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71.
We established that acetylacetone and acetone photolytically sensitize norbornene to undergo an efficient radical addition
of solvent (ranging from hexane, cyclic ethers, haloalkanes, acetone, alcohols and acetonitrile) across the double bond. In
view of its synthetic applicability, sensitized photoreactions of norbornene were reviewed and their mechanisms were compared.
Photolysis of acetylacetone in the presence of norbornene in hexane induced i) acetylacetone to cycloadd to norbornene giving
the expected 1,5-diketone, and ii) sensitization by triplet excited acetylacetone to generate reactive norbornene, which underwent
dimerization as well as the addition of a solvent molecule by radical chain processes. In other solvents, the radical chain
addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts
to norbornene. While the excited species of acetylacetone for the sensitization was deduced to be its spectroscopic triplet
excited state, that for the cycloaddition should involve a different one which may be a twisted triplet acetylacetone; sensitization
experiments showed that the cycloaddition did not occur from the spectroscopic triplet state. Triplet excited acetone sensitized
norbornene to undergo the same solvent addition more efficiently and cleanly than acetylacetone did. In view of various conflicts
existing in the proposed energy transfer mechanism, the sensitized norbornene reactions were rationalized with electron transfer
and a cation radical chain mechanism. 相似文献
72.
73.
One of the shortcomings of R&D evaluation is a lack of emphasis on analytical assessment of the value of an on-going R&D project. This paper addresses the problem concerning the distributive aspect of access to superior knowledge. Decision tree analysis and probability models appear to be appropriate tools for assessing the values of an intermediate result and patent reward of a firm's R&D decision in an environment of perfect information and oligopolistic competition. The assessed values are used as minimum prices acceptable to the firm when the knowledge is disseminated to the public. This paper will attempt to resolve this problem through the determination of the appropriate values of the reservation price of the first-stage invention in terms of the final reward and of a patent reward for which the inventor is willing to apply. 相似文献
74.
在水热晶化合成一系列NASICON型化合物的基础上,应用固体高分辨31P和29Si MAS NMR,研究了几种NASICON化合物的结构,观察其骨架原子P和Si在结构中的状态及分布,并解释了由于在结构中发生取代作用而引起,Si或P的化学位移的变化. 相似文献
75.
一类Narcissistic反应过渡态的优化 总被引:1,自引:0,他引:1
我们对一类narcissistic 反应XCH_2-CH_2Y→[过渡态TS]→YCH_2—CH_2X (1)进行了研究,结果表明其过渡态能在对称性限制下由能量极小化方法较容易地给出. 采用IMSPAK分子轨道从头算程序,在IBM VM/370计算机系统上用STO—3G极小基组以平衡几何构型的能量梯度优化方法,在对称性限制下对反应(1)的几种反应体系的过渡态构型进行了优化,其结果列于表1. 相似文献
76.
To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007 相似文献
77.
78.
Q.-Y. Shao A.-D. Li J.-B. Cheng H.-Q. Ling D. Wu Z.-G. Liu N.-B. Ming C. Wang H.-W. Zhou B.-Y. Nguyen 《Applied Physics A: Materials Science & Processing》2005,81(6):1181-1185
LaAlO3 (LAO) gate dielectric films were deposited on Si substrates by low-pressure metalorganic chemical vapor deposition. The interfacial structure and composition distribution were investigated by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectroscopy (SIMS), and Auger-electron spectroscopy (AES). HRTEM confirms that there exists an interfacial layer between LAO and Si in most samples. AES, SIMS, and XPS analyses indicate that the interfacial layer is compositionally graded La–Al silicate and the Al element is severely deficient close to the Si surface. Electrical properties of LAO films were evaluated. No evident difference in electrical properties between samples with and without native SiO2 layers was observed. The electrical properties are discussed in terms of LAO growth mechanisms, in relation to the interfacial structure. PACS 73.40.Qv; 81.15.Gh; 77.55.+f; 68.35.-p 相似文献
79.
一个推广的Hardy-Hilbert型不等式及其逆式 总被引:1,自引:0,他引:1
本文引入单参数λ及应用Beta函数,给一个Hardy-Hilbert型不等式以具有最佳常数因子的推广,作为应用,给出了它的逆向形式. 相似文献
80.