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871.
872.
Peng Teng Geoffrey M. Gray Mengmeng Zheng Sylvia Singh Xiaopeng Li Lukasz Wojtas Arjan vanderVaart Jianfeng Cai 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7860-7864
Peptide‐mediated self‐assembly is a prevalent method for creating highly ordered supramolecular architectures. Herein, we report the first example of orthogonal C?X???X?C/C?X???π halogen bonding and hydrogen bonding driven crystalline architectures based on synthetic helical peptides bearing hybrids of l ‐sulfono‐γ‐AApeptides and natural amino acids. The combination of halogen bonding, intra‐/intermolecular hydrogen bonding, and intermolecular hydrophobic interactions enabled novel 3D supramolecular assembly. The orthogonal halogen bonding in the supramolecular architecture exerts a novel mechanism for the self‐assembly of synthetic peptide foldamers and gives new insights into molecular recognition, supramolecular design, and rational design of biomimetic structures. 相似文献
873.
Sheng‐Cai Zheng Qian Wang Jieping Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(27):9313-9317
Racemic 3,4‐dihydro‐2H‐pyrroles, hypothetical intermediates of the Barton–Zard reaction, were synthesized in a highly diastereoselective manner and fully characterized for the first time. Kinetic resolution of the dihydropyrroles with a quinine‐derived thiourea afforded the (+)‐3‐arylpyrrole products and recovered (+)‐3,4‐dihydro‐2H‐pyrroles with high efficiency (s‐factor up to 153). The resolved (+)‐3,4‐dihydro‐2H‐pyrroles underwent subsequent aromatization with a quinidine‐derived thiourea catalyst to afford (?)‐3‐arylpyrroles with excellent central‐to‐axial chirality transfer. In contrast to the well‐accepted Barton–Zard mechanism, the aromatization of the 3,4‐dihydro‐2H‐pyrroles in the presence of a bifunctional catalyst is believed to proceed by an unprecedented sequence involving syn elimination of HNO2 and aromatization. 相似文献
874.
Jianyou Mao Zhiting Wang Xinyu Xu Guoqing Liu Runsheng Jiang Haixing Guan Zhipeng Zheng Patrick J. Walsh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(32):11149-11154
Indoles are essential heterocycles in medicinal chemistry, and therefore, novel and efficient approaches to their synthesis are in high demand. Among indoles, 2‐aryl indoles have been described as privileged scaffolds. Advanced herein is a straightforward, practical, and transition‐metal‐free assembly of 2‐aryl indoles. Simply combining readily available 2‐fluorotoluenes, nitriles, LiN(SiMe3)2, and CsF enables the generation of a diverse array of indoles (38 examples, 48–92 % yield). A range of substituents can be introduced into each position of the indole backbone (C4 to C7, and aryl groups at C2), providing handles for further elaboration. 相似文献
875.
Jia Zhang Yue Yuan Minling Gao Zheng Han Chengyan Chu Yuguo Li Peter C. M. vanZijl Mingyao Ying Jeff W. M. Bulte Guanshu Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(29):9976-9980
While carbon dots (C‐dots) have been extensively investigated pertaining to their fluorescent, phosphorescent, electrochemiluminescent, optoelectronic, and catalytic features, their inherent chemical exchange saturation transfer magnetic resonance imaging (CEST MRI) properties are unknown. By virtue of their hydrophilicity and abundant exchangeable protons of hydroxyl, amine, and amide anchored on the surface, we report here that C‐dots can be adapted as effective diamagnetic CEST (diaCEST) MRI contrast agents. As a proof‐of‐concept demonstration, human glioma cells were labeled with liposomes with or without encapsulated C‐dots and implanted in mouse brain. In vivo CEST MRI was able to clearly differentiate labeled cells from non‐labeled cells. The present findings may encourage new applications of C‐dots for in vivo imaging in deep tissues, which is currently not possible using conventional fluorescent (near‐infrared) C‐dots. 相似文献
876.
金属/氮/碳催化剂(M/N/C,M=Fe、Co等)是最有发展前景的非贵金属电催化剂之一,其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳(g-C3N4)富含类吡啶氮和亚纳米孔腔结构,将g-C3N4包覆在高导电性碳纳米笼(hCNC)表面,进而利用表层g-C3N4的配位和限域作用锚定大量Co2+离子,获得的Co/g-C3N4/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性,其起始电位(0.97 V)与商业Pt/C催化剂相当,且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略. 相似文献
877.
Developing efficient water oxidation catalysts (WOCs) with earth-abundant elements still remains a challenging task for artificial photosynthesis. Iron-based WOC is a promising candidate because it is economically cheap, little toxic and environmentally friendly. In this study, we found that the catalytic water oxidation activity on amorphous iron-based oxide/hydroxide (FeOx) can be decreased by an order of magnitude after the dehydration process at room temperature. Thermogravimetric analysis, XRD and Raman results indicated that the dehydration process of FeOx at room temperature causes the almost completely loss of water molecule with no bulk structural changes. Based on this finding, we prepared hydrated ultrasmall (ca. 2.2 nm) FeOx nanoparticles of amorphous feature, which turns out to be extremely active as WOC with turnover frequency (TOF) up to 9.3 s?1 in the photocatalytic Ru(bpy)32+-Na2S2O8 system. Our findings suggest that future design of active iron-based oxides as WOCs requires the consideration of their hydration status. 相似文献
878.
Zhi-min Zheng Cai-hong Xu Jian Jiang Chang-yu Ren Wei Gao Ze-min Xie Center for Molecular Science Institute of Chemistry Chinese Academy of Sciences Beijing China 《高分子科学》2002,(6):559-564
Silicone rubber (SIR) shows superior performance when used outdoors, but its surface can be transformed frominherently hydrophobic to hydrophilic by the adsorption of contaminants. Al(OH)_3, Al_2O_3, quartz powder and active carbonwere selected as authentic contaminants. Hydrophobicity of the surface was determined using contact angle measurement.The results indicate that the adsorbability of the contaminants can strongly affect the hydrophobicity of contaminated SIRsurface. The increasing rate of contact angle of specimens contaminated by Al(OH)_3 was much faster than that by Al_2O_3 andquartz due to the adsorption of migrated low molecular weight (LMW) polydimethylsiloxanes. Specimens contaminated byactive carbon could achieve sunde hydrophobicity within 15 min because active carbon has high adsorbability. Surfaces ofcontaminated ultrapure SIR, polytetrafluoroethylene (PTFE) and glass remain hydrophilic because they contain no mobileLMW components. The addition of oligomeric polydimethylsiloxanes has little effect on the hydrophobicity of contaminantscovered on SIR surface. 相似文献
879.
IntroductionThemethoxyradical (CH3O)isanimportantinter mediateinthephotochemicaloxidationofhydrocarbonsintheatmosphere ,1 3andplaysasignificantroleintrans formingnitricoxidetonitrogendioxide .4 Similarly ,thereactionmechanismsofhydroxylandcarbonmonoxide5,6ando… 相似文献
880.
Zhen Jun WANG* Zheng Hua SONG Department of Chemistry Northwest University Xian 《中国化学快报》2003,14(3):283-286
Benzoicacidisacommonadditiveusedwidelyasfoodpreservativeandplasticizer.Itcouldpromoteseverereactiontoallergicpopulationevenatlowconcentrationlevel1.Routinemethodsfortheassayofbenzoicacidincludeschromatographic2-6,spectrophotometry7,8,capillaryelectrophoresis9-13andelectrochemicaltitration14.Stokes15etal.monitoredairbornebenzoicacidbasedonsurface-enhancedRamanscatteringtechniques.Thereisalsoreportonamicrobialsensorusingpseudomonasforbenzoicacidandtheirderivativesinaqua16.Interestofusinglumines… 相似文献