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1.
Cheng-Cheng Tsai Zhi-Yao Tsai Ming-Yu Tseng Wei-Ping Hu 《International journal of quantum chemistry》2020,120(14):e26238
We have developed a new database of structures and bond energies of 59 noble-gas-containing molecules. The structures were calculated by CCSD(T)/aug-cc-pVTZ methods and the bond energies were obtained using the CCSD(T)/complete basis set method. Many wavefunction-based and density functional theory methods have been benchmarked against the 59 accurate bond energies. Our results show that the MPW1B95, B2GP-PLYP, and DSD-BLYP functionals with the aug-cc-pVTZ basis set excel in predicting the bond energies of noble-gas molecules with mean unsigned errors (MUEs) of 2.0 to 2.1 kcal/mol. When combinations of Dunning's basis sets are used, the MPW1B95, B2GP-PLYP, DSD-BLYP, and BMK functionals give significantly lower MUEs of 1.6 to 1.9 kcal/mol. Doubly hybrid methods using B2GP-PLYP and DSD-BLYP functionals and MP2 calculation also provide satisfactory accuracy with MUEs of 1.4 to 1.5 kcal/mol. If the Ng bond energies and the total atomization energies of a group of 109 main-group molecules are considered at the same time, the MPW1B95/aug-cc-pVTZ single-level method (MUE = 2.7 kcal/mol) and the B2GP-PLYP and DSD-PLYP functionals with combinations of basis sets or using the doubly hybrid method (MUEs = 1.9-2.2 kcal/mol) give the overall best result. 相似文献
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This study describes the development of a simple, enzyme-free, label-free, sensitive, and selective system for detecting adenosine based on the use of Tween 20-stabilized gold nanoparticles (Tween 20-AuNPs) as an efficient fluorescence quencher for boron dipyrromethene-conjugated adenosine 5′-triphosphate (BODIPY-ATP) and as a recognition element for adenosine. BODIPY-ATP can interact with Tween 20-AuNPs through the coordination between the adenine group of BODIPY-ATP and Au atoms on the NP surface, thereby causing the fluorescence quenching of BODIPY-ATP through the nanometal surface energy transfer (NSET) effect. When adenosine attaches to the NP surface, the attached adenosine exhibits additional electrostatic attraction to BODIPY-ATP. As a result, the presence of adenosine enhances the efficiency of AuNPs in fluorescence quenching of BODIPY-ATP. The AuNP-induced fluorescence quenching of BODIPY-ATP progressively increased with an increase in the concentration of adenosine; the detection limit at a signal-to-noise ratio of 3 for adenosine was determined to be 60 nM. The selectivity of the proposed system was more than 1000-fold for adenosine over any adenosine analogs and other nucleotides. The proposed system combined with a phenylboronic acid-containing column was successfully applied to the determination of adenosine in urine. 相似文献
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Journal of Nanoparticle Research - Ni-doped (CeO2?δ )–YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been... 相似文献
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Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase 下载免费PDF全文
Kai‐Ti Chu Dr. Yu‐Chiao Liu Yi‐Lan Huang Dr. Gene‐Hsiang Lee Dr. Mei‐Chun Tseng Prof. Ming‐Hsi Chiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6852-6861
The one‐electron oxidations of a Fe2 complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe2 species, mixed‐valent Fe4, and Fe8 complexes. The unpaired spin in the Fe2 radical species delocalizes over the Fe2 and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe2 to the Fe4 retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe8, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe8 is converted to Fe4. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes. 相似文献
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Structural Chemistry - Alternariol and alternariol monomethyl ether are mycotoxins occasionally found in food and beverages that have been contaminated by certain fungi of the Alternaria genus.... 相似文献
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Wei Shyang Tan Ting‐Yin Lee Sheng‐Fang Tseng Ying‐Feng Hsu Masanori Ebina Tetsuya Taketsugu Shing‐Jong Huang Jye‐Shane Yang 《中国化学会会志》2019,66(9):1141-1156
Despite the long history of polyaniline chemistry, backbone‐substituted polyanilines are limited. Here, we report the synthesis of pentiptycene‐incorporated polyanilines through acidic aniline oxidative polymerization with three pentiptycene derivatives, TA, DA, and TP, as nucleate additives. The reactivity of TA > DA ? TP, as evidenced by structural and property analysis of the corresponding polyaniline products, demonstrates a radical coupling mechanism and the formation of Dewar π‐complex intermediates for the chain propagation. In addition, the iptycene substituent effect on enhancing the electrochemical stability and charge storage capability of polyaniline are discussed with a clip model, namely, the threading of neighboring polyaniline chains through the U‐ and V‐shaped cavities of pentiptycene restricts lateral motions of the polymer chains and promotes interchain conductivity. Density function theory (DFT) calculations suggest a larger clipping effect for the U versus V cavities. Both the conclusion of a terminal planar p‐phenylenediamine (ppda) group being the key component of an effective nucleate and the concept of interchain clipping for enhanced electrochemical performance should facilitate the design and synthesis of novel polyanilines for electronic applications. 相似文献
10.
Biodegradable multi‐l ‐arginyl‐poly‐l ‐aspartate (MAPA), more commonly cyanophycin, prepared with recombinant Escherichia coli contains a polyaspartate backbone with lysine and arginine as side chains. Two assemblies of polyelectrolyte multilayers (PEMs) are fabricated at three different concentration ratios of insoluble MAPA (iMAPA) with hyaluronic acid (iMAPA/HA) and with γ‐polyglutamic acid (iMAPA/γ‐PGA), respectively, utilizing a layer‐by‐layer approach. Both films with iMAPA and its counterpart, HA or γ‐PGA, as the terminal layer are prepared to assess the effect on film roughness, cell growth, and cell migration. iMAPA incorporation is higher for a higher concentration of the anionic polymer due to better charge interaction. The iMAPA/HA films when compared to iMAPA/γ‐PGA multilayers show least roughness. The growth rates of L929 fibroblast cells on the PEMs are similar to those on glass substrate, with no supplementary effect of the terminal layer. However, the migration rates of L929 cells increase for all PEMs. γ‐PGA incorporated films impart 50% enhancement to the cell migration after 12 h of culture as compared to the untreated glass, and the smooth films containing HA display a maximum 82% improvement. The results present the use of iMAPA to construct a new layer‐by‐layer system of polyelectrolyte biopolymers with a potential application in wound dressing. 相似文献