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排序方式: 共有654条查询结果,搜索用时 15 毫秒
91.
Jordan Meyet Keith Searles Mark A. Newton Michael Wrle Alexander P. vanBavel Andrew D. Horton Jeroen A. vanBokhoven Christophe Copret 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(29):9946-9950
Monomeric CuII sites supported on alumina, prepared using surface organometallic chemistry, convert CH4 to CH3OH selectively. This reaction takes place by formation of CH3O surface species with the concomitant reduction of two monomeric CuII sites to CuI, according to mass balance analysis, infrared, solid‐state nuclear magnetic resonance, X‐ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH3OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina‐supported CuII sites reveal that C?H bond activation, along with the formation of CH3O‐ surface species, can occur on pairs of proximal monomeric CuII sites in a short reaction time. 相似文献
92.
Dr. Stefan van der Vorm Thomas Hansen Dr. Erwin R. van Rijssel Rolf Dekkers Jerre M. Madern Prof. Dr. Herman S. Overkleeft Dr. Dmitri V. Filippov Prof. Dr. Gijsbert A. van der Marel Dr. Jeroen D. C. Codée 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(29):7149-7157
The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of SN1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2-azide, C2-fluoride and C4-carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2-cis products, except for the reactions in the xylose series. The 1,2-cis selectivity for the ribo-, arabino- and lyxo-configured furanosides can be traced back to the lowest-energy 3E or E3 conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations. 相似文献
93.
Jan Rinkel Simon T. Steiner Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2019,58(27):9230-9233
Three diterpene synthases from actinomycetes have been studied. The first enzyme from Streptomyces cattleya produced the novel compound cattleyene. The other two enzymes from Nocardia testacea and Nocardia rhamnosiphila were identified as phomopsene synthases. The cyclisation mechanism of cattleyene synthase and the EIMS fragmentation mechanism of its product were extensively studied by incubation experiments with isotopically labelled precursors. Oxidative transformations expanded the chemical space of these unique diterpenes. 相似文献
94.
Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2019,58(45):15964-15976
This Minireview summarises recent developments in the biosynthesis of diterpenes by diterpene synthases in bacteria. It is structured by the class of enzyme involved in the first committed step towards diterpenes, starting with type I diterpene synthases, followed by type II enzymes and the more recently discovered UbiA‐related diterpene synthases. A special emphasis lies on the reaction mechanisms of diterpene synthases that convert simple linear precursors through cationic cascades into structurally complex, usually polycyclic carbon skeletons with multiple stereogenic centres. A further main focus of this Minireview is a discussion of how these mechanisms can be unravelled. Downstream modifications to bioactive molecules are also covered. 相似文献
95.
Keiichi Murai Lukas Lauterbach Kazuya Teramoto Zhiyang Quan Lena Barra Tsuyoshi Yamamoto Kenichi Nonaka Kazuro Shiomi Makoto Nishiyama Tomohisa Kuzuyama Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2019,58(42):15046-15050
The skeletons of some classes of terpenoids are unusual in that they contain a larger number of Me groups (or their biosynthetic equivalents such as olefinic methylene groups, hydroxymethyl groups, aldehydes, or carboxylic acids and their derivatives) than provided by their oligoprenyl diphosphate precursor. This is sometimes the result of an oxidative ring‐opening reaction at a terpene‐cyclase‐derived molecule containing the regular number of Me group equivalents, as observed for picrotoxan sesquiterpenes. In this study a sesquiterpene cyclase from Trichoderma spp. is described that can convert farnesyl diphosphate (FPP) directly via a remarkable skeletal rearrangement into trichobrasilenol, a new brasilane sesquiterpene with one additional Me group equivalent compared to FPP. A mechanistic hypothesis for the formation of the brasilane skeleton is supported by extensive isotopic labelling studies. 相似文献
96.
Alex van der Ham Thomas Hansen Dr. Gerrit Lodder Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Dr. Dmitri V. Filippov 《Chemphyschem》2019,20(16):2103-2109
Lithium ion selective crown ethers have been the subject of much research for a multitude of applications. Current research is aimed at structurally rigidifying crown ethers, as restructuring of the crown ether ring upon ion binding is energetically unfavorable. In this work, the lithium ion binding ability of the relatively rigid 8-crown-4 was investigated both computationally by density functional theory calculations and experimentally by 1H and 7Li NMR spectroscopy. Although both computational and experimental results showed 8-crown-4 to bind lithium ion, this binding was found to be weak compared to larger crown ethers. The computational analysis revealed that the complexation is driven by enthalpy rather than entropy, illustrating that rigidity is only of nominal importance. To elucidate the origin of the favorable interaction of lithium ion with crown ethers, activation strain analyses and energy decomposition analyses were performed pointing to the favorable interaction being mainly electrostatic in nature. 8-crown-4 presents the smallest crown ether reported to date capable of binding lithium ion, possessing two distinct conformations from which it is able to do so. 相似文献
97.
Diederik Aerts Bart D’Hooghe Andrzej Posiewnik Jaroslaw Pykacz Jeroen Dehaene Bart De Moor 《International Journal of Theoretical Physics》2008,47(1):61-68
We show that it is possible to play ‘restricted’ two-player quantum games proposed originally by Marinatto and Weber (Phys.
Lett. A 272:291–303, 2000) by purely macroscopic means, in the simplest case having as the only equipment a pack of 10 cards. Our example shows also
that some apparently ‘genuine quantum’ results, even those that emerge as a consequence of dealing with entangled states,
can be obtained by suitable application of Kolmogorovian probability calculus and secondary-school mathematics, without application
of the ‘Hilbert space machinery’. 相似文献
98.
Schimmel O van de Par S Breebaart J Kohlrausch A 《The Journal of the Acoustical Society of America》2008,124(2):1130-1145
The ability to segregate two spectrally and temporally overlapping signals based on differences in temporal envelope structure and binaural cues was investigated. Signals were a harmonic tone complex (HTC) with 20 Hz fundamental frequency and a bandpass noise (BPN). Both signals had interaural differences of the same absolute value, but with opposite signs to establish lateralization to different sides of the medial plane, such that their combination yielded two different spatial configurations. As an indication for segregation ability, threshold interaural time and level differences were measured for discrimination between these spatial configurations. Discrimination based on interaural level differences was good, although absolute thresholds depended on signal bandwidth and center frequency. Discrimination based on interaural time differences required the signals' temporal envelope structures to be sufficiently different. Long-term interaural cross-correlation patterns or long-term averaged patterns after equalization-cancellation of the combined signals did not provide information for the discrimination. The binaural system must, therefore, have been capable of processing changes in interaural time differences within the period of the harmonic tone complex, suggesting that monaural information from the temporal envelopes influences the use of binaural information in the perceptual organization of signal components. 相似文献
99.
We describe the development and validation of a high-resolution screening (HRS) platform which couples gradient reversed-phase
high-performance liquid chromatography (RP-HPLC) on-line to estrogen receptor α (ERα) affinity detection using fluorescence
polarization (FP). FP, which allows detection at high wavelengths, limits the occurrence of interference from the autofluorescence
of test compounds in the bioassay. A fluorescein-labeled estradiol derivative (E2-F) was synthesized and a binding assay was
optimized in platereader format. After subsequent optimization in flow-injection analysis (FIA) mode, the optimized parameters
were translated to the on-line HRS bioassay. Proof of principle was demonstrated by separating a mixture of five compounds
known to be estrogenic (17β-estradiol, 17α-ethinylestradiol and the phytoestrogens coumestrol, coumarol and zearalenone),
followed by post-column bioaffinity screening of the individual affinities for ERα. Using the HRS-based FP setup, we were
able to screen affinities of off-line-generated metabolites of zearalenone for ERα. It is concluded that the on-line FP-based
bioassay can be used to screen for the affinity of compounds without the disturbing occurrence of autofluorescence. 相似文献
100.