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991.
Modifying the Steric Properties in the Second Coordination Sphere of Designed Peptides Leads to Enhancement of Nitrite Reductase Activity 下载免费PDF全文
Dr. Karl J. Koebke Dr. Fangting Yu Elvin Salerno Casey Van Stappen Dr. Alison G. Tebo Prof. James E. Penner‐Hahn Prof. Vincent L. Pecoraro 《Angewandte Chemie (International ed. in English)》2018,57(15):3954-3957
Protein design is a useful strategy to interrogate the protein structure‐function relationship. We demonstrate using a highly modular 3‐stranded coiled coil (TRI‐peptide system) that a functional type 2 copper center exhibiting copper nitrite reductase (NiR) activity exhibits the highest homogeneous catalytic efficiency under aqueous conditions for the reduction of nitrite to NO and H2O. Modification of the amino acids in the second coordination sphere of the copper center increases the nitrite reductase activity up to 75‐fold compared to previously reported systems. We find also that steric bulk can be used to enforce a three‐coordinate CuI in a site, which tends toward two‐coordination with decreased steric bulk. This study demonstrates the importance of the second coordination sphere environment both for controlling metal‐center ligation and enhancing the catalytic efficiency of metalloenzymes and their analogues. 相似文献
992.
Active Intracellular Delivery of a Cas9/sgRNA Complex Using Ultrasound‐Propelled Nanomotors 下载免费PDF全文
Malthe Hansen‐Bruhn Dr. Berta Esteban‐Fernández de Ávila Dr. Mara Beltrán‐Gastélum Prof. Jing Zhao Dr. Doris E. Ramírez‐Herrera Pavimol Angsantikul Prof. Kurt Vesterager Gothelf Prof. Liangfang Zhang Prof. Joseph Wang 《Angewandte Chemie (International ed. in English)》2018,57(10):2657-2661
Direct and rapid intracellular delivery of a functional Cas9/sgRNA complex using ultrasound‐powered nanomotors is reported. The Cas9/sgRNA complex is loaded onto the nanomotor surface through a reversible disulfide linkage. A 5 min ultrasound treatment enables the Cas9/sgRNA‐loaded nanomotors to directly penetrate through the plasma membrane of GFP‐expressing B16F10 cells. The Cas9/sgRNA is released inside the cells to achieve highly effective GFP gene knockout. The acoustic Cas9/sgRNA‐loaded nanomotors display more than 80 % GFP knockout within 2 h of cell incubation compared to 30 % knockout using static nanowires. More impressively, the nanomotors enable highly efficient knockout with just 0.6 nm of the Cas9/sgRNA complex. This nanomotor‐based intracellular delivery method thus offers an attractive route to overcome physiological barriers for intracellular delivery of functional proteins and RNAs, thus indicating considerable promise for highly efficient therapeutic applications. 相似文献
993.
Naoki Wada Dr. Roland D. Kersten Takahiro Iwai Shoukou Lee Dr. Fumie Sakurai Dr. Takashi Kikuchi Dr. Daishi Fujita Prof. Makoto Fujita Prof. Jing‐Ke Weng 《Angewandte Chemie (International ed. in English)》2018,57(14):3671-3675
Characterization of complex natural product mixtures to the absolute structural level of their components often requires significant amounts of starting materials and lengthy purification process, followed by arduous structure elucidation efforts. The crystalline sponge (CS) method has demonstrated utility in the absolute structure elucidation of isolated organic compounds at miniscule quantities compared to conventional methods. In this work, we developed a new CS‐based workflow that greatly expedites the in‐depth structural analysis of crude natural product extracts. Using a crude extract of the red alga Laurencia pacifica, we showed that CS affinity screening prior to compound isolation enables prioritization of analytes present in the extract, and we subsequently resolved the molecular structures of six sesquiterpenes with stereochemical clarity from around 10 mg crude extract. This study demonstrates a new chemotyping workflow that can greatly accelerate natural product discovery from complex samples. 相似文献
994.
Dr. Javeed Mahmood Seok‐Jin Kim Hyuk‐Jun Noh Dr. Sun‐Min Jung Ishfaq Ahmad Dr. Feng Li Jeong‐Min Seo Prof. Jong‐Beom Baek 《Angewandte Chemie (International ed. in English)》2018,57(13):3415-3420
A three‐dimensional (3D) cage‐like organic network (3D‐CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D‐CON can be prepared using an easy but powerful route, which is essential for commercial scale‐up. The resulting fused aromatic 3D‐CON exhibited a high Brunauer–Emmett–Teller (BET) specific surface area of up to 2247 m2 g?1. More importantly, the 3D‐CON displayed outstanding low pressure hydrogen (H2, 2.64 wt %, 1.0 bar and 77 K), methane (CH4, 2.4 wt %, 1.0 bar and 273 K), and carbon dioxide (CO2, 26.7 wt %, 1.0 bar and 273 K) uptake with a high isosteric heat of adsorption (H2, 8.10 kJ mol?1; CH4, 18.72 kJ mol?1; CO2, 31.87 kJ mol?1). These values are among the best reported for organic networks with high thermal stability (ca. 600 °C). 相似文献
995.
Photocatalytic Hydrogen Production Coupled with Selective Benzylamine Oxidation over MOF Composites 下载免费PDF全文
Hang Liu Caiyun Xu Dr. Dandan Li Prof. Dr. Hai‐Long Jiang 《Angewandte Chemie (International ed. in English)》2018,57(19):5379-5383
Photocatalytic water splitting requires separation of the mixed H2 and O2 products and is often hampered by the sluggish O2‐producing half reaction. An approach is now reported to address these issues by coupling the H2‐producing half reaction with value‐added benzylamine oxidation reaction using metal–organic framework (MOF) composites. Upon MOF photoexcitation, the electrons rapidly reduce the protons to generate H2 and the holes promote considerable benzylamine oxidation to N‐benzylbenzaldimine with high selectivity. Further experimental characterizations and theoretical calculation reveal that the highly conjugated s‐triazine strut in the MOF structure is crucial to the efficient charge separation and excellent photocatalytic activity. 相似文献
996.
A Multi‐signal Fluorescent Probe with Multiple Binding Sites for Simultaneous Sensing of Cysteine,Homocysteine, and Glutathione 下载免费PDF全文
Guo‐xing Yin Ting‐ting Niu Ya‐bing Gan Ting Yu Dr. Peng Yin Prof. Hai‐min Chen Prof. You‐yu Zhang Prof. Hai‐tao Li Prof. Shou‐zhuo Yao 《Angewandte Chemie (International ed. in English)》2018,57(18):4991-4994
A novel fluorescent probe was developed by integrating chlorinated coumarin and benzothiazolylacetonitrile and exploited for simultaneous detection of cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). Featuring four binding sites and different reaction mechanisms for different biothiols, this probe exhibited rapid fluorescence turn‐on for distinguishing Cys, Hcy, and GSH with 108‐, 128‐, 30‐fold fluorescence increases at 457, 559, 529 nm, respectively, across different excitation wavelengths. Furthermore, the probe was successfully applied to the fluorescence imaging of endogenous Cys and GSH and exogenous Cys, Hcy, and GSH in living cells. 相似文献
997.
Lingxiang Wang Dr. Liang Wang Jian Zhang Xiaolong Liu Hai Wang Prof. Wei Zhang Qi Yang Jingyuan Ma Xue Dong Seung Jo Yoo Dr. Jin‐Gyu Kim Xiangju Meng Prof. Feng‐Shou Xiao 《Angewandte Chemie (International ed. in English)》2018,57(21):6104-6108
Methods for the hydrogenation of CO2 into valuable chemicals are in great demand but their development is still challenging. Herein, we report the selective hydrogenation of CO2 into ethanol over non‐noble cobalt catalysts (CoAlOx), presenting a significant advance for the conversion of CO2 into ethanol as the major product. By adjusting the composition of the catalysts through the use of different prereduction temperatures, the efficiency of CO2 to ethanol hydrogenation was optimized; the catalyst reduced at 600 ° gave an ethanol selectivity of 92.1 % at 140 °C with an ethanol time yield of 0.444 mmol g?1 h?1. Operando FT‐IR spectroscopy revealed that the high ethanol selectivity over the CoAlOx catalyst might be due to the formation of acetate from formate by insertion of *CHx, a key intermediate in the production of ethanol by CO2 hydrogenation. 相似文献
998.
Ana Sánchez‐Iglesias Nathalie Claes Dr. Diego M. Solís Dr. Jose M. Taboada Prof. Sara Bals Prof. Luis M. Liz‐Marzán Dr. Marek Grzelczak 《Angewandte Chemie (International ed. in English)》2018,57(12):3183-3186
A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions. 相似文献
999.
Transient and Persistent Room‐Temperature Mechanoluminescence from a White‐Light‐Emitting AIEgen with Tricolor Emission Switching Triggered by Light 下载免费PDF全文
Jian‐An Li Jinghong Zhou Dr. Zhu Mao Dr. Zongliang Xie Dr. Zhan Yang Prof. Bingjia Xu Prof. Cong Liu Xin Chen Dingyang Ren Hui Pan Prof. Guang Shi Prof. Yi Zhang Prof. Zhenguo Chi 《Angewandte Chemie (International ed. in English)》2018,57(22):6449-6453
Persistent luminescence from purely organic materials is basically triggered by light and electricity, which largely confines its practical applications. A purely organic AIEgen exhibits not only persistent photoluminescence, but also transient and persistent room‐temperature mechanoluminescence. By simply turning on and off a UV lamp, tricolor emission switching between blue, white, and yellow was achieved. The data from single‐crystal structure analysis and theoretical calculation suggest that mechanism of the observed persistent mechanoluminescence (pML) is correlated with the strong spin–orbit coupling of the bromine atom, as well as the formation of H‐aggregates and restriction of intramolecular motions in noncentrosymmetric crystal structure. These results outline a fundamental principle for the development of new pML materials, providing an important step forward in expanding the application scope of persistent luminescence. 相似文献
1000.
Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs 下载免费PDF全文
Dr. Bartosz Szyszko Monika Przewoźnik Dr. Michał J. Białek Dr. Agata Białońska Prof. Dr. Piotr J. Chmielewski Dr. Jakub Cichos Prof. Dr. Lechosław Latos‐Grażyński 《Angewandte Chemie (International ed. in English)》2018,57(15):4030-4034
Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene. 相似文献