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1.
Besides all their conformational degrees of freedom, drug‐like molecules and natural products often also undergo tautomeric interconversions. Compared to the huge efforts made in experimental investigation of tautomerism, open and free algorithmic solutions for prototropic tautomer generation are surprisingly rare. The few freely available software packages limit their output to a subset of the possible configurational space by sometimes unwanted prior assumptions and complete neglection of ring‐chain tautomerism. Here, we describe an adjustable fully automatic tautomer enumeration approach, which is freely available and also incorporates the detection of ring‐chain variants. The algorithm is implemented in the MolTPC framework and accessible on SourceForge. © 2013 Wiley Periodicals, Inc.  相似文献   
2.
Two dinuclear succinato‐bridged nickel(II) complexes [Ni(RR‐L)]2(μ‐SA)(ClO4)2 ( 1 ) and [Ni(SS‐L)]2(μ‐SA)(ClO4)2 ( 2 ) (L = 5, 5, 7, 12, 12, 14‐hexamethyl‐1, 4, 8, 11‐tetraazacyclotetradecane, SA = succinic acid) were synthesized and characterized by EA, Circular dichroism (CD), as well as IR and UV/Vis spectroscopy. Single crystal X‐ray diffraction analyses revealed that the NiII atoms display a distorted octahedral coordination arrangement, and the succinato ligand bridges two central NiII atoms in a bis bidentate fashion to form dimers in 1 and 2 . The monomers of {[Ni(RR‐L)]2(μ‐SA)}2+ and {[Ni(SS‐L)]2(μ‐SA)}2+ are connected by O–H ··· O and N–H ··· O hydrogen bonds into a 1D right‐handed and left‐handed helical chain along the b axis, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.  相似文献   
3.
多能耦合系统是未来分布式能源供给方式的重要发展方向。为了实现电热耦合能源供给系统的合理规划、促进能源供给与消费的经济与环保的协调发展,提出一种面向电热耦合能源系统的综合能源系统双阶段规划优化方法。模型的第一阶段是在投资和环境最优的目标下实现电热耦合综合能源系统的合理规划,第二阶段是在考虑设备运行特性的基础上对规划的结果进行运行优化,以获得能源系统的最优运行方案,并从多个指标验证规划方案的合理性。利用NSGA-II算法求得模型进的帕累托解集,使用多准则妥协优化法从帕累托解集中决策出最优配置方案。仿真结果表明,提出的双阶段多目标综合能源规划方法能够实现能源供给系统的经济与环保双优。  相似文献   
4.
针对由一个拥有线上直销渠道的制造商以及一个线下零售商组成的供应链,考虑消费者对不同渠道的偏好构建了供应链博弈模型,研究了竞争环境下制造商与零售商的最优BOPS合作策略,并分析了BOPS合作在改善交通拥堵方面的作用。研究表明,BOPS合作在缓解供应链双重边际效应的同时会加剧渠道之间的价格竞争,所以并不总是对供应链有利;仅当消费者线上渠道偏好程度比较低且线下麻烦成本比较大时,制造商和零售商才会都从BOPS合作中受益从而自愿达成合作,其他情形下制造商可根据供应链利润变化设计转移支付契约促成与线下零售商的BOPS合作并实现双赢;此外,一定条件下BOPS合作能够通过调整渠道需求结构,在保证供应链成员利润的同时对交通拥堵改善也带来正向作用。  相似文献   
5.
Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO2 photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO2-scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO2 photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation.  相似文献   
6.
Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006  相似文献   
7.
We have reported that intramolecular chain‐transfer reaction takes place in radical polymerization of itaconates at high temperatures and/or at low monomer concentrations. In this article, radical polymerizations of di‐n‐butyl itaconate (DBI) were carried out in toluene at 60 °C in the presence of amide compounds. The 13C‐NMR spectra of the obtained poly(DBI)s indicated that the intramolecular chain‐transfer reaction was suppressed as compared with in the absence of amide compounds. The NMR analysis of DBI and N‐ethylacetamide demonstrated both 1:1 complex and 1:2 complex were formed at 60 °C through a hydrogen‐bonding interaction. The ESR analysis of radical polymerization of diisopropyl itaconate (DiPI) was conducted in addition to the NMR analysis of the obtained poly(DiPI). It was suggested that the suppression of the intramolecular chain‐transfer reaction with the hydrogen‐bonding interaction was achieved by controlling the conformation of the side chain at the penultimate monomeric unit of the propagating radical with an isotactic stereosequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4895–4905, 2004  相似文献   
8.
The aim of this paper is to present an online economical quality-control procedure for attributes in a process subject to quality deterioration after random shift and misclassification errors during inspections. The process starts in control (State I) and, in a random time, it shifts to out of control (State II). Once at State II, the non-conforming fraction increases according to a non-decreasing function ψ(z), where z is the number of items produced after a shift. The monitoring procedure consists of inspecting a single item at every m produced items, which is examined r times independently to decide its condition. Once an inspected item is declared non-conforming, the process is stopped and adjusted. A direct search technique is used to find the optimum parameters which minimize the expected cost function. The proposed model is illustrated by a numerical example. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   
9.
10.
Let \begin{align*}{\mathcal T}\end{align*}n be the compact convex set of tridiagonal doubly stochastic matrices. These arise naturally in probability problems as birth and death chains with a uniform stationary distribution. We study ‘typical’ matrices T∈ \begin{align*}{\mathcal T}\end{align*}n chosen uniformly at random in the set \begin{align*}{\mathcal T}\end{align*}n. A simple algorithm is presented to allow direct sampling from the uniform distribution on \begin{align*}{\mathcal T}\end{align*}n. Using this algorithm, the elements above the diagonal in T are shown to form a Markov chain. For large n, the limiting Markov chain is reversible and explicitly diagonalizable with transformed Jacobi polynomials as eigenfunctions. These results are used to study the limiting behavior of such typical birth and death chains, including their eigenvalues and mixing times. The results on a uniform random tridiagonal doubly stochastic matrices are related to the distribution of alternating permutations chosen uniformly at random.© 2012 Wiley Periodicals, Inc. Random Struct. Alg., 42, 403–437, 2013  相似文献   
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