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951.
Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} Polyoxometalates under Supramolecular Control 下载免费PDF全文
Caihong Zhan Jamie M. Cameron Jing Gao Jamie W. Purcell De‐Liang Long Leroy Cronin 《Angewandte Chemie (International ed. in English)》2014,53(39):10362-10366
We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}‐in‐{W76} cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO32?, Cl?, and Ag+ play in the self‐assembly of compounds 1 – 3 . 相似文献
952.
A Borinic Acid Polymer with Fluoride Ion‐ and Thermo‐responsive Properties that are Tunable over a Wide Temperature Range 下载免费PDF全文
Dr. Wen‐Ming Wan Dr. Fei Cheng Prof. Dr. Frieder Jäkle 《Angewandte Chemie (International ed. in English)》2014,53(34):8934-8938
A new type of smart borinic acid polymer with luminescence and multiple stimuli‐responsive properties is reported. In DMSO with small amounts of water, the homopolymer PBA shows a tunable upper critical solution temperature (UCST). As the amount of water increases from 0 to 2.5 % (v/v), the UCST rises linearly from 20 °C to 100 °C (boiling point of water). Thus, the thermal responsive behavior can be tuned over a wide temperature range. Furthermore, polymer solutions in DMSO show a reversible response to fluoride ions, which can be correlated to the presence of the Lewis acidic borinic acid groups. Upon addition of fluoride, the polymer becomes soluble because the functional R2BOH groups are converted into ionic [R2BF2]? groups, but turns insoluble again upon addition of H2O, which reverses this process. 相似文献
953.
Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3 下载免费PDF全文
Ming Shang Shang‐Zheng Sun Dr. Hong‐Li Wang Dr. Brian N. Laforteza Prof. Dr. Hui‐Xiong Dai Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2014,53(39):10439-10442
The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF3 has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (SEAr), as the key step. 相似文献
954.
Synthesis of Two‐Dimensional Transition‐Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium‐Ion Battery Applications 下载免费PDF全文
Dan Yang Dr. Ziyang Lu Dr. Xianhong Rui Xiao Huang Dr. Hai Li Dr. Jixin Zhu Wenyu Zhang Prof. Yeng Ming Lam Prof. Huey Hoon Hng Prof. Hua Zhang Prof. Qingyu Yan 《Angewandte Chemie (International ed. in English)》2014,53(35):9352-9355
Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well‐defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two‐dimensional (2D) nanoflakes of transition‐metal phosphates, including FePO4, Mn3(PO4)2, and Co3(PO4)2, with highly ordered mesoporous structures in a nonpolar solvent. The as‐obtained nanoflakes with thicknesses of about 3.7 nm are constructed from a single layer of parallel‐packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO4 nanoflakes were used as the cathode for a lithium‐ion battery, which exhibits excellent stability and high rate capabilities. 相似文献
955.
Nanxi Wang Dr. Yue Li Dr. Wei Niu Dr. Ming Sun Dr. Ronald Cerny Prof. Qingsheng Li Prof. Jiantao Guo 《Angewandte Chemie (International ed. in English)》2014,53(19):4867-4871
A safe and effective vaccine against human immunodeficiency virus type 1 (HIV‐1) is urgently needed to combat the worldwide AIDS pandemic, but still remains elusive. The fact that uncontrolled replication of an attenuated vaccine can lead to regaining of its virulence creates safety concerns precluding many vaccines from clinical application. We introduce a novel approach to control HIV‐1 replication, which entails the manipulation of essential HIV‐1 protein biosynthesis through unnatural amino acid (UAA*)‐mediated suppression of genome‐encoded blank codon. We successfully demonstrate that HIV‐1 replication can be precisely turned on and off in vitro. 相似文献
956.
Highly Enantioselective Kinetic Resolution of Axially Chiral BINAM Derivatives Catalyzed by a Brønsted Acid 下载免费PDF全文
Dr. Dao‐Juan Cheng Liang Yan Prof. Dr. Shi‐Kai Tian Ming‐Yue Wu Lu‐Xin Wang Zi‐Li Fan Dr. Sheng‐Cai Zheng Prof. Dr. Xin‐Yuan Liu Prof. Dr. Bin Tan 《Angewandte Chemie (International ed. in English)》2014,53(14):3684-3687
A highly efficient strategy for the kinetic resolution of axially chiral BINAM derivatives involving a chiral Brønsted acid‐catalyzed imine formation and transfer hydrogenation cascade process was developed. The kinetic resolution provides a convenient route to chiral BINAM derivatives in high yields with excellent enantioselectivities. 相似文献
957.
Combinatorially Designed Lipid‐like Nanoparticles for Intracellular Delivery of Cytotoxic Protein for Cancer Therapy 下载免费PDF全文
Dr. Ming Wang Kyle Alberti Shuo Sun Carlos Luis Arellano Prof. Dr. Qiaobing Xu 《Angewandte Chemie (International ed. in English)》2014,53(11):2893-2898
An efficient and safe method to deliver active proteins into the cytosol of targeted cells is highly desirable to advance protein‐based therapeutics. A novel protein delivery platform has been created by combinatorial design of cationic lipid‐like materials (termed “lipidoids”), coupled with a reversible chemical protein engineering approach. Using ribonuclease A (RNase A) and saporin as two representative cytotoxic proteins, the combinatorial lipidoids efficiently deliver proteins into cancer cells and inhibit cell proliferation. A study of the structure–function relationship reveals that the electrostatic and hydrophobic interactions between the lipidoids and the protein play a vital role in the formation of protein–lipidoid nanocomplexes and intracellular delivery. A representative lipidoid (EC16‐1) protein nanoparticle formulation inhibits cell proliferation in vitro and suppresses tumor growth in a murine breast cancer model. 相似文献
958.
Silver‐Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion 下载免费PDF全文
Dr. Feng Hu Xinxin Shao Dianhu Zhu Prof. Dr. Long Lu Prof. Dr. Qilong Shen 《Angewandte Chemie (International ed. in English)》2014,53(24):6105-6109
A silver‐catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver‐catalyzed decarboxylation in the “oil‐in‐water” droplets, could easily react with the trifluoromethylthiolating reagent to form the product. 相似文献
959.
Po‐Yeng Feng Yi‐Hung Liu Prof. Tien‐Sung Lin Prof. Shie‐Ming Peng Prof. Ching‐Wen Chiu 《Angewandte Chemie (International ed. in English)》2014,53(24):6237-6240
Chemical reduction of a hydroxyphenyl‐substituted borane triggers a sequential electron‐ and intramolecular hydrogen‐atom‐transfer process to afford a hydridoborate phenoxide dianion. On the other hand, hydrogen‐atom abstraction of the borane leads to the isolation of a neutral borylated phenoxyl radical, which can be transformed to the corresponding benzoquinone borataalkene derivative by reduction with cobaltocene. 相似文献
960.
Qi Wang Chenxi Zhang Dr. Bruce C. Noll Dr. Hai Long Dr. Yinghua Jin Prof. Dr. Wei Zhang 《Angewandte Chemie (International ed. in English)》2014,53(40):10663-10667
Shape‐persistent covalent organic polyhedrons (COPs) with ethynylene linkers are usually prepared through kinetically controlled cross‐coupling reactions. The high‐yielding synthesis of ethynylene‐linked rigid tetrameric cages via one‐step alkyne metathesis from readily accessible triyne precursors is presented. The tetrameric cage contains two macrocyclic panels and exhibits D2h symmetry. The assembly of such a COP is a thermodynamically controlled process, which involves the initial formation of macrocycles as key intermediates followed by the connection of two macrocycles with ethynylene linkages. With a large internal cavity, the cage exhibits a high binding selectivity toward C70 (K=3.9×103 L mol?1) over C60 (no noticeable binding). 相似文献