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11.
The SCCC MO method has been used to calculate the electronic structure and spectrum of Mo(CN)
8
4–
and Mo(CN)
8
3–
ions of a D
4d
symmetry. All metal-ligand and ligand-ligand interactions and all overlap integrals (over products of HF atomic orbitals) have been included within the SCCC MO scheme. Basing on these calculations a new assignment of some absorption bands is proposed. The overall agreement between the calculated and observed electronic spectrum is satisfactory.
The authors are grateful to Prof. W. Jakób, Dr. Z. Stasicka and Dr. A. Samotus for many interesting discussions, to Prof. J. Chojnacki for providing us with new X-ray results before publication and to Dr. A. J. Sadlej for a help in dealing with the computer. 相似文献
Zusammenfassung Elektronenstruktur und Spektrum der [Mo(CN)8]–4- und [Mo(CN)8]–3-Ionen in D 4d -Symmetrie wurden mit der SCCC-MO-Methode berechnet. Alle Metall-Ligand- und Ligand-Ligand-Wechsel-wirkungen und Überlappungsintegrale wurden berücksichtigt. Die Bandenzuordnung wurde neu vorgenommen. Die Übereinstimmung der berechneten und gemessenen Spektren ist befriedigend.
Résumé Application à Mo(CN) 8 4– et Mo(CN) 8 3– de la méthode SCCC MO basée sur des orbitales atomiques HF approchées, en tenant compte du recouvrement et de toutes les interactions ligand-ligand. Dans la partie I on discute le cas de la symétrie D 4d . L'accord global avec l'expérience est satisfaisant en ce qui concerne les spectres. On montre aussi que toutes les attributions antérieures basées sur la théorie du champ cristallin semblent inadéquates.
The authors are grateful to Prof. W. Jakób, Dr. Z. Stasicka and Dr. A. Samotus for many interesting discussions, to Prof. J. Chojnacki for providing us with new X-ray results before publication and to Dr. A. J. Sadlej for a help in dealing with the computer. 相似文献
12.
13.
Go Takikawa 《Tetrahedron letters》2006,47(37):6509-6511
Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl β,β-difluoro-α-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl β-substituted-β,β-difluoropyruvate in good yields. 相似文献
14.
[reaction: see text]. Stereocontrolled synthesis of the ABC ring framework of zoanthenol has been achieved. Our studies show that a beta,beta-disubstituted enone can act as a good acceptor of arylpalladium intermediates in the formation of a congested benzylic quaternary carbon center through an intramoleculer Mizoroki-Heck reaction. The cis B/C ring system was stereoselectively converted to the trans-fused framework through a SmI2-promoted deoxygenation of the alpha-hydroxy ketone. 相似文献
15.
A C1-class of plane closed curves is considered, which contains all ovals and rosettes. This class is divided into some subclasses for which greatest lower bounds of numbers of antipodal and arc-antipodal sets are determined. 相似文献
16.
We review the progress and future possibilities in the emerging area of molecular spintronics. We first provide an overview of the different transport regimes in which electronic nanodevices can operate, then briefly overview the important characteristics of molecular magnetic materials that can be useful for application in spintronics and we eventually present several schemes to include such systems into spintronic nanodevices. We hightlight the importance of a chemical approach to the area, and in the last section we showcase some approaches to the creation of hybrids made of carbon nanostructures and molecular magnets, which are gaining increasing attention. 相似文献
17.
The semicontinuous emulsion polymerization of vinyl acetate has been studied. Poly(vinyl alcohol) as a protective colloid and ethoxylated cetyl alcohol as a coemulsifier were used. The conversion and particle diameter were affected by the stirring speed and the coemulsifier distribution between initial reactor charge and continuously introduced monomer. The amount of unreacted monomer oscillates with time. 相似文献
18.
19.
X. Cahís A. Benavent-Climent A. Catalán Goñi 《Revista Internacional de Métodos Numéricos para Cálculo y Dise?o en Ingeniería》2013,29(4):248-259
Waffle-flat-plate structures have been widely used for residential and office buildings in the South of Europe between the seventies and nineties of the last century. These buildings were designed with old seismic codes and its vulnerability needs to be evaluated to determine whether they need to be seismic retrofitted or not. This article proposes a simple model that represents the moment transfer between plate and column, for existing exterior connections loaded in the direction normal to the building façade. The model takes into account singularities of existing waffle-flat-plate structures such as the concentration of reinforcement in the direction of the joints, and the existence of punching shear reinforcement. The model consists of frame elements for the columns and shell elements for the slabs, both connected with flexural and torsion hinges. The strength of the flexural hinges is obtained by estimating the portion of longitudinal reinforcement of the plate that transfers directly the unbalanced moment to the column by flexure. The yielding deformations of the flexural and torsion hinges are estimated with simple expressions. The ductility of the flexural hinges is taken from FEMA 356, while infinite ductility is adopted for the torsional hinges in accordance with previous experimental studies. It is shown that the proposed model provides a good approximation of the experimental response of the connection under monotonically increasing lateral displacements, in terms of stiffness, strength and ductility. 相似文献
20.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献