Ru/CeO2催化剂催化苯乙烯氢甲氧基羰基化反应高选择性制备直链酯类化合物

酯类化合物在工业上具有广泛应用,例如可用于合成香水、调味剂(味精)、洗涤剂和表面活性剂等.其中,烯烃的氢烷氧基羰基化反应是一种合成酯类化合物的重要方法,其低消耗、100%的原子经济性和原料的易获得等优势使其在制备酯类化合物中成为一个有效且实际可行的方法.对于该反应,文献多采用Pd或Rh的络合均相催化剂,其中控制反应过程中直链酯类化合物(L)和支链酯类化合物(B)的选择性是一项颇具挑战性的课题.虽然目前可通过配体的设计和修饰来调节,但多集中在均相催化体系,因此在选择性调变方面的研究仍很欠缺.相对于均相催化,多相催化由于产物易分离和提纯、催化剂可循环使用等优势而逐渐引起了研究者的广泛关注.在多相催化体系中, Pd负载在强酸性树脂作为催化剂已被应用于苯乙烯氢甲氧基羰基化反应,但在该反应中支链酯类化合物为主要产物.因此,寻找一个可有效改善多相反应体系中选择性问题的方法是非常有意义的.在本研究工作中,我们分别以CeO2纳米颗粒(NP)、CeO2纳米棒(Rod)和CeO2纳米立方体为载体,利用浸渍法制备了Ru/CeO2、Ru/CeO2-rod和Ru/CeO2-cube三种催化剂,并进一步用于苯乙烯氢甲氧基羰基化反应.探究了CO压力、反应温度和反应时间对三种催化剂催化苯乙烯氢甲氧基羰基化反应的影响.结果表明, Ru/CeO2作为多相催化剂催化苯乙烯氢甲氧基羰基化反应时,苯乙烯选择性高于99%,直链酯选择性为83%,支链酯选择性为12%.机理研究表明,该反应为自由基机理.动力学分析表明,该反应的反应活化能为48.50 k Jmol^–1.结合三种催化剂的反应活性以及HRTEM结构表征结果可知,该反应中L/B比值与Ru的尺寸有较大关系.进一步的拉曼表征和NH3-TPD表征结果证明, Ru的尺寸与金属-载体之间的相互作用以及催化剂表面的氧空位浓度有直接关系.     

低渗透油藏爆炸压裂产能分析及压裂改造区域优化设计

基于爆炸压裂裂缝分布规律,提出爆炸压裂缝网双重介质复合流动产能模型,应用Laplace变换Stehfest数值反演,得到了定压条件下封闭外边界低渗透油藏爆炸压裂生产井产能表达式。在模型正确性验证的基础上结合某低渗透油藏储层特征参数研究了爆炸压裂改造区域参数对封闭边界油藏产量的影响,同时对爆炸压裂改造改造体积优化设计进行了研究。研究结果表明,爆炸压裂改造区域半径主要影响生产中期产能,改造区域渗透率对生产早期和中期影响比较大,且对于实例油藏爆炸压裂改造比为0.1时效果最好。     

Design and fabrication of subwavelength nanogratings based light-emitting diodes

Linearly polarized light from InGaN green light emitting diode grown on (0001) oriented sapphire is demonstrated by using subwavelength metallic nanogratings. Polarization ratio can reach 7:1 (∼88%), the highest ever reported from a single light emitting device. We discuss the design and fabrication of this device in detail.     

聚变实验增殖堆FEB-E粒子抽除和抽气系统(英文)

ＦＥＢ－Ｅ的粒子抽除是通过偏滤器进行的。由４８ 个楔形气室模件环形组装而成的ＦＥＢ－Ｅ偏滤器，位于真空室的下部，与抽气系统和冷却系统相连。ＦＥＢ－Ｅ抽气系统有二个子系统：环粗抽系统和环高真空系统。环高真空系统是由一组处于真空室内１６ 个下部舱口内的低温泵和一组处于生物屏蔽层外的附加涡轮分子泵组成的。这些低温泵能提供的名义总抽速为５７６ｍ ３·ｓ－ １。在偏滤器高中性压力（＞ １Ｐａ）情况下，低温泵入口阀节流控制抽气粒子流。由于偏滤器抽气槽路以及偏滤器下侧通至真空室下部舱口的有限的通导能力，这些低温泵在偏滤器幽僻区域有效抽速为１６０ｍ ３·ｓ－ １。这意味着偏滤器幽僻区域的中性压力应在０．５－ １．０Ｐａ 范围内，以得到８０－ １６０Ｐａ·ｍ ３·ｓ－ １（在预期的偏滤器抽气槽路温度为４７３Ｋ时）范围内的抽气流量。低温泵每次在聚变实验增殖堆燃烧１０００ｓ 后受激运行     

Molecular simulation of the interaction between novel type rhodanine derivative probe and bovine serum albumin

The interaction between 3-(4′-methylphenyl)-5-(4′-methyl-2′-sulfophenylazo) rhodanine (M4MRASP) and bovine serum albumin (BSA) was studied by using spectrofluorimetry. It was shown in fluorescence spectrums that the quenching mechanism of BSA by M4MRASP was a static quenching. Meanwhile, the binding constant and binding site numbers were calculated. The action distance (r = 8.03 nm) and energy transfer efficiency (E = 0.12) between donor (BSA) and acceptor (M4MRASP) were obtained according to the theory of Förster non-radiation energy transfer. The effect of M4MRASP on the conformation of BSA was further analyzed by using synchronous fluorescence spectrometry. A new model of the interaction between small organic molecule and biomacromolecule was established. The results offered a reference for the studies on the biological effects and action mechanism of small molecule with protein.     

Double-Network Heparin Dynamic Hydrogels: Dynagels as Anti-bacterial 3D Cell Culture Scaffolds

Double cross-linked dynamic hydrogels, dynagels, have been prepared through reversible imine bonds and supramolecular interactions, which showed good pH responsiveness, injectability, self-healing property and biocompatibility. With the further encapsulation of heparin, the obtained hydrogels exhibited good anti-bacterial activity and promotion effects for 3D cell culture.     

A Survey of Calculator Usage in High Schools

This survey investigated the current status of calculator use in classrooms and schools. The results indicated that the prevailing policy in the sample of high schools is to allow the use of calculators during classroom learning activities and tests. Scientific calculators are more frequently used than graphing calculators in algebra I and geometry; whereas, graphing calculators are more frequently used in algebra II and precalculus/trigonometry. At the time of this survey, school policies regarding the use of graphing calculators with symbolic algebra capabilities were still not determined.     

半导体激光器纵向泵浦准连续Cr∶LiSAF激光器的实验研究

用波长为653.2nm的半导体激光器实现了纵向泵浦Cr∶LiSAF激光器的准连续运转，晶体平均吸收功率为140mW时获得激光输出，在LD最大输出功率范围内，晶体平均吸收功率为680mW时，可获得最大平均输出功率32mW，斜效率5.6%.     

A ZnO/TiO2 composite nanorods photoanode with improved performance for dye‐sensitized solar cells

A dye‐sensitized solar cell (DSSC) based on ZnO/TiO₂ composite nanorods (NRs) photoanode is fabricated. The power conversion efficiency (PCE) of the ZnO/TiO₂ composite NRs film DSSC is 4.36%, which is obviously higher than that of DSSCs based on pure TiO₂ NRs (0.6%) and ZnO NRs (3.10%). The enhanced performance of ZnO/TiO₂ composite NRs film DSSC can be attributed to the combined effects of ZnO and TiO₂ NRs. In this architecture, the thick ZnO NRs overlayer offers a large surface area for enough dye absorption, while the thin TiO₂ NRs underlayer not only offers a direct and quick pathway for photoinjected electron transfer along the photoanode but also acts as a blocking layer, which effectively hinders the direct contact between the substrate and the electrolyte resulting in lower carrier recombination.     

Electrochemical biosensor based on nanogold-modified poly-eriochrome black T film for BCR/ABL fusion gene assay by using hairpin LNA probe

A novel electrochemical biosensor is described for detection of breakpoint cluster region gene and a cellular abl (BCR/ABL) fusion gene in chronic myelogenous leukemia (CML) by using thiolated-hairpin locked nucleic acids (LNA) as the capture probe. The hairpin LNA probe was immobilized on the nanogold (NG)/poly-eriochrome black T (EBT) film-modified glassy carbon electrode (GCE). The immobilized LNA probe could selectively hybridize with its target DNA on LNA/NG/EBT/GCE surface. The immobilization and hybridization of the LNA probe were characterized with cyclic voltammetry and electrochemical impedance spectroscopy. The hybridization of the immobilized LNA probe with the target DNA was detected by differential pulse voltammetry with the electroactive methylene blue as an indicator. The results indicated this new method has excellent specificity for single-base mismatch and complementary after hybridization, and a high sensitivity. This novel electrochemical biosensor has been used for assay of PCR real sample with satisfactory result.