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611.
A mild, thermal Alder-ene reaction of enallenes has been developed. The allenic double bond acts as the "ene" and generates a carbon-carbon bond to an unactivated olefinic "enophile" in DMF at 120 degrees C to give [n.3.0] bicyclic systems (n = 3-5) in good yields. Except for a minor [2 + 2] cycloaddition byproduct, the reaction proceeded with complete atom economy, as there is no requirement of a catalyst or additional reactants, and no waste products are formed in the process. 相似文献
612.
Chelated amino acid ester enolates are excellent nucleophiles for allylic alkylations. With these enolates, even terminal pi-allyl palladium complexes react without significant isomerization. This allows a transfer of the cis-olefin geometry from the substrate into the product. Chiral substrates also show a reasonably good 1,5-induction. 相似文献
613.
Amino acids are important targets for metabolic profiling. For decades, amino acid analysis has been accomplished by either
cation-exchange or reversed-phase liquid chromatography coupled to UV absorbance or fluorescence detection of pre-column or
post-column-derivatized amino acids. Recent years have seen great progress in the development of direct-infusion or hyphenated
mass spectrometry in the analysis of free amino acids in physiological fluids, because mass spectrometry not only matches
optical detection in sensitivity, but also offers superior selectivity. The advent of cryo-probes has also brought NMR spectroscopy
within the detection limits required for the analysis of free amino acids. But there is still room for further improvement,
including expansion of the analyte spectrum, reduction of sample preparation and analysis time, automation, and synthesis
of affordable isotope standards.
Figure Fully automated gas chromatography-mass spectrometry analysis of amino acids. 相似文献
614.
A crystal plasticity model and a homogenization method are used to analyze the local and global mechanical behavior of a ferritic stainless steel. In the first step the material constants are determined based on tensile tests and used to simulate the local deformation behavior on the grain scale in the second step. For that 2D EBSD data are discretized by finite elements. The computed local grain reorientations of three different BCC slip systems are compared to experimental data at the state of 20% elongation. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
615.
Dr. Katja S. Håheim Dr. Bjarte Aarmo Lund Prof. Magne O. Sydnes 《European journal of organic chemistry》2023,26(13):e202300137
A large number of diversely functionalized analogs of the bioactive natural products neocryptolepine and isocryptolepine have been prepared from a series of 3-bromoquinoline derivatives. The neocryptolepines were obtained by a Pd0-catalyzed C−C bond coupling followed by C−N bond formation in yields up to 80 %, whereas the indoloquinolines were prepared by a Suzuki-Miyaura cross-coupling followed by azidation-photochemical cyclization in yields ranging from traces to 95 % yield. 相似文献
616.
Electrostatic self‐assembly can be used to form supramolecular vesicles in aqueous solution. Vesicles consist of cationic G8 poly(amidoamine) dendrimers and the trivalent sulfonate dye Ar27. No classical amphiphiles are present but the interplay of electrostatics, π–π interaction and geometric factors influences the structure formation. Labeled guest molecules, both small molecules and peptides, can be included inside these vesicles and vesicles imaged by fluorescence techniques. The structure was studied by dynamic and static light scattering, small‐angle neutron scattering, confocal laser scanning microscopy, and fluorescence correlation spectroscopy. The study indicates the prospect of constructing functional nanoobjects by the self‐assembly of charged molecules in aqueous solution.
617.
618.
Andrew J. Devine Dr. Alice E. Parnell Dr. Catherine R. Back Dr. Nicholas R. Lees Dr. Samuel T. Johns Ainul Z. Zulkepli Rob Barringer Dr. Katja Zorn Dr. James E. M. Stach Prof. Matthew P. Crump Prof. Martin A. Hayes Dr. Marc W. van der Kamp Prof. Paul R. Race Prof. Christine L. Willis 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202213053
Abyssomicin C and its atropisomer are potent inhibitors of bacterial folate metabolism. They possess complex polycyclic structures, and their biosynthesis has been shown to involve several unusual enzymatic transformations. Using a combination of synthesis and in vitro assays we reveal that AbyV, a cytochrome P450 enzyme from the aby gene cluster, catalyses a key late-stage epoxidation required for the installation of the characteristic ether-bridged core of abyssomicin C. The X-ray crystal structure of AbyV has been determined, which in combination with molecular dynamics simulations provides a structural framework for our functional data. This work demonstrates the power of combining selective carbon-13 labelling with NMR spectroscopy as a sensitive tool to interrogate enzyme-catalysed reactions in vitro with no need for purification. 相似文献