负载型Pd/SBA-15催化剂的双烯选择性加氢催化性能

用微型反应器评价体系结合程序升温还原CO、化学吸附、BET比表面积测试和高分辨率透射电子显微镜等多种表征方法研究了负载型Pd/SBA-15催化剂的长链正构双烯选择性加氢的催化性能.结果表明,与Pd/-γAl2O3工业催化剂相比,Pd/SBA-15催化剂双烯选择性加氢的催化性能更优良,且Pd/SBA-15催化剂双烯选择性加氢催化性能与Pd负载量密切相关.随Pd负载量增加,Pd/SBA-15催化剂的金属分散度和长链正构双烯加氢选择性急剧下降.     

对单电子近似方法的介绍

介绍单电子近似的引入、处理方法和改进,并分析了单电子近似带来的误差（相关能效应）和校正误差的方法。     

轨道和波函数

分子（或原子）轨道是化学的基本概念之一。本文从Bohr原子轨道入手,介绍轨道概念的演化,以及轨道与波函数之间的关系,分子轨道与原子轨道之间的关系,并结合量化计算介绍基组与分子轨道的关系。     

一种演示全反射消逝波的简便方法

建立了一套演示光全内反射产生的消逝波的实验装置。在罗丹明B溶液中的棱镜表面处,观察到了由532纳米的激光束全内反射产生的消逝波激发的荧光。     

Synthesis of biodegradable thermoplastic elastomers from ε‐caprolactone and lactide

This article reports the synthesis and the properties of novel thermoplastic elastomers of A‐B‐A type triblock copolymer structure, where the hard segment A is poly(l ‐lactide) (PLLA) and the soft segment B is poly(ε‐caprolactone‐stat‐d ,l ‐lactide) (P(CL‐stat‐DLLA)). The P(CL‐stat‐DLLA) block with DLLA content of 30 mol % was applied because of its amorphous nature and low glass transition temperature (T_g = approximately ?40 °C). Successive polymerization of l ‐lactide afforded PLLA‐block‐P(CL‐stat‐DLLA)‐block‐PLLAs, which exhibited melting temperature (T_m = approximately 150 °C) for the crystalline PLLA segments and still low T_g (approximately ?30 °C) of the soft segments. The triblock copolymers showed very high elongation at break up to approximately 2800% and elastic properties. The corresponding d ‐triblock copolymers, PDLA‐block‐P(CL‐stat‐DLLA)‐block‐PDLAs (PDLA = poly(d ‐lactide)) were also prepared with the same procedure using d ‐lactide in place of l ‐lactide. When the PLLA‐block‐P(CL‐stat‐DLLA)‐block‐PLLA was blended with PDLA‐block‐P(CL‐stat‐DLLA)‐block‐PDLA, stereocomplex crystals were formed to enhance their T_m as well as tensile properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 489–495     

3D-Printed Nanocellulose-Based Cushioning–Antibacterial Dual-Function Food Packaging Aerogel

Cushioning and antibacterial packaging are the requirements of the storage and transportation of fruits and vegetables, which are essential for reducing the irreversible quality loss during the process. Herein, the composite of carboxymethyl nanocellulose, glycerin, and acrylamide derivatives acted as the shell and chitosan/AgNPs were immobilized in the core by using coaxial 3D-printing technology. Thus, the 3D-printed cushioning–antibacterial dual-function packaging aerogel with a shell–core structure (CNGA/C–AgNPs) was obtained. The CNGA/C–AgNPs packaging aerogel had good cushioning and resilience performance, and the average compression resilience rate was more than 90%. Although AgNPs was slowly released, CNGA/C–AgNPs packaging aerogel had an obvious antibacterial effect on E. coli and S. aureus. Moreover, the CNGA/C–AgNPs packaging aerogel was biodegradable. Due to the customization capabilities of 3D-printing technology, the prepared packaging aerogel can be adapted to more application scenarios by accurately designing and regulating the microstructure of aerogels, which provides a new idea for the development of food intelligent packaging.     

Organoantimony(III)‐Containing Tungstoarsenates(III): From Controlled Assembly to Biological Activity

A family of three sandwich‐type, phenylantimony(III)‐containing tungstoarsenates(III), [(PhSb^III){Na(H₂O)}As^III₂W₁₉O₆₇(H₂O)]^11? ( 1 ), [(PhSb^III)₂As^III₂W₁₉O₆₇(H₂O)]^10? ( 2 ), and [(PhSb^III)₃(B‐α‐As^IIIW₉O₃₃)₂]^12? ( 3 ), have been synthesized by one‐pot procedures and isolated as hydrated alkali metal salts, Cs₃K_3.5Na_4.5[(PhSb^III){Na(H₂O)}As^III₂W₁₉O₆₇(H₂O)]?41H₂O ( CsKNa ‐ 1 ), Cs_4.5K_5.5[(PhSb^III)₂As^III₂W₁₉O₆₇(H₂O)]?35H₂O ( CsK‐2 ), and Cs_4.5Na_7.5[(PhSb^III)₃(B‐α‐As^IIIW₉O₃₃)₂]?42H₂O ( CsNa ‐ 3 ). The number of incorporated {PhSb^III} units could be selectively tuned from one to three by careful control of the reaction parameters. The three compounds were characterized in the solid state by single‐crystal XRD, IR spectroscopy, and thermogravimetric analysis. The aqueous solution stability of sandwich polyanions 1 – 3 was also studied by multinuclear (¹H, ¹³C, ¹⁸³W) NMR spectroscopy. Effective inhibitory activity against six different kinds of bacteria was identified for all three polyanions, for which the activity increased with the number of incorporated {PhSb^III} groups.     

液体推进剂爆炸理论与实验研究

建立了自燃液体火箭推进剂爆炸热辐射效应和冲击波特性理论模型，介绍了实验研究的方法，给出了Ｎ２Ｏ４／ＵＤＭＨ液体推进剂爆炸产生的火球直径、火球温度、火球辐射热流、爆炸冲击波超压值等参数计算与实验观测结果，结果表明计算结果与实验观测结果吻合。由Ｎ２Ｏ４／ＵＤＭＨ液体火箭推进剂爆炸产生的火球最大直径Ｄｍａｘ和火球持续时间ｔ０是推进剂总重量Ｗ０的函数，根据实验数据整理的函数关系式:利用该理论模型预测了大型Ｎ２Ｏ４／ＵＤＭＨ组元液体推进剂运载火箭发生爆炸事故产生的上述参数，以及热辐射和冲击波不发生破坏和危害的安全距离。该计算模型可为载人航天器逃逸系统及航天靶场设计提供理论数据。     

Facile Way to Synthesize Nα‐Boc‐Nβ‐Cbz‐2,3‐ Diaminopropionic Acid Derivatives via 5‐Oxazolidinone

An economical and facile synthesis of N^α‐Boc‐N^β‐Cbz‐2,3‐diaminopropionic acid derivatives is reported. The key aspect of this method is employment of N‐Boc‐5‐oxazolidinone moiety to simultaneously provide proper protection of α‐amido and α‐carboxyl functional groups and affords the desired isocyanate 5 successfully by a Curtius rearrangement. The obtained intermediate 6 can be readily converted to various derivatives of N^α‐Boc‐N^β‐Cbz‐2,3‐diaminopropionic acid by conventional procedure.     

Synthesis and properties of cationic ionomers from poly(ester‐urethane)s based on polylactide

l ‐Lactide (l ‐LA) was polymerized in the presence of N‐methyldiethanolamine as an initiator and Sn(Oct)₂ as a catalyst to give hydroxy‐telechelic poly(l ‐lactide) (PLLA‐diol) bearing a tertiary amine group at the center of the polymer chain. Successive chain extension of the PLLA‐diol with hexamethylene diisocyanate afforded PLLA‐based poly(ester‐urethane)s (PEU) with equally spaced tertiary amine groups. Treatment of the PEU with iodomethane converted tertiary amine groups to quaternary ammonium groups to give cationic ionomers (PEU‐MeI). The thermal, mechanical, hydrophilic, and biodegradation properties of the obtained polymers were investigated. The thermal properties of the PEUs and the PEU‐MeIs were similar each other. The PEU‐MeIs exhibited higher tensile modulus than those of the starting PEUs. The contact angles of water on the PEU‐MeIs were lower than those of the PEUs with similar NMDA content indicating their higher hydrophilicity. In compost degradation tests, the PEU‐MeIs showed slower degradation than those of the PEUs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4423–4428