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61.
[reaction: see text] Reported herein is a strategy employing a Mukaiyama reaction in tandem with a hydrogen transfer reaction for the elaboration of 2,3-anti-3,4-anti and 2,3-anti-3,4-syn propionate motifs. The mode of complexation is controlled through monodentate or chelate pathways for the Mukaiyama reaction to give access to either syn or anti aldol products, precursors of the free-radical reduction reaction. Boron Lewis acid is used to control the free-radical reaction through the exocyclic pathway. 相似文献
62.
Dr. Julian J. Holstein Priv.‐Doz. Dr. Birger Dittrich Miriam Simon Dr. Sylvain Prévost Prof. Dr. Michael Gradzielski Prof. Dr. Guido H. Clever 《Angewandte Chemie (International ed. in English)》2018,57(41):13652-13656
A series of metal‐mediated cages, having multiple cavities, was synthesized from PdII cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd3L14] cage deriving from the tris‐monodentate ligand L1 could be quantitatively converted into its interpenetrated [5Cl@Pd6L18] dimer featuring a linear {[Pd‐Cl‐]5Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small‐angle neutron scattering (SANS) experiments showed that the cigar‐shaped assembly with a length of 3.7 nm aggregates into mono‐layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta‐cationic [5Cl@Pd6L18] cage was found to interact with polyanionic oligonucleotide double‐strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non‐covalent DNA binding. 相似文献
63.
Inoue S Wang W Präsang C Asay M Irran E Driess M 《Journal of the American Chemical Society》2011,133(9):2868-2871
The first N-donor-stabilized phosphasilene LSi(SiMe(3))═PSiMe(3) (L = PhC(NtBu)(2)) has been synthesized in 87% yield through 1,2-silyl migration of the (Me(3)Si)(2)P-substituted, N-heterocyclic silylene [LSi-P(SiMe(3))(2)]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph(3)PCl(2) to give the unprecedented 4π-electron Si(2)P(2)-cycloheterobutadiene [(LSi)(2)P(2)] with two-coordinate phosphorus atoms. The striking molecular structures as well as the (29)Si and (31)P NMR spectroscopic features of both products indicate the presence of zwitterionic Si═P bonds which is also in accordance with results by DFT calculations. 相似文献
64.
W. Seidel M. Bravin M. Bruckmayer C. Bucci S. Cooper P. DiStefano F. V. Feilitzsch T. Frank J. Jochum R. Keeling H. Kraus M. Loidl J. Marchese O. Meier P. Meunier U. Nagel D. Pergolesi F. Pröbst Y. Ramachers J. Schnagl I. Sergeyev M. Sisti L. Stodolsky S. Uchaikin L. Zerle 《Physics of Atomic Nuclei》2000,63(7):1242-1248
We discuss the short-and long-term perspectives of the CRESST (Cryogenic Rare Event Search using Superconducting Thermometers) project and present the current status of the experiment and new results concerning detector development. In the search for elementary particle dark matter, CRESST is presently the most advanced deep underground, low-background, cryogenic facility. The basic technique involved is to search for WIMPs (Weakly Interacting Massive Particles) by the measurement of nonthermal phonons, as created by WIMP-induced nuclear recoils. Combined with our newly developed method for the simultaneous measurement of scintillation light, strong background discrimination is possible, resulting in a substantial increase in WIMP detection sensitivity. This will allow a test of the reported positive evidence for a WIMP signal by the DAMA Collaboration in the near future. In the long term, the present CRESST setup permits the installation of a detector mass up to 100 kg. In contrast to other projects, CRESST technology allows the employment of a large variety of detection materials. This offers a powerful tool in establishing a WIMP signal and in investigating WIMP properties in the event of a positive signal. 相似文献
65.
66.
A Visible Light Photocatalytic Cross‐Dehydrogenative Coupling/Dehydrogenation/6π‐Cyclization/Oxidation Cascade: Synthesis of 12‐Nitroindoloisoquinolines from 2‐Aryltetrahydroisoquinolines 下载免费PDF全文
Fabian Rusch Lisa‐Natascha Unkel Dirk Alpers Dr. Frank Hoffmann Prof. Dr. Malte Brasholz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8336-8340
A visible light‐induced photocatalytic dehydrogenation/6π‐cyclization/oxidation cascade converts 1‐(nitromethyl)‐2‐aryl‐1,2,3,4‐tetrahydroisoquinolines into novel 12‐nitro‐substituted tetracyclic indolo[2,1‐a]isoquinoline derivatives. Various photocatalysts promote the reaction in the presence of air and a base, the most efficient being 1‐aminoanthraquinone in combination with K3PO4. Further, the 12‐nitroindoloisoquinoline products can be accessed directly from C1‐unfunctionalized 2‐aryl‐1,2,3,4‐tetrahydroisoquinolines by extending the one‐pot protocol with a foregoing photocatalytic cross‐dehydrogenative coupling reaction, resulting in a quadruple cascade transformation. 相似文献
67.
Malte Krack Sebastian TatzkoLars Panning-von Scheidt Jörg Wallaschek 《Journal of sound and vibration》2014
A novel probabilistic approach for the design of mechanical structures with friction interfaces is proposed. The objective function is defined as the probability that a specified performance measure of the forced vibration response is achieved subject to parameter uncertainties. The practicability of the approach regarding the extensive amount of required design evaluations is strictly related to the computational efficiency of the nonlinear dynamic analysis. Therefore, it is proposed to employ a recently developed parametric reduced order model (ROM) based on nonlinear modes of vibration, which can facilitate a decrease of the computational burden by several orders of magnitude. 相似文献
68.
Mareike Prüfer Christian Wenger Frank F. Bier Eva-Maria Laux Ralph Hölzel 《Electrophoresis》2022,43(18-19):1920-1933
Dielectrophoresis (DEP) is an AC electrokinetic effect mainly used to manipulate cells. Smaller particles, like virions, antibodies, enzymes, and even dye molecules can be immobilized by DEP as well. In principle, it was shown that enzymes are active after immobilization by DEP, but no quantification of the retained activity was reported so far. In this study, the activity of the enzyme horseradish peroxidase (HRP) is quantified after immobilization by DEP. For this, HRP is immobilized on regular arrays of titanium nitride ring electrodes of 500 nm diameter and 20 nm widths. The activity of HRP on the electrode chip is measured with a limit of detection of 60 fg HRP by observing the enzymatic turnover of Amplex Red and H2O2 to fluorescent resorufin by fluorescence microscopy. The initial activity of the permanently immobilized HRP equals up to 45% of the activity that can be expected for an ideal monolayer of HRP molecules on all electrodes of the array. Localization of the immobilizate on the electrodes is accomplished by staining with the fluorescent product of the enzyme reaction. The high residual activity of enzymes after AC field induced immobilization shows the method's suitability for biosensing and research applications. 相似文献
69.
70.
Summary. Total positivity is an important concept which has been studied by Gantmacher, Karlin and Schoenberg. In section 1, new properties
of totally positive functions are given. The concept of totally monotonic families of sequences (TMFS), by mean of positivity
of some determinant, is defined and studied.
Applications to extrapolation algorithms are given.
Received October 22, 1997 / Revised version received April 14, 1998 / Published online August 19, 1999 相似文献