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941.
Photochemical Regulation of Gene Expression Using Caged siRNAs with Single Terminal Vitamin E Modification 下载免费PDF全文
Yuzhuo Ji Jiali Yang Dr. Li Wu Dr. Lijia Yu Prof. Xinjing Tang 《Angewandte Chemie (International ed. in English)》2016,55(6):2152-2156
Caged siRNAs with a single photolabile linker and/or vitamin E (vitE) modification at the 5′ terminal were rationally designed and synthesized. These virtually inactive caged siRNAs were successfully used to photoregulate both firefly luciferase and GFP gene expression in cells with up to an 18.6‐fold enhancement of gene silencing activity, which represents one of the best reported photomodulation of gene silencing efficiencies to date. siRNA tracking and vitE competition experiments indicated that the inactivity of vitE‐modified siRNAs was not due to the bulky moiety of vitE; rather, the involvement of vitE‐binding proteins has a large contribution to caged siRNA inactivation by preventing the dissociation of siRNA/lipo complexes and/or siRNA release. Further patterning experiments revealed the ability to spatially regulate gene expression through simple light irradiation. 相似文献
942.
Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β‐Aminoketone Derivatives 下载免费PDF全文
Simon M. Nicolle Dr. William Lewis Prof. Dr. Christopher J. Hayes Prof. Dr. Christopher J. Moody 《Angewandte Chemie (International ed. in English)》2016,55(11):3749-3753
A highly stereoselective route to functionalized pyrrolidines by the metal‐catalyzed diverted N?H insertion of a range of diazocarbonyl compounds with β‐aminoketone derivatives is described. A number of catalysts (rhodium(II) carboxylate dimers, copper(I) triflate, and an iron(III) porphyrin) are shown to promote the process under mild conditions to give a wide range of highly substituted proline derivatives. The reaction starts as a metallocarbene N?H insertion but is diverted by an intermolecular aldol reaction. 相似文献
943.
Nitrogen‐Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics 下载免费PDF全文
Dr. Guang‐Hui Wang Dr. Zhengwen Cao Dr. Dong Gu Norbert Pfänder Ann‐Christin Swertz Bernd Spliethoff Hans‐Josef Bongard Dr. Claudia Weidenthaler Dr. Wolfgang Schmidt Dr. Roberto Rinaldi Prof. Dr. Ferdi Schüth 《Angewandte Chemie (International ed. in English)》2016,55(31):8850-8855
Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio‐oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen‐doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and “real‐world” biomass‐derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass‐derived phenolic stream is achieved under conditions of low severity. 相似文献
944.
Dr. Xiaoyu Han Wai‐Lun Chan Dr. Weijun Yao Dr. Yongjiang Wang Prof. Dr. Yixin Lu 《Angewandte Chemie (International ed. in English)》2016,55(22):6492-6496
Phosphine‐catalyzed enantioselective annulation reactions involving ketimines are a daunting synthetic challenge owing to the intrinsic low reactivity of ketimine substrates. A highly enantioselective [3+2] cycloaddition reaction that makes use of isatin‐derived ketimines as reaction partners was developed. Notably, both simple and γ‐substituted allenoates could be utilized, and various 3,2′‐pyrrolidinyl spirooxindoles with a tetrasubstituted stereocenter were obtained in excellent yields and with nearly perfect enantioselectivity (>98 % ee in all cases). 相似文献
945.
A Single Excitation‐Duplexed Imaging Strategy for Profiling Cell Surface Protein‐Specific Glycoforms 下载免费PDF全文
Na Wu Lei Bao Prof. Dr. Lin Ding Prof. Dr. Huangxian Ju 《Angewandte Chemie (International ed. in English)》2016,55(17):5220-5224
This work develops a site‐specific duplexed luminescence resonance energy transfer system on cell surface for simultaneous imaging of two kinds of monosaccharides on a specific protein by single near‐infrared excitation. The single excitation‐duplexed imaging system utilizes aptamer modified upconversion luminescent nanoparticles as an energy donor to target the protein, and two fluorescent dye acceptors to tag two kinds of cell surface monosaccharides by a dual metabolic labeling technique. Upon excitation at 980 nm, only the dyes linked to protein‐specific glycans can be lit up by the donor by two parallel energy transfer processes, for in situ duplexed imaging of glycoforms on specific protein. Using MUC1 as the model, this strategy can visualize distinct glycoforms of MUC1 on various cell types and quantitatively track terminal monosaccharide pattern. This approach provides a versatile platform for profiling protein‐specific glycoforms, thus contributing to the study of the regulation mechanisms of protein functions by glycosylation. 相似文献
946.
Radical Hydrodeiodination of Aryl,Alkenyl, Alkynyl,and Alkyl Iodides with an Alcoholate as Organic Chain Reductant through Electron Catalysis 下载免费PDF全文
Abhishek Dewanji Dr. Christian Mück‐Lichtenfeld Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2016,55(23):6749-6752
A simple and efficient method for radical hydrodeiodination is reported. The novel approach uses electron catalysis. In situ generated Na‐alcoholates are introduced as radical chain reducing reagents and reactions work with O2 as cheap initiator. Hydrodeiodination works on aryl, alkenyl, alkynyl iodides and a tert‐alkyl iodide also gets reduced applying the method. Albeit less general, the method is also applicable to the reduction of aryl bromides. The novel reagent is successfully used to conduct typical reductive radical cyclization reactions and mechanistic studies are reported. 相似文献
947.
Dr. Sreekumar Vellalath Prof. Dr. Daniel Romo 《Angewandte Chemie (International ed. in English)》2016,55(45):13934-13943
Although acylammonium salts are well‐studied, chiral α,β‐unsaturated acylammonium salts have received much less attention. While these intermediates are convenient synthons, which are readily available from several commodity unsaturated acids and acid chlorides, and possess three reactive sites, their application in organic synthesis has been limited because of the lack of appropriate chiral Lewis bases for their generation. In recent years, the utility of chiral, unsaturated acylammonium salts has expanded considerably, thus demonstrating the unique reactivity of this intermediate leading to the development of a diverse array of catalytic, asymmetric transformations including organocascade processes. This Minireview highlights the recent and growing interest in these intermediates which might spark further research into their untapped potential for asymmetric organocascade catalysis. A cursory comparison is made to related unsaturated iminium and acylazolium intermediates. 相似文献
948.
Dry Reforming of Methane on a Highly‐Active Ni‐CeO2 Catalyst: Effects of Metal‐Support Interactions on C−H Bond Breaking 下载免费PDF全文
B. Sc. Zongyuan Liu Dr. David C. Grinter Dr. Pablo G. Lustemberg Dr. Thuy‐Duong Nguyen‐Phan Dr. Yinghui Zhou B. Sc. Si Luo Dr. Iradwikanari Waluyo Dr. Ethan J. Crumlin Dr. Dario J. Stacchiola Prof. Jing Zhou Dr. Javier Carrasco Prof. H. Fabio Busnengo Dr. M. Verónica Ganduglia‐Pirovano Dr. Sanjaya D. Senanayake Prof. José A. Rodriguez 《Angewandte Chemie (International ed. in English)》2016,55(26):7455-7459
Ni‐CeO2 is a highly efficient, stable and non‐expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density‐functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO2?x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C 1s XPS region. The reforming of methane proceeds in a clean and efficient way. 相似文献
949.
Zongyang Qiu Prof. Li Song Prof. Jin Zhao Prof. Zhenyu Li Prof. Jinlong Yang 《Angewandte Chemie (International ed. in English)》2016,55(34):9918-9921
Metal‐nanoparticle‐catalyzed cutting is a promising way to produce graphene nanostructures with smooth and well‐aligned edges. Using a multiscale simulation approach, we unambiguously identified a “Pac‐Man” cutting mechanism, characterized by the metal nanoparticle “biting off” edge carbon atoms through a synergetic effect of multiple metal atoms. By comparing the reaction rates at different types of edge sites, we found that etching of an entire edge carbon row could be triggered by a single zigzag‐site etching event, which explains the puzzling linear dependence of the overall carbon‐atom etching rate on the nanoparticle surface area observed experimentally. With incorporation of the nanoparticle size effect, the mechanisms revealed herein open a new avenue to improve controllability in graphene cutting. 相似文献
950.
Isolating Reactions at the Picoliter Scale: Parallel Control of Reaction Kinetics at the Liquid–Liquid Interface 下载免费PDF全文
Gia Chuong Phan‐Quang Hiang Kwee Lee Prof. Xing Yi Ling 《Angewandte Chemie (International ed. in English)》2016,55(29):8304-8308
Miniaturized liquid–liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid–liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water‐in‐decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface‐enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p‐dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min?1 for the first‐order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods. 相似文献