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41.
42.
Unexpected products are often found in the synthesis of sulfur-containing glycosides where the sulfur-containing group is acquired through substitution of a leaving group by a thioacetate reagent. Thus low yields have to be born. The reason has been disclosed to originate from the basicity and nucleophilicity of sulfur atom leading to a thioacetyl group migration in this study. The migration may occur through a five or six-membered ring tetrahedral intermediate, followed by cleavage of CS bond of this intermediate to form a sulfhydryl anion and subsequently another acetyl group migration from the thioacetate reagent to the sulfhydryl anion, leading to an unexpected product with an acetylated neighboring hydroxyl group. The occurrence of the migration may depend on the concentration of thioacetate reagent and the steric and stereoelectronic effects of the substrate itself. Based on these results, the yields for synthesis of sulfur-containing glycosides can be highly improved. 相似文献
43.
电磁力的计算是电磁成形这一新型加工工艺的关键问题之一,目前在工程界多采用近似的磁压力公式pm=B2/2μ0。该公式对加工工件半径较大且外加磁场频率较高时较为适用,在外加磁场频率较低或工件半径较小时有较大误差。本文基于Maxwell方程组推导了在外加横向磁场作用下金属圆板上涡电流分布的特征,进而给出了电磁力解析表达式,在此基础上得到修正的电磁压力公式。分析结果表明:本文得到的修正磁压力公式在工件半径较大,外加磁场频率较高时和原磁压力公式趋于一致,对于小尺寸,外加磁场频率较低的情形也能进行模拟.这对低频磁场下,小尺寸工件的磁致成形工艺具有指导意义。 相似文献
44.
建立一种结合便携式高分辨离子迁移谱(IMS)快速简便萃取唾液中的苯海拉明(DPH)的分散液-液微萃取法(DLLM E)。取2 mL唾液,采用10%(w:V)硫酸锌沉淀蛋白,以2 mL二氯甲烷为萃取剂对唾液中的苯海拉明进行萃取,萃取时间5 min,离心(3500 r/min,20 min),取二氯甲烷层,45℃真空干燥,甲醇复溶后进行IMS分析。结果表明,该方法可在短时间内完成对DPH的萃取分离及分析,DPH在39.4~1080 ng/mL范围内线性关系良好,标准曲线方程为I=3.62×103-0.754(R2=0.978),检出限和定量限分别为11.8和39.4 ng/mL,平均回收率为89.0%~112%,RSD≤1.5%。该方法可实现对人体唾液中苯海拉明的快速测定。 相似文献
45.
Yubin Fu Huan Yang Yixuan Gao Dr. Li Huang Dr. Reinhard Berger Dr. Junzhi Liu Dr. Hongliang Lu Dr. Zhihai Cheng Prof. Shixuan Du Prof. Hong-Jun Gao Prof. Xinliang Feng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8958-8964
We report the first bottom-up synthesis of NBN-doped zigzag-edged GNRs (NBN-ZGNR1 and NBN-ZGNR2) through surface-assisted polymerization and cyclodehydrogenation based on two U-shaped molecular precursors with an NBN unit preinstalled at the zigzag edge. The resultant zigzag-edge topologies of GNRs are elucidated by high-resolution scanning tunneling microscopy (STM) in combination with noncontact atomic force microscopy (nc-AFM). Scanning tunneling spectroscopy (STS) measurements and density functional theory (DFT) calculations reveal that the electronic structures of NBN-ZGNR1 and NBN-ZGNR2 are significantly different from those of their corresponding pristine fully-carbon-based ZGNRs. Additionally, DFT calculations predict that the electronic structures of NBN-ZGNRs can be further tailored to be gapless and metallic through one-electron oxidation of each NBN unit into the corresponding radical cations. This work reported herein provides a feasible strategy for the synthesis of GNRs with stable zigzag edges yet tunable electronic properties. 相似文献
46.
Dong H Zhou Y Pan X Cui F Liu W Liu J Ramström O 《The Journal of organic chemistry》2012,77(3):1457-1467
Organotin-mediated regioselective protection has been extensively used in organic synthesis for many years. However, the mechanistic origin of the resulting regioselectivity is still not clear. By the comparison of the steric and stereoelectronic effects controlling the geometry of five-membered rings formed from neighboring group participation, from intramolecular acyl group migration, or from orthoester transesterification on pyranoside rings, a theory on the pattern resulting from the reaction with dibutyltin oxide is presented. It is thus suggested that the regioselectivity of organotin-mediated protection is controlled by analogous steric and stereoelectronic effects as in neighboring group participation and acyl group migration, mainly dependent on the stereoelectronic effects of the pyranoside itself, and not related to complex stannylene structures. An organotin protection mechanism is also suggested, emanating from steric and stereoelectronic effects, nucleophilicity, and organotin acyl migration. 相似文献
47.
以新药设计原理中的拼合原理为指导,将对苯二酚一侧酚羟基与具有生物活性的氨基酸进行偶联,以期得到活性更好、毒性更低的对苯二酚氨基酸缀合物。 将对苯二酚的一侧酚羟基进行保护得到对苄氧基苯酚,将氨基被保护的氨基酸与其酚羟基进行偶联,去掉保护基后得到8种对苯二酚的氨基酸缀合物。 在对苄氧基苯酚的酚羟基上引入乙酸连接片段,与氨基酸甲酯盐酸盐进行偶联,去掉保护基后得到8种对苯二酚的氨基酸缀合物。 通过IR、1H NMR、13C NMR和ESI-MS等技术手段对所合成的16种氨基酸缀合物进行了结构表征。 对目标产物进行了美白活性研究。 结果表明,化合物HQ-3b、HQ-3c、HQ-4a、HQ-4b、HQ-7c和HQ-8a对酪氨酸酶的抑制作用优于阳性对照物α-熊果苷(IC50=3.60),其中HQ-4b的IC50值低至0.15,有望成为新型化妆品美白剂。 相似文献
48.
磺化杯芳烃具有非常强的分子键合能力, 被广泛用于水相超分子自组装研究. 介绍了磺化杯芳烃与客体阳离子形成超分子组装体的主要驱动力和形貌调控因素; 总结了包括主体诱导客体聚集、客体诱导主体聚集及主客体共组装在内的三种主要聚集模式; 并展望了其在刺激响应材料、药物传递载体、多功能超分子平台和超分子催化等领域的重要应用前景. 相似文献
49.
Qihui Shen Yixuan Shan Yang Lü Peng Xue Xian Shu Dongmei Li Yan Liu Xiaoyang Liu 《中国化学会会志》2019,66(8):815-821
In this study, a facile, efficient, and surfactant‐free method to synthesize silica nanosphere‐supported ultrafine silver nanoparticles (AgNPs) (~2.5 nm) was developed, and their antibacterial effects were investigated. In the synthesis process, the hydrolysis of 3‐mercaptopropyltrimethoxysilane was adopted to provide thiol groups and in situ reduce Ag+ to Ag0 for ultrafine AgNPs formation on the surface of the silica nanosphere. Electron microscopy characterization of the complex formed revealed that the ultrafine AgNPs were not agglomerated and grow without any surfactants because there were no excess electrons transported from the shell to reduce the silver ions to silver atoms. The antibacterial effects of the supported ultrafine AgNPs with the surfactant‐free surface were evaluated against the Escherichia coli even at very low dosage. After incubation with 20 μg/mL silica‐supported AgNPs up to 120 min, 99.7% of the E. coli were inactivated, according to the bacterial viability measured by flow cytometry. 相似文献
50.
通过对部分力学专业本科生和研究生的问卷调查, 了解学生对计算力学相关
方法与知识的掌握与使用情况, 并结合对学生相关调查现状分析的基础上, 探讨了计算
力学课程的内容与模式. 结合计算力学系列课程的开设与实践, 阐述了计算力学课程体系建
设与改革的一些思想和做法. 相似文献