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121.
Vacuum Ultraviolet Free-Electron Laser Photoionization Mass Spectrometry of Alpha-pinene Ozonolysis 下载免费PDF全文
Xiangyu Zang Zhaoyan Zhang Chong Wang Tiantong Wang Huijun Zheng Hua Xie Jiayue Yang Dongxu Dai Guorong Wu Weiqing Zhang Gang Li Xueming Yang Ling Jiang 《化学物理学报(中文版)》2022,35(2):281-288
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使用纳米粒子进行疾病的诊断和治疗是当前研究的一个热点. 由于受到黏液层的阻碍, 纳米粒子对于黏膜上皮细胞的进入效果不佳, 从而限制了其对黏膜相关疾病的诊断和治疗. 本文设计合成了一种具有黏惰性的酸敏感纳米粒子(MSNs-pCBMA-DMMA), 可有效穿透黏液层进入黏膜上皮细胞. 首先采用溶胶-凝胶法合成了表面氨基化的介孔二氧化硅纳米粒子(MSNs-NH2), 然后通过原子转移自由基聚合法(ATRP)使两性离子羧基甜菜碱甲基丙烯酸酯(CBMA)在MSNs-NH2表面上聚合形成聚羧基甜菜碱甲基丙烯酸酯(pCBMA), 获得惰性化的粒子(MSNs-pCBMA), 最后将酸响应性分子2,3-二甲基马来酸酐(DMMA)修饰于MSNs-pCBMA表面, 制备了MSNs-pCBMA-DMMA. 场发射透射电子显微镜(TEM)、 傅里叶变换红外光谱(FTIR)、 氢核磁共振波谱(1H NMR)和纳米粒度Zeta电位测定仪等分析结果表明, 本文合成了MSNs-pCBMA-DMMA, 且粒子表面电位随pH值降低显著增加, 在pH=7.4~5.7范围内具有酸敏感能力. Transwell?小室实验表明, pCBMA的接枝提高了粒子在模拟黏液中的渗透速率, 而DMMA的修饰则进一步增强了粒子的扩散能力, 4 h内MSNs-pCBMA-DMMA的模拟黏液渗透率达到16.3%, 为MSNs-pCBMA的1.9倍, MSNs-NH2的3倍, 而以MSNs-NH2的表观渗透系数(Papp)为标准计算得到的MSNs-pCBMA-DMMA的相对表观渗透系数达到了2.96. 细胞毒性试验验证MSNs-pCBMA-DMMA粒子的生物安全性良好. 细胞摄取试验表明, 相比于其它粒子MSNs-pCBMA-DMMA能够更快的被黏膜上皮细胞摄取. 本文所构建的纳米粒子能够快速渗透黏液且易于被黏膜上皮细胞摄取, 为其应用于黏膜相关疾病的活体诊断和治疗提供了基础. 相似文献
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Cheng Sheng Dr. Zheng Ling Dr. Tanveer Ahmad Prof. Dr. Fang Xie Prof. Dr. Wanbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(23):e202200128
Regioselective [3+3] annulation of alkynyl ketimines with α-cyano ketones for the synthesis of polysubstituted 4H-pyran derivatives with a quaternary CF3-containing center has been realized by using Cu(OAc)2 as the catalyst. The novel strategy tolerates a wide range of α-CF3 alkynyl ketimines and α-cyano ketones with both aryl and alkyl substitutents. A preliminary asymmetric synthesis of chiral product 3 has been attempted by using copper and chiral thiourea as the cocatalyst with excellent yields (86-99 %) and good enantioselectivities (71–78 % ee). Furthermore, product 3 aa could be obtained on a gram-scale reaction with 75 % yield and 99 % ee after recrystallization. Several products were also transformed readily. Control experiments indicate that the reaction involves a process with a base-catalyzed or chiral thiourea-catalyzed Mannich-type reaction followed by a highly regioselective copper-catalyzed ring-closing reaction on the alkynyl moiety in a 6-endo-dig fashion. 相似文献
125.
Guanlin Li Ling Zhao Yicong Luo Youbin Peng Kai Xu Dr. Xiaohong Huo Prof. Dr. Wanbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200273
Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity. 相似文献
126.
Herein, we investigated the analytical features of potentiometric immunosensors for detection of alpha-fetoprotein (AFP) in hepatocellular carcinoma at different electrodes, such as carbon fiber microelectrode (CFME) and carbon-disk electrode (CDE), respectively. To construct such an immunosensor, anti-AFP capture antibodies were first conjugated covalently onto the activated electrodes through typical carbodiimide coupling. Thereafter, one-step immunoreaction protocol was successfully introduced to develop a new potentiometric immunoassay upon addition of AFP. Accompanying the antigen-antibody reaction, the surface charges of the modified electrodes were changed for the readout of electric potential. Results indicated that the linear range of CDE-based immunosensor was 0.1–100 ng mL−1 AFP, whereas the assay sensitivity by using CFME could be further increased to 3.2 pg mL−1 with the linear range from 0.01 to 500 ng mL−1 AFP. Meanwhile, CFME-based immunosensor showed high sensitivity, good reproducibility and specificity, and could be utilized for the analysis of human serum specimens with consistent results relative to commercialized ELISA kit. 相似文献
127.
Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device. 相似文献
128.
Microfluidic CE (MCE) is an effective solution for rapid and sensitive determination of multiple analytes. Herein, a dynamic coated cyclic olefin copolymer microchip was developed having an on-chip micropump for fluid velocity adjusting in electrophoretic separations. This micropump was fabricated by constructing a polyacrylamide gel membrane at one channel terminal. Once applying electric field across the membrane, a pressure-driven flow generated automatically to balance the electroosmotic flow (EOF) mismatch at the channel-membrane interface. The influence of gel precursor concentration and operating voltages on the fluid velocity was carefully evaluated. Moreover, the highly integration of injection, separation, and pumping units of the MCE system minimized the dead volume and provides satisfied column efficiency. Experiments showed that by adjusting of pumping voltage reduced the fluid velocity by a factor of 6, resulting six- and threefold resolving power enhancements of rhodamine dye mixture and amino acid mixture, respectively. Furthermore, the developed MCE method was applied for rhodamines and amino acids quantitation in food and cosmetics, with standard addition recoveries of 87.3–106.9% and 89.9–117.4%, respectively. These results were also confirmed by standard HPLC method, revealing the application potential in fast and onsite analysis of complex samples. 相似文献
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二氧化碳(CO2)光催化还原技术因兼具解决能源和全球变暖问题的潜力而受到关注。金属铁络合物作为分子型催化剂,具有价格低廉、量子效率高、结构可调控和选择性好等优势,表现出优异的CO2光催化还原性能,成为CO2光催化还原领域的研究热点。本文综述了近年来基于金属铁络合物光催化二氧化碳还原研究进展。介绍了铁金属络合物(如:铁卟啉、铁多吡啶、五齿铁配合物)CO2均相光催化还原体系,总结了体系的构成以及作用机理等,着重关注了体系的催化效率和产物的选择性。此外,综述了以半导体纳米材料/量子点作为光敏剂,金属铁络合物作为催化剂的非均相催化体系的研究进展。最后,对该领域未来的研究方向和所面临的挑战做出展望。 相似文献