Microwave irradiation facilitated the reaction course. Mild reaction conditions afford the symmetrical and unsymmetrical aryl ketones in reasonable to high yields within a short time. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on aryl ring of acid chloride as well as on boronic acid were examined and high yields of ketones were produced.     

Monodisperse thermosensitive particles prepared by emulsifier-free emulsion polymerization with microwave irradiation

The emulsifier-free emulsion polymerization of styrene (St) and N-isopropylacrylamide (NIPAAm) was successfully carried out with microwave irradiation, and the monodisperse thermoresponsive poly(styrene-co-N-isopropylacrylamide) (poly(St-co-NIPAAm)) particles with diameters in the range 100–130 nm were prepared. The morphology, size and size distribution of the poly(St-co-NIPAAm) particles were characterized by transmission electron microscopy, scanning electron microscopy (SEM) and photon correlation spectroscopy (PCS), respectively. The results showed that poly(St-co-NIPAAm) particles had spherical morphology, and the poly(St-co-NIPAAm) particles prepared by emulsifier-free emulsion polymerization with microwave irradiation were smaller, more uniform than those obtained with conventional heating. The hydrodynamic diameters of poly(St-co-NIPAAm) particles were decreased as the temperature increased from 25 °C to 40 °C, and poly(St-co-NIPAAm) particles collapsed remarkably at 32 °C, which is the lower critical solution temperature of the poly(N-isopropylacrylamide). The morphology of the assembled poly(St-co–NIPAAm) particles was observed by SEM, it was found that monodisperse poly(St-co-NIPAAm) particles could assemble to form the two-dimensional order structures.     

微波辐射-酶耦合催化(MIECC)反应

将微波辐射用于非水相酶催化可以获得很多有别于常规加热下的反应结果.本文讨论了微波的非热效应在酶促反应中的表现,探讨了微波辐射对酶的结构、构象、活性及酶催化反应动力学的影响,以及微波辐射-酶耦合催化对反应的对映选择性、底物专一性、前手性选择性和区域选择性的影响.在大多数场合,适当的微波辐射不会损伤酶活而且可以提高反应速率,而对酶特异性的影响则不一而论.     

A mild and efficient method for halogenation of 3,5-dimethyl pyrazoles by ultrasound irradiation using N-halosuccinimides

The 4-halo-3,5-dimethyl pyrazoles have been synthetisized in good yields in short reaction times in the absence of a catalyst by reaction of 3,5-dimethyl pyrazoles with N-halosuccinimides (NBS, NCS and NIS) under ultrasound irradiation. Finally, the halogenation of pyrazoles with Br₂, ICl and I₂ was showed in similar conditions.     

Synergistic effect of combination of Irganox 1010 and zinc stearate on thermal stabilization of electron beam irradiated HDPE/EVA both in hot water and oven

Thermo-oxidative stability of HDPE/EVA blends can be considerably increased by combination of a high-molecular weight phenolic antioxidant and zinc stearate. In this work, the post-irradiation thermal stability of HDPE/EVA blends has been studied. High-density polyethylene and its blends with ethylene-vinylacetate copolymer in both pure form and mixed with Irganox 1010 and zinc stearate were exposed to electron beam radiation at doses between 80 and 150 kGy, at room temperature, in air. In order to evaluate the thermal stability of the samples, post-irradiation heat treatments were done in both hot water bath at 95 °C and in an oven at 140 °C. The mechanical properties and changes in the chemical structure were determined during thermal aging in hot water and oven. The gel content was enhanced by increasing EVA concentration in all applied doses. The stabilized blends have lower gel content than the unstabilized samples. From the results of heat aging treatments it was observed that the thermal stability of the unstabilized blend samples was lower than HDPE. Thermal stability of the samples has been improved by incorporation of Irganox 1010 and zinc stearate. Formation of hydroxyl group was insignificant for stabilized samples during heat aging in both conditions. Also, the changes in the value of oxidation induction time (OIT) for the stabilized samples were negligible after prolonged immersion in hot water.     

氧气氛中紫外光辐照官能化HDPE的结构与性能研究

采用FT－IR，XPS，WAXD，DXC，凝胶和表面自由能力分析，研究了氧化氛中紫外辐照官能化高密度聚乙烯（HDPE）的化学结构、晶体结构和表面自由能的变化。与空气相比，在氧气氛中紫外辐照HDPE能提高C－O，C（＝O）O和C＝O等含氧基团的引入速度，同时又能降低HDPE中的凝胶含量，在空气和氧气氛中紫外辐照后，HDPE的晶型没有发生变化，仍为正交晶系；HDPE的晶胞参数a,b,c以及（110），（200），（020），（011），（111）等晶面间距基本保持不变；HDPE的熔融温度下降，但熔融热焓升高，结晶度增大，表面自由能增大，且在氧气氛中辐照HDPE的变化幅度较大。     

Improvement of plant parameters of the ROBO gamma irradiation facility due to design modification

Two industrial scale, “ROBO” type ⁶⁰Co gamma irradiation facilities have recently been put into operation in Syria and Peru, and the dosimetry commissioning of both plants have been carried out to determine dose distribution within products and to calculate plant parameters such as efficiency, dose uniformity ratio and throughput. There are some design modifications between the two plants in connection with the location of the carriers with respect to the source plaque and also to each other. The effect of these construction modifications on the plant parameters is discussed in the analysis of the dose distribution data measured in the carriers with depth and height among the four irradiation rows on both sides of the source plaque. The plant parameters were also calculated for different product densities using the technical data of the facilities, and the calculated and measured results were compared to each other.     

Reduction of the IgE-binding ability and maintenance of immunogenicity of gamma-irradiated Dermatophagoides farinae

House dust mites, Dermatophagoides farinae (DF) and Dermatophagoides pteronyssinus, are major allergens in the most common indoor allergen and are important risk factor for asthma. The modified antigen has been studied to treat allergic disorder. This study was carried out to measure possibility of modified allergen using gamma irradiation to treat allergy such as asthma. DF solutions (2 mg/ml) as target allergen were irradiated with Co-60 at 50 and 100 kGy. Conformational alternation of irradiated DF was observed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). Levels of anti-irradiated DF mouse IgGs (sub-isotypes) against intact DF were measured similar to that of anti-intact DF IgGs. The binding abilities of house dust mite-allergic patients’ IgE were reduced depending on radiation dose, and irradiation could inhibit the binding ability of patients’ IgE more than 40%. This study has shown that the binding ability of IgE was reduced by conformational alteration by irradiation and the irradiated DF had epitopes capable to induce immunogeniciy.     

EPR study of free radicals in a main chain thermotropic polymer

Free radicals were generated in a rigid rod-like copolymer via mechanical route and by gamma radiation. The (EPR) method was used for studying free radicals formed at 123 K. The spectra of free radicals observed and the influence of molecular motions on the transport of radical centers in the fracture surface layer are discussed.