含有冠醚基团的有机硅化合物 Ⅲ.烯氧甲基15-冠-5和18-冠-6的硅氢化

本文报道了烯丙氧甲基及十一烯氧甲基15-冠-5与18-冠-6的合成、硅氢化、固载化,以及所得到的气相法二氧化硅固载的冠醚和含冠醚侧基的有机硅树脂对苦味酸钠、钾的络合容量和正溴壬烷碘代反应的相转移催化活性。     

基于萘基块新型开链冠醚的合成及晶体结构研究

以3,6-二溴-2,7-二羟基萘为起始原料,经与2-溴-N-苯基乙酰胺醚化,再用硼氢化钠和三氟化硼乙醚还原得基于萘基块新型的开链冠醚,两步总收率为96%.利用单晶X衍射研究其结构,晶体为三斜晶系,P-1空间群,a=9.588(3),b=10.898(3),c=13.060(4),α=103.190(4)°,β=93.953(4)°,γ=115.622(5)°,V=1176.0(6)3,Z=2,Dc=1.571 g/cm3,λ=0.71075 nm,μ(Mo Kα)=3.472 mm-1,Mr=353.22,F(000)=560.在晶体结构中,分子中的一个N—H基团与另外一分子形成双分叉氢键N—H…Br和N—H…O,进而组装成二聚体.这些中心对称的二聚体进一步通过C—H…π相互作用叠加成二维层状结构平行于(110)面.     

Fatty acid amide hydrolase inhibitors. 2. Novel synthesis of sterically hindered azabenzhydryl ethers and an improved synthesis of VER-156084

We report an improved synthesis of the fatty acid amide hydrolase (FAAH) inhibitor VER-156084. The key step is a novel, environmentally benign etherification to form an unusual, highly hindered azabenzhydryl ether. The method is applied to a variety of primary and secondary alcohols.     

Degradation-fragmentation of marine plastic waste and their environmental implications: A critical review

This review critically evaluates the plastic accumulation challenges and their environmental (primarily) and human (secondarily) impacts. It also emphasizes on their degradation and fragmentation phenomena under marine conditions. In addition, it takes into account the leachability of the various chemical substances (additives) embedded in plastic products to improve their polymeric properties and extend their life. Regardless of their effectiveness in enhancing the polymeric function of plastic products, these additives can potentially contaminate air, soil, food, and water. Several findings have shown that, regardless of their types and sizes, plastics can be degraded and/or fragmented under marine conditions. Therefore, the estimation of fragmentation and degradation rates via a reliable developed model is required to better understand the marine environmental status. The main parameter, which is responsible for initiating the fragmentation of plastics, is sunlight/UV radiation. Yet, UV- radiation alone is not enough to fragment some plastic polymer types under marine conditions, additional factors are needed such as mechanical abrasion. It should be also mentioned that most current studies on plastic degradation and fragmentation centered on the primary stages of degradation. Thus, further studies are needed to better understand these phenomena and to identify their fate and environmental effects.     

Cellulose filter paper immobilized α-glucosidase and its application to screening inhibitors from traditional Chinese medicine

In this study, α-glucosidase was successfully immobilized on cellulose filter paper and further applied to screening inhibitors from traditional Chinese medicines combined with capillary electrophoresis analysis. For α-glucosidase immobilization, a cellulose filter paper was used as the carrier and grafted with amino groups by coating chitosan, then α-glucosidase was covalently bonded on the amino-modified carrier via epoxy ring-opening reaction using polyethylene glycol diglycidyl ether as the crosslinker. Several parameters influencing the enzyme immobilization were optimized and the optimal values were enzyme concentration of 4 U/mL, polyethylene glycol diglycidyl ether concentration of 1.25%, chitosan concentration of 7.5 mg/mL, immobilization pH 7.0, crosslinking time of 4 h and immobilization time of 2 h. The immobilized α-glucosidase exhibited good batch-to-batch reproducibility (RSD = 2.1%, n = 5), excellent storage stability (73.5% of its initial activity after being stored at 4°C for 15 days), and reusability (75% of its initial activity after 10 repeated cycles). The Michaelis constant of immobilized α-glucosidase and half-maximal inhibitory concentration of acarbose were calculated to be 1.12 mM and 0.38 μM, respectively. Finally, the immobilized α-glucosidase was used for screening inhibitors from 14 kinds of Traditional Chinese Medicine extracts, and Sanguisorbae Radix showed the strongest inhibitory effect on α-glucosidase.     

Preparation and Properties of Poly（ether ether ketone）/Carbon Nanotube Modified Polypropylene Janus Composite Separator北大核心CSCD

Lithium-ion batteries （LIBs）have attracted wide attention because of their broad prospects in electric vehicles. However,the safety problems and low multiplier performance of the commercial polyolefin separator limit their further development,due to the poor dimensional thermal stability and low electrolyte absorption rate. Poly（ether ether ketone）（PEEK）and carbon nanotube（CNT）are compounded to coat on polypropylene （PP） to prepare Janus composite separator （PP@C） through the phase inversion method. PP@C composite separator does not deform at 180 ℃ for 0. 5 h（only slight deformation）,illustrating excellent thermal stability. The electrolyte absorption rate of PP@C2 is 193. 8%. The electrolyte uptake rate of the PP@C2 composite membrane was 193. 8%,which was 64. 5% higher than the PP membrane,showing a superduper electrolyte permeability. As a result,the specific discharge capacity of LIBs assembled with PP@C2 composite separator is 157. 6 mA·h/g at 0. 2 C and 129. 8 mA·h/g at 2 C,showing good rate performance with the capacity recovery rate of more than 99%. This might be attributed to the ultra-high thermal stability of PEEK,the good affinity of the electrolyte,the high conductivity of CNT,as well as the uniform dispersion of Li+ ,so that the separator can have excellent electrochemical performance while improving safety. © 2022, Science Press (China). All rights reserved.     

计算化学在正丁醚制备实验教学中的应用*

正丁醚的制备是重要的大学有机化学实验,为提高学生对该实验所涉及的反应机理和关键操作要点的深入了解,采用Gaussian计算软件对正丁醇在酸催化下和无催化剂下的反应体系进行了研究,重点考察了酸催化下反应的主、副反应方向的反应机理。结果表明无催化剂下,正丁醇在常压液相下几乎不能发生反应;在酸催化下,正丁醇发生取代反应生成醚的反应路径是优势反应通道;酸催化下正丁醇的取代和消除反应速率常数均随温度增加而迅速增大,但消除反应的反应速率随温度增加更快,温度超过420 K消除反应将变得很明显,综合考虑,制备正丁醚的反应温度应控制在130~140 ℃之间较为合适。利用计算化学以图、表和动图等形式直观、动态、量化地解释了正丁醇成醚和成烯反应的竞争,该结果有助于更好地控制该反应体系,可用作实验教材的补充内容。     

无催化剂下醇和酚的高效O-硅基化

硅醚类化合物广泛应用于有机合成、 分离分析和精细化工等领域. 六甲基二氮硅烷是近年来发展的一种新型硅基化试剂, 被用于硅醚的高效合成, 但由于六甲基硅烷较为惰性, 通常需要加入催化剂活化. 本文报道了一种无催化剂下醇、 酚的高效硅基化新方法. 研究结果表明, 该方法可以兼容一级苄醇、 杂芳基苄醇、 脂肪醇, 二级醇甚至三级醇, 多数反应可以实现定量转化, 无需柱层析即可实现产物的分离纯化. 该方法可以拓展到酚的高效硅醚化, 也可以很方便地放大到100 mmol, 收率达到99%, 表明该方法具有较好的实用价值.     

咔唑-N，S-杂冠醚类荧光探针的合成及其检测Ag+性质

以双(2?氯乙基)氨基甲酸叔丁酯、2,2?(乙烷?1,2?二丁基(氧基))二乙硫醇和N?乙基咔唑为起始原料,设计、合成了一种含有杂冠醚基团的新型荧光探针分子L,其结构经¹H NMR、¹³C NMR及高分辨质谱进行了表征。随后利用荧光光谱在水/乙醇溶剂(4∶1,V/V)中研究了探针L对Ag⁺的选择性识别。研究结果表明,探针L与Ag⁺以1∶1的比例配位。通过计算得到配位常数K_a为2.01×10⁵ L·mol^-1,检测限为4.13μmol·L^-1。通过实验证明,该探针分子可应用于河流等环境水样中Ag⁺的检测。     

Photochromic crown ethers

An amphiphilic crown-containing styryl dye (1) was synthesized, and the effects of irradiation, temperature, and alkali and alkali-earth metal ions on the conductivity and optical spectra of its solutions in dioctyl phthalate were studied. Compound1 in thetrans-form almost completely exists as ion pairs (IP). Irradiation at a long-wavelength absorption maximum (λ_max) results in a reversible increase in the conductivity and, hence, a degree of dissociation of IP (α); these parameters decrease when complexes with metal ions are formed. The relaxation times for the photoinduced conductivity coincide with a decrease in the extinction within experimental error in the 20–60°C temperature range. The photoinduced increase in α is caused bytrans—cis-isomerization and an increase in steric hindrances for the interaction of the ClO₄ ⁻ anion with the N⁺ atom of benzothiazolium in thecis-form of1. The activation energies for the darkcis—trans-relaxation, absolute α values, and thermodynamic parameters of dissociation of IP in thetrans-form, as well as the α values in a photostationary mixture ofcis—trans-isomers, were estimated. The decrease in α after binding with metal ions is likely caused by the redistribution of the positive charge to benzothiazolium through the conjugated system of1. Correlations between the decrease in conductivity (decrease in α) and the hypsochromic shift Δλ_max after the formation of complexes between1 and metal ions were observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1296–1301, July, 1997.