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31.
Hao Zhuo Xin Chi Mengtian Jiang Prof. Dr. Haibing Xu Prof. Dr. Minghua Zeng 《化学:亚洲杂志》2021,16(9):1165-1170
Attaching AIE-active L1 ([1,1′:2′,1′′:4′′,1′′′-quaterphenyl]-2-yldiphenylphosphane) to AuCl, shortened the distances of P−C bonds to promote electron cloud overlap between AuI and L1 , affords 1 ( L1 AuCl) with aggregation-induced phosphorescence enhancement (AIPE) activity by 3LMCT transitions. Then substituting the coplanar L2 (9-ethynylanthracene) for the Cl− in 1 providing 2 , switches the luminescence to aggregation-caused quenching (ACQ) activity. Furthermore, we restore the performance from ACQ to AIPE by metathesis reactions to transfer 2 into 1 . It is versatile synthetic strategy of reversible transformation between 1 and 2 that switches the luminescence of organogold(I) between AIPE and ACQ through balancing auxiliary ligands around the given metal. 相似文献
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Xiao-Guang Yang Feng-Huan Du Jun-Jie Li Prof. Dr. Chi Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200272
The development of convenient new methods for the synthesis of organic azides is highly desirable. Herein, we report a practical method for dehydroxyazidation of alcohols via an SN2 pathway involving PPh3 and trifunctional benziodazolone-based hypervalent azido-iodine(III) reagents, which function as an electrophilic center, an azido source, and a base. This mild, chemoselective method was used for late-stage azidation of structurally complex alcohols, as well as for a new synthetic route to the antiepileptic drug rufinamide. The reaction mechanism was also investigated both experimentally and computationally. 相似文献
34.
One‐Step Pyro‐Synthesis of a Nanostructured Mn3O4/C Electrode with Long Cycle Stability for Rechargeable Lithium‐Ion Batteries 下载免费PDF全文
Muhammad Hilmy Alfaruqi Dr. Jihyeon Gim Sungjin Kim Jinju Song Pham Tung Duong Jeonggeun Jo Dr. Joseph Paul Baboo Dr. Zhiliang Xiu Dr. Vinod Mathew Prof. Jaekook Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2039-2045
A nanostructured Mn3O4/C electrode was prepared by a one‐step polyol‐assisted pyro‐synthesis without any post‐heat treatments. The as‐prepared Mn3O4/C revealed nanostructured morphology comprised of secondary aggregates formed from carbon‐coated primary particles of average diameters ranging between 20 and 40 nm, as evidenced from the electron microscopy studies. The N2 adsorption studies reveal a hierarchical porous feature in the nanostructured electrode. The nanostructured morphology appears to be related to the present rapid combustion strategy. The nanostructured porous Mn3O4/C electrode demonstrated impressive electrode properties with reversible capacities of 666 mAh g?1 at a current density of 33 mA g?1, good capacity retentions (1141 mAh g?1 with 100 % Coulombic efficiencies at the 100th cycle), and rate capabilities (307 and 202 mAh g?1 at 528 and 1056 mA g?1, respectively) when tested as an anode for lithium‐ion battery applications. 相似文献
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36.
Jian Xu Qingsong Xu Lunzhao Yi Chi‐On Chan Daniel Kam‐Wah Mok 《Journal of Chemometrics》2016,30(1):37-45
High throughput data are frequently observed in contemporary chemical studies. Classification through spectral information is an important issue in chemometrics. Linear discriminant analysis (LDA) fails in the large‐p‐small‐n situation for two main reasons: (1) the sample covariance matrix is singular when p > n and (2) there is an accumulation of noise in the estimation of the class centroid in high dimensional feature space. The Independence Rule is a class of methods used to overcome these drawbacks by ignoring the correlation information between spectral variables. However, a strong correlation is an essential characteristic of spectral data. We proposed a new correlation‐assisted nearest shrunken centroid classifier (CA‐NSC) to incorporate correlation information into the classification. CA‐NSC combines two sources of information [class centroid (mean) and correlation structure (variance)] to generate the classification. We used two real data analyses and a simulation study to verify our CA‐NSC method. In addition to NSC, we also performed a comparison with the soft independent modeling of class analogy (SIMCA) approach, which uses only correlation structure information for classification. The results show that CA‐NSC consistently improves on NSC and SIMCA. The misclassification rate of CA‐NSC is reduced by almost half compared with NSC in one of the real data analyses. Generally, correlation among variables will worsen the performance of NSC, even though the discriminatory information contained in the class centroid remains unchanged. If only correlation structure information is used (as in the case of SIMCA), the result will be satisfactory only when the correlation structure alone can provide sufficient information for classification. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
37.
Solventless Formation of G‐Quartet Complexes Based on Alkali and Alkaline Earth Salts on Au(111) 下载免费PDF全文
Chi Zhang Likun Wang Lei Xie Huihui Kong Prof. Dr. Qinggang Tan Liangliang Cai Qiang Sun Prof. Dr. Wei Xu 《Chemphyschem》2015,16(10):2099-2105
Template cations have been extensively employed in the formation, stabilization and regulation of structural polymorphism of G‐quadruplex structures in vitro. However, the direct addition of salts onto solid surfaces, especially under ultra‐high‐vacuum (UHV) conditions, to explore the feasibility and universality of the formation of G‐quartet complexes in a solventless environment has not been reported. By combining UHV‐STM imaging and DFT calculations, we have shown that three different G‐quartet‐M (M: Na/K/Ca) complexes can be obtained on Au(111) using alkali and alkaline earth salts as reactants. We have also identified the driving forces (intra‐quartet hydrogen bonding and electrostatic ionic bonding) for the formation of these complexes and quantified the interactions involved. Our results demonstrate a novel route to fabricate G‐quartet‐related complexes on solid surfaces, providing an alternative feasible way to bring metal elements to surfaces for constructing metal–organic systems. 相似文献
38.
A Filled‐Honeycomb‐Structured Crystal Formed by Self‐Assembly of a Janus Polyoxometalate–Silsesquioxane (POM–POSS) Co‐Cluster 下载免费PDF全文
Chi Ma Han Wu Zi‐Han Huang Dr. Ruo‐Hai Guo Dr. Min‐Biao Hu Dr. Christian Kübel Prof. Dr. Li‐Tang Yan Prof. Dr. Wei Wang 《Angewandte Chemie (International ed. in English)》2015,54(52):15699-15704
Clusters with diverse structures and functions have been used to create novel cluster‐assembled materials (CAMs). Understanding their self‐assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo‐functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell‐shaped Janus co‐cluster. In a mixed solvent of acetonitrile and water, it self‐assembles into a crystal with a honeycomb superstructure constructed by hexagonal close‐packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse‐grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano‐architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications. 相似文献
39.
Density functional calculations are performed to study the energetic, structural, and electronic properties of graphene and silicene functionalized with hydrogen. Our calculations predict that H atoms bind much more strongly to silicene than to graphene. The adsorbed H atoms tend to cooperatively stabilize each other leading to a two‐dimensional nucleation and growth mechanism. The different structural and electronic modifications induced by H in fully functionalized graphene and silicene (known as graphane and silicane) are also explained. Finally, the electronic properties of defective graphane with multiple hydrogen vacancies are investigated. Engineering the vacancies in graphane offers a way to modify the electronic properties of this material. 相似文献
40.
Acetyl Methyl Torsion in N‐Ethylacetamide: A Challenge for Microwave Spectroscopy and Quantum Chemistry 下载免费PDF全文
Raphaela Kannengießer Marcel J. Lach Prof. Dr. Wolfgang Stahl Dr. Ha Vinh Lam Nguyen 《Chemphyschem》2015,16(9):1906-1911
The gas‐phase structures and parameters describing acetyl methyl torsion of N‐ethylacetamide are determined with high accuracy, using a combination of molecular beam Fourier‐transform microwave spectroscopy and quantum chemical calculations. Conformational studies at the MP2 level of theory yield four minima on the energy surface. The most energetically favorable conformer, which possesses C1 symmetry, is assigned. Due to the torsional barrier of 73.4782(1) cm?1 of the acetyl methyl group, fine splitting up to 4.9 GHz is found in the spectrum. The conformational structure is not only confirmed by the rotational constants, but also by the orientation of the internal rotor. The 14N quadrupole hyperfine splittings are analyzed and the deduced coupling constants are compared with the calculated values. 相似文献