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231.
David D. Evanoff Jr. Joseph B. Carroll Ryan D. Roeder Zachary J. Hunt Justin R. Lawrence Stephen H. Foulger 《Journal of polymer science. Part A, Polymer chemistry》2008,46(23):7882-7897
Methyl methacrylate derived monomers functionalized with pendant carbazole and oxadiazole moieties were synthesized and could be copolymerized to form a random copolymer. The glass transition temperature of the copolymers could be predicted with a Fox equation and ranged from 140 to 191 °C. The photoluminescent characteristics of the copolymers, both in solution and in solid films, exhibited emission that was a combination of sharp and broad peaks, suggestive of monomeric and chromophore aggregation emission. These trends were also apparent in the electroluminescent response of the copolymers, where the appearance of an electromer emission was evident and was tentatively assigned to the carbazole moieties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7882–7897, 2008 相似文献
232.
Gary S. Groenewold Christopher M. Leavitt Ryan P. Dain Jos Oomens Jeffrey D. Steill Michael J. van Stipdonk 《Rapid communications in mass spectrometry : RCM》2009,23(17):2706-2710
Tandem mass spectrometry and wavelength‐selective infrared photodissociation were used to generate an infrared spectrum of gas‐phase triethylphosphate cationized by attachment of K+. Prominent absorptions were observed in the region of 900 to 1300 cm?1 that are characteristic of phosphate P?O and P? O? R stretches. The relative positions and intensities of the IR absorptions were reproduced well by density functional theory (DFT) calculations performed using the B3LYP functional and the 6‐31+G(d), 6‐311+G(d,p) and 6‐311++G(3df,2pd) basis sets. Because of good correspondence between experiment and theory for the cation, DFT was then used to generate a theoretical spectrum for neutral triethylphosphate, which in turn accurately reproduces the IR spectrum of the neat liquid when solvent effects are included in the calculations. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
233.
A class of differential-delay systems with hysteresis is considered. Conditions ensuring boundedness of solutions and related asymptotic and integrability properties are expressed in terms of data associated with the linear component of the overall system and a Lipschitz constant associated with the hysteretic component. 相似文献
234.
Controlling the extent of orientation is of great interest in polymer processing and is effected by the choice of polymer, the fabrication technique and the processing conditions. Understanding the crystalline transitions that form highly oriented fibrils is necessary for modeling the changes in physical properties, relative to degree of orientation. A model is proposed to describe the mechanical properties of drawn semicrystalline polymer films based on structural transitions. With a minimal amount of experimental data (requiring testing on only two drawn films samples), this model can be used to predict film properties. These properties include the critical and maximum draw ratios, the moduli at the maximum draw ratio, the moduli of the fiber, the modulus of the nonfibrous gel relative to draw ratio, the volume fraction of fibers, and the rate of fibrillation. Where high degrees of uniaxial orientation are required, the polymer is typically drawn in the solid state, meaning the polymer is stretched in a single direction at temperatures below the melting point. During this process, pre‐existing crystallites are transformed into fiber‐like structures with large aspect ratios. The presence of these rigid asymmetric structures significantly enhances the moduli and break strength of the polymer. This work presents a model that describes the formation of fiber‐like structures. The volume fraction of fibers is predicted to be linear in draw ratio. The derived relationship between volume fraction of fibers and draw ratio can then be used for the prediction of the various properties of the oriented film. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 607–618, 2008 相似文献
235.
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237.
Paulo A. Machicao Scott R. Burt Ryan K. Christensen Nathan B. Lohner J.D. Singleton Matt A. Peterson 《Tetrahedron letters》2017,58(24):2318-2321
Treatment of N-[(4-hydroxy-6-phenyl)pyrimidin-2-yl]cyanamide with 1° alkyl or arylamines in isopropyl alcohol for only 10 min at 110–120 °C under microwave conditions gave the corresponding N′-alkyl(aryl)guanidine derivatives in excellent yields (65–84%). Isolated yields were greatest when >1.0 equiv. of amines were employed, but excellent results were also obtained when aryl and alkylamines were reacted with a more atom-economical loading (1.0 equiv.; 70% and 72% ave. yields, respectively). Arylamines with either highly electron withdrawing substituents (e.g. CO2H) or pi-deficient heterocycles (e.g. variously substituted aminopyridines) did not work well under these conditions, and reaction with ureas and/or amino acids did not give detectable products. Work-up was exceedingly simple, and involved simple collection and washing of product on a sintered glass funnel. Products were obtained in analytically pure form and required approximately 1 h to prepare, start to finish. 相似文献
238.
The fabrication of a novel sheathless interface for capillary electrophoresis–electrospray–mass spectrometry (CE–ESI–MS) is described. A programmable CO2 laser was used to ablate small channels in the walls of a polyimide capillary near the terminus. Subsequent exposure of the channel region to a cellulose acetate solution followed by drying resulted in the formation of an electrically conductive semi-permeable membrane. Application of an appropriate voltage to the reservoir resulted in the simultaneous establishment of an electrical connection for CE and ESI. Interface viability was demonstrated by conducting a CE separation of a peptide mixture, with detection accomplished via positive ion mode ESI–MS. For the peptide Val-Tyr-Val, a limit of detection of 0.1 femtomole (S/N 3) was achieved using single reaction monitoring. Attributes of the interface include structural robustness, ease of fabrication, minimal interface dead volume, and the ability to alter post-separation analyte ionization status by use of appropriate buffers in the interface reservoir. 相似文献
239.
Ann M. Anderson Mary K. Carroll Emily C. Green Jason T. Melville Michael S. Bono 《Journal of Sol-Gel Science and Technology》2010,53(2):199-207
Hydrophobic silica aerogels have been prepared using the rapid supercritical extraction (RSCE) technique. The RSCE technique
is a one-step methanol supercritical extraction method for producing aerogel monoliths in 3 to 8 h. Standard aerogels were
prepared from a tetramethoxysilane (TMOS) recipe with a molar ratio of TMOS:MeOH:H2O:NH4OH of 1.0:12.0:4.0:7.4 × 10−3. Hydrophobic aerogels were prepared using the same recipe except the TMOS was replaced with a mixture of TMOS and one of
the following organosilane co-precursors: methytrimethoxysilane (MTMS), ethyltrimethoxysilane (ETMS), or propyltrimeth-oxysilane
(PTMS). Results show that, by increasing the amount of catalyst and increasing gelation time, monolithic aerogels can be prepared
out of volume mixtures including up to 75% MTMS, 50% ETMS or 50% PTMS in 7.5–15 h. As the amount of co-precursor is increased
the aerogels become more hydrophobic (sessile tests with water droplets yield contact angles up to 155°) and less transparent
(transmission through a 12.2-mm thick sample decreases from 83 to 50% at 800 nm). The skeletal and bulk density decrease and
the surface area increases (550–760 m2/g) when TMOS is substituted with increasing amounts of MTMS. The amount of co-precursor does not affect the thermal conductivity.
SEM imaging shows significant differences in the nanostructure for the most hydrophobic surfaces. 相似文献
240.
The dynamics of many biological processes of interest, such as the folding of a protein, are slow and complicated enough that a single molecular dynamics simulation trajectory of the entire process is difficult to obtain in any reasonable amount of time. Moreover, one such simulation may not be sufficient to develop an understanding of the mechanism of the process, and multiple simulations may be necessary. One approach to circumvent this computational barrier is the use of Markov state models. These models are useful because they can be constructed using data from a large number of shorter simulations instead of a single long simulation. This paper presents a new Bayesian method for the construction of Markov models from simulation data. A Markov model is specified by (τ,P,T), where τ is the mesoscopic time step, P is a partition of configuration space into mesostates, and T is an N(P)×N(P) transition rate matrix for transitions between the mesostates in one mesoscopic time step, where N(P) is the number of mesostates in P. The method presented here is different from previous Bayesian methods in several ways. (1) The method uses Bayesian analysis to determine the partition as well as the transition probabilities. (2) The method allows the construction of a Markov model for any chosen mesoscopic time-scale τ. (3) It constructs Markov models for which the diagonal elements of T are all equal to or greater than 0.5. Such a model will be called a "consistent mesoscopic Markov model" (CMMM). Such models have important advantages for providing an understanding of the dynamics on a mesoscopic time-scale. The Bayesian method uses simulation data to find a posterior probability distribution for (P,T) for any chosen τ. This distribution can be regarded as the Bayesian probability that the kinetics observed in the atomistic simulation data on the mesoscopic time-scale τ was generated by the CMMM specified by (P,T). An optimization algorithm is used to find the most probable CMMM for the chosen mesoscopic time step. We applied this method of Markov model construction to several toy systems (random walks in one and two dimensions) as well as the dynamics of alanine dipeptide in water. The resulting Markov state models were indeed successful in capturing the dynamics of our test systems on a variety of mesoscopic time-scales. 相似文献