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41.
We study the existence and non-existence of positive singular solutions of second-order non-divergence type elliptic inequalities of the form $\sum\limits_{i,j = 1}^N {a_{ij} (x)\frac{{\partial ^2 u}} {{\partial x_i \partial x_j }}} + \sum\limits_{i = 1}^N {b_i (x)\frac{{\partial u}} {{\partial x_i }} \geqslant K(x)u^p ,} - \infty < p - \infty , $ with measurable coefficients in a punctured ball B R \{0} of ? N , N ≥ 1. We prove the existence of a critical value p* which separates the existence region from the non-existence region. We show that in the critical case p = p*, the existence of a singular solution depends on the rate at which the coefficients (a i j ) and (b i ) stabilize at zero, and we provide some optimal conditions in this setting. 相似文献
42.
Marius Dadarlat 《Advances in Mathematics》2009,222(5):1850-2880
Let X be a finite dimensional compact metrizable space. We study a technique which employs semiprojectivity as a tool to produce approximations of C(X)-algebras by C(X)-subalgebras with controlled complexity. The following applications are given. All unital separable continuous fields of C*-algebras over X with fibers isomorphic to a fixed Cuntz algebra On, n∈{2,3,…,∞}, are locally trivial. They are trivial if n=2 or n=∞. For n?3 finite, such a field is trivial if and only if (n−1)[A1]=0 in K0(A), where A is the C*-algebra of continuous sections of the field. We give a complete list of the Kirchberg algebras D satisfying the UCT and having finitely generated K-theory groups for which every unital separable continuous field over X with fibers isomorphic to D is automatically locally trivial or trivial. In a more general context, we show that a separable unital continuous field over X with fibers isomorphic to a KK-semiprojective Kirchberg C*-algebra is trivial if and only if it satisfies a K-theoretical Fell type condition. 相似文献
43.
In this paper we use a double penalization procedure in order to reduce a set-valued optimization problem with functional constraints to an unconstrained one. The penalization results are given in several cases: for weak and strong solutions, in global and local settings, and considering two kinds of epigraphical mappings of the set-valued map that defines the constraints. Then necessary and sufficient conditions are obtained separately in terms of Bouligand derivatives of the objective and constraint mappings. 相似文献
44.
45.
Stefani Gamboa-Ramirez Dr. Bruno Faure Dr. Marius Réglier Dr. A. Jalila Simaan Dr. Maylis Orio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(66):e202202206
The stereoselective copper-mediated hydroxylation of intramolecular C−H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C−H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated ( L1 ) or non-activated ( L2 ) C−H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species ( P ) in equilibrium with the key intermediate bis-(μ-oxo) isomer ( O ) responsible for the C−H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C−H activation step, where the complex bearing the non-activated C−H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions. 相似文献
46.
Characterizing Methyl‐Bearing Side Chain Contacts and Dynamics Mediating Amyloid β Protofibril Interactions Using 13Cmethyl‐DEST and Lifetime Line Broadening 下载免费PDF全文
Dr. Nicolas L. Fawzi Dr. David S. Libich Dr. Jinfa Ying Dr. Vitali Tugarinov Dr. G. Marius Clore 《Angewandte Chemie (International ed. in English)》2014,53(39):10345-10349
Many details pertaining to the formation and interactions of protein aggregates associated with neurodegenerative diseases are invisible to conventional biophysical techniques. We recently introduced 15N dark‐state exchange saturation transfer (DEST) and 15N lifetime line‐broadening to study solution backbone dynamics and position‐specific binding probabilities for amyloid β (Aβ) monomers in exchange with large (2–80 MDa) protofibrillar Aβ aggregates. Here we use 13Cmethyl DEST and lifetime line‐broadening to probe the interactions and dynamics of methyl‐bearing side chains in the Aβ‐protofibril‐bound state. We show that all methyl groups of Aβ40 populate direct‐contact bound states with a very fast effective transverse relaxation rate, indicative of side‐chain‐mediated direct binding to the protofibril surface. The data are consistent with position‐specific enhancements of 13Cmethyl‐${R{{{\rm tethered}\hfill \atop 2\hfill}}}$ values in tethered states, providing further insights into the structural ensemble of the protofibril‐bound state. 相似文献
47.
Marius Murariu Miroslaw Pluta Michaël Alexandre Philippe Dubois 《European Polymer Journal》2008,44(11):3842-3852
Large amounts of stable β-anhydrite II (AII), a specific type of dehydrated gypsum and a by-product of lactic acid production process, can be melt-blended with bio-sourced and biodegradable polylactide (PLA) to produce economically interesting novel composites with high tensile strength and thermal stability.To enhance their toughness, while preserving an optimal stiffness, selected low molecular weight plasticizers (bis(2-ethylhexyl) adipate and glyceryl triacetate) and polymeric adipates with different molecular weights have been mixed with a specific PLA (l/d isomer ratio of 96/4) and 40 wt% of AII using an internal kneader. Addition of up to 10 wt% plasticizer into these highly filled compositions can trigger a fourfold increase of the impact strength with respect to the compositions without any modifier, cold crystallization properties and a significant decrease of their glass transition temperature. Moreover, these ternary compositions (PLA-AII-plasticizer) are clearly characterized by easier processing, notable thermo-mechanical performances and good filler dispersion. This study represents a new approach in formulating novel melt-processable polyester grades with improved characteristic features using PLA as biodegradable polymer matrix. 相似文献
48.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
49.
Kuszewski J Schwieters CD Garrett DS Byrd RA Tjandra N Clore GM 《Journal of the American Chemical Society》2004,126(20):6258-6273
The major rate-limiting step in high-throughput NMR protein structure determination involves the calculation of a reliable initial fold, the elimination of incorrect nuclear Overhauser enhancement (NOE) assignments, and the resolution of NOE assignment ambiguities. We present a robust approach to automatically calculate structures with a backbone coordinate accuracy of 1.0-1.5 A from datasets in which as much as 80% of the long-range NOE information (i.e., between residues separated by more than five positions in the sequence) is incorrect. The current algorithm differs from previously published methods in that it has been expressly designed to ensure that the results from successive cycles are not biased by the global fold of structures generated in preceding cycles. Consequently, the method is highly error tolerant and is not easily funnelled down an incorrect path in either three-dimensional structure or NOE assignment space. The algorithm incorporates three main features: a linear energy function representation of the NOE restraints to allow maximization of the number of simultaneously satisfied restraints during the course of simulated annealing; a method for handling the presence of multiple possible assignments for each NOE cross-peak which avoids local minima by treating each possible assignment as if it were an independent restraint; and a probabilistic method to permit both inactivation and reactivation of all NOE restraints on the fly during the course of simulated annealing. NOE restraints are never removed permanently, thereby significantly reducing the likelihood of becoming trapped in a false minimum of NOE assignment space. The effectiveness of the algorithm is demonstrated using completely automatically peak-picked experimental NOE data from two proteins: interleukin-4 (136 residues) and cyanovirin-N (101 residues). The limits of the method are explored using simulated data on the 56-residue B1 domain of Streptococcal protein G. 相似文献
50.
Two-dimensional electrophoresis of membrane proteins 总被引:1,自引:0,他引:1
One third of all genes of various organisms encode membrane proteins, emphasizing their crucial cellular role. However, due
to their high hydrophobicity, membrane proteins demonstrate low solubility and a high tendency for aggregation. Indeed, conventional
two-dimensional gel electrophoresis (2-DE), a powerful electrophoretic method for the separation of complex protein samples
that applies isoelectric focusing (IEF) in the first dimension and sodium dodecyl sulfate polyacrylamide gel electrophoresis
(SDS-PAGE) in the second dimension, has a strong bias against membrane proteins. This review describes two-dimensional electrophoretic
techniques that can be used to separate membrane proteins. Alternative methods for performing conventional 2-DE are highlighted;
these involve replacing the IEF with electrophoresis using cationic detergents, namely 16-benzyldimethyl-n-hexadecylammonium chloride (16-BAC) and cetyl trimethyl ammonium bromide (CTAB), or the anionic detergent SDS. Finally, the
separation of native membrane protein complexes through the application of blue and clear native gel electrophoresis (BN/CN-PAGE)
is reviewed, as well as the free-flow electrophoresis (FFE) of membranes. 相似文献