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61.
Acceleration of self‐consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function 下载免费PDF全文
The Lagrange interpolation of molecular orbital (LIMO) method, which reduces the number of self‐consistent field iterations in ab initio molecular dynamics simulations with the Hartree–Fock method and the Kohn–Sham density functional theories, is extended to the theory of multiconfigurational wave functions. We examine two types of treatments for the active orbitals that are partially occupied. The first treatment, as denoted by LIMO(C), is a simple application of the conventional LIMO method to the union of the inactive core and the active orbitals. The second, as denoted by LIMO(S), separately treats the inactive core and the active orbitals. Numerical tests to compare the two treatments clarify that LIMO(S) is superior to LIMO(C). Further applications of LIMO(S) to various systems demonstrate its effectiveness and robustness. © 2014 Wiley Periodicals, Inc. 相似文献
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Yoshiyuki Uchiyama Takahiro Hayasaka Noritaka Masaki Yoshiko Watanabe Kazuma Masumoto Tetsuji Nagata Fuminori Katou Mitsutoshi Setou 《Analytical and bioanalytical chemistry》2014,406(5):1307-1316
Most oral cancers are oral squamous cell carcinoma (OSCC). The anatomical features of OSCC have been histochemically evaluated with hematoxylin and eosin. However, the border between the cancer and stromal regions is unclear and large portions of the cancer and stromal regions are resected in surgery. To reduce the resected area and maintain oral function, a new method of diagnosis is needed. In this study, we tried to clearly distinguish the border on the basis of biomolecule distributions visualized by imaging mass spectrometry (IMS). In the IMS dataset, eleven signals were significantly different in intensity (p?<?0.01) between the cancer and stromal regions. Two signals at m/z 770.5 and m/z 846.6 were distributed in each region, and a clear border was revealed. Tandem mass spectrometric (MS/MS) analysis identified these signals as phosphatidylcholine (PC) (16:0/16:1) at m/z 770.5 in the cancer region and PC (18:1/20:4) at m/z 846.6 in the stromal region. Moreover, the distribution of PC species containing arachidonic acid in the stromal region suggests that lymphocytes accumulated in response to the inflammation caused by cancer invasion. In conclusion, the cancer and stromal regions of OSCCs were clearly distinguished by use of these PC species and IMS analysis, and this molecular identification can provide important information to elucidate the mechanism of cancer invasion. 相似文献
63.
Asobe M Tadanaga O Umeki T Yanagawa T Nishida Y Magari K Suzuki H 《Optics letters》2007,32(23):3388-3390
We propose a novel quasi-phase-matched (QPM) device that can generate unequally spaced multiple wavelengths. Unequally spaced multiple QPM peaks can be obtained by employing the optimized phase modulation of a periodic domain structure. We fabricated a LiNbO3 waveguide device for 3.2-3.4 microm band difference frequency generation based on the design. Using the multiple mid-infrared outputs, we demonstrate the detection of multiple hydrocarbon gases, namely, methane, ethylene, and ethane. 相似文献
64.
The CyanoP protein is a cyanobacterial homolog of the PsbP protein, which is an extrinsic subunit of photosystem II (PSII) in green plant species. The molecular function of CyanoP has been investigated in mutant strains of Synechocystis but inconsistent results have been reported by different laboratories. In this study, we generated and characterized a Synechocystis mutant in which entire region of the CyanoP gene was eliminated. After repeated subculture in CaCl2-depleted medium, growth retardation was clearly observed for a CyanoP knockout mutant of Synechocystis sp. PCC 6803 (?P). The PSII-mediated oxygen-evolving activity of the ?P cells was more susceptible to depletion of CaCl2 than that of wild-type cells. The 77 K fluorescence emission spectra indicated that energy coupling between phycobilisome and PSII was perturbed in both wild-type and ?P cells under CaCl2-depleted conditions, and was more evident for the ?P mutant. To examine the association of CyanoP with PSII complexes, we tested several detergents for solubilization of thylakoid membranes and showed that CyanoP was partly included in fractions containing large protein complexes in gel-filtration analysis. These results indicate that CyanoP constitutively stabilizes PSII functionality in vivo. 相似文献
65.
Daisuke Saito Dr. Tomohiro Ogawa Dr. Masaki Yoshida Junichi Takayama Dr. Satoshi Hiura Prof. Dr. Akihiro Murayama Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18882-18889
A series of assembled PtII complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups, [Pt(CN)2(R-impy)] (R-impyH+=1-alkyl-3-(2-pyridyl)-1H-imidazolium, R=Me ( Pt-Me ), Et ( Pt-Et ), iPr ( Pt- i Pr ), and tBu ( Pt- t Bu )). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield of 0.51–0.81 in the solid state at room temperature, originating from the triplet metal-metal-to-ligand charge transfer (3MMLCT) state. Their emission colors cover the entire visible region from red for Pt-Me to blue for Pt- t Bu . Importantly, Pt- t Bu is the first example that exhibits blue 3MMLCT emission. The 3MMLCT emission was proved and characterized based on the temperature dependences of the crystal structures and emission properties. The wide-range color tuning of luminescence using the 3MMLCT emission presents a new strategy of superfine control of the emission color. 相似文献
66.
Soumen Dutta Nitee Kumari Sateesh Dubbu Sun Woo Jang Amit Kumar Hiroyoshi Ohtsu Junghoon Kim Seung Hwan Cho Masaki Kawano In Su Lee 《Angewandte Chemie (International ed. in English)》2020,59(9):3416-3422
Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields. 相似文献
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69.
Prof. Makoto Tadokoro Masaki Itoh Ryota Nishimura Kensuke Sekiguchi Dr. Norihisa Hoshino Dr. Hajime Kamebuchi Prof. Jun Miyazaki Dr. Fumiya Kobayashi Prof. Motohiro Mizuno Prof. Tomoyuki Akutagawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201397
A new H-bonded crystal [RuIII(Him)3(Im)3] with three imidazole (Him) and three imidazolate (Im−) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the RuIII complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10−5 S cm−1 at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [RuIII(Him)3(Im)3] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state 2H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered. 相似文献
70.
A solid-supported acidic oxazolium perchlorate was investigated as a heterogeneous catalyst in N-glycosylation reactions using silylated modified pyrimidines and an acylated ribose or glucose to afford the corresponding pyrimidine nucleosides. This salt is a nonhygroscopic and stable powder whose activity is comparable to that of 2-methyl-5-phenylbenzoxazolium perchlorate. A reaction with this polymer catalyst can be conducted on a gram scale. Reusability of the solid-supported catalyst was also investigated. 相似文献