全文获取类型
收费全文 | 638篇 |
免费 | 41篇 |
国内免费 | 4篇 |
专业分类
化学 | 490篇 |
力学 | 9篇 |
数学 | 76篇 |
物理学 | 108篇 |
出版年
2024年 | 5篇 |
2023年 | 22篇 |
2022年 | 26篇 |
2021年 | 34篇 |
2020年 | 54篇 |
2019年 | 27篇 |
2018年 | 13篇 |
2017年 | 15篇 |
2016年 | 37篇 |
2015年 | 29篇 |
2014年 | 30篇 |
2013年 | 32篇 |
2012年 | 32篇 |
2011年 | 42篇 |
2010年 | 15篇 |
2009年 | 17篇 |
2008年 | 16篇 |
2007年 | 15篇 |
2006年 | 26篇 |
2005年 | 12篇 |
2004年 | 12篇 |
2003年 | 10篇 |
2002年 | 3篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1998年 | 9篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 11篇 |
1994年 | 7篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1988年 | 7篇 |
1985年 | 14篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1970年 | 3篇 |
1938年 | 2篇 |
1932年 | 2篇 |
1910年 | 2篇 |
1898年 | 2篇 |
1895年 | 2篇 |
1891年 | 2篇 |
排序方式: 共有683条查询结果,搜索用时 0 毫秒
81.
Yartys VA Denys RV Maehlen JP Frommen C Fichtner M Bulychev BM Emerich H 《Inorganic chemistry》2007,46(4):1051-1055
Aluminum trihydride (alane) is one of the most promising among the prospective solid hydrogen-storage materials, with a high gravimetric and volumetric density of hydrogen. In the present work, the alane, crystallizing in the gamma-AlH3 polymorphic modification, was synthesized and then structurally characterized by means of synchrotron X-ray powder diffraction. This study revealed that gamma-AlH3 crystallizes with an orthorhombic unit cell (space group Pnnm, a = 5.3806(1) A, b = 7.3555(2) A, c = 5.77509(5) A). The crystal structure of gamma-AlH3 contains two types of AlH6 octahedra as the building blocks. The Al-H bond distances in the structure vary in the range of 1.66-1.79 A. A prominent feature of the crystal structure is the formation of the bifurcated double-bridge bonds, Al-2H-Al, in addition to the normal bridge bonds, Al-H-Al. This former feature has not been previously reported for Al-containing hydrides so far. The geometry of the double-bridge bond shows formation of short Al-Al (2.606 A) and Al-H (1.68-1.70 A) bonds compared to the Al-Al distances in Al metal (2.86 A) and Al-H distances for Al atoms involved in the formation of normal bridge bonds (1.769-1.784 A). The crystal structure of gamma-AlH3 contains large cavities between the AlH6 octahedra. As a consequence, the density is 11% less than for alpha-AlH3. 相似文献
82.
Dr. Jie Wang Dr. Tian Qin Dr. Tie‐Gen Chen Dr. Laurin Wimmer Jacob T. Edwards Dr. Josep Cornella Benjamin Vokits Dr. Scott A. Shaw Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2016,55(33):9676-9679
A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross‐coupling between alkyl‐carboxylic acids and boronic acids is described. This Ni‐catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox‐active ester derivatives, specifically N‐hydroxy‐tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2?6 H2O—$9.5 mol?1, Et3N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption. 相似文献
83.
Maximilian Krempe Dr. Rainer Lippert Dr. Frank Hampel Prof. Dr. Ivana Ivanović‐Burmazović Prof. Dr. Norbert Jux Prof. Dr. Rik R. Tykwinski 《Angewandte Chemie (International ed. in English)》2016,55(47):14802-14806
A 4‐ethynylpyridyl derivative with sterically shielding phenyl groups in the 3‐ and 5‐positions has been synthesized and used to terminate a series of polyynes. This approach allows for the synthesis of stable polyynes up to an octayne, twice as long as previous accessible for “unstabilized” pyridyl‐endcapped polyynes. The potential of these polyynes as wire‐like linkers to metal centers is demonstrated by axial coordination of pyridyl groups to zinc‐ and ruthenium‐metalloporphyrins. 相似文献
84.
Wilhelm Maximilian Hützler Ernst Egert Michael Bolte 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(9):705-715
A path to new synthons for application in crystal engineering is the replacement of a strong hydrogen‐bond acceptor, like a C=O group, with a weaker acceptor, like a C=S group, in doubly or triply hydrogen‐bonded synthons. For instance, if the C=O group at the 2‐position of barbituric acid is changed into a C=S group, 2‐thiobarbituric acid is obtained. Each of the compounds comprises two ADA hydrogen‐bonding sites (D = donor and A = acceptor). We report the results of cocrystallization experiments of barbituric acid and 2‐thiobarbituric acid, respectively, with 2,4‐diaminopyrimidine, which contains a complementary DAD hydrogen‐bonding site and is therefore capable of forming an ADA/DAD synthon with barbituric acid and 2‐thiobarbituric acid. In addition, pure 2,4‐diaminopyrimidine was crystallized in order to study its preferred hydrogen‐bonding motifs. The experiments yielded one ansolvate of 2,4‐diaminopyrimidine (pyrimidine‐2,4‐diamine, DAPY), C4H6N4, (I), three solvates of DAPY, namely 2,4‐diaminopyrimidine–1,4‐dioxane (2/1), 2C4H6N4·C4H8O2, (II), 2,4‐diaminopyrimidine–N,N‐dimethylacetamide (1/1), C4H6N4·C4H9NO, (III), and 2,4‐diaminopyrimidine–1‐methylpyrrolidin‐2‐one (1/1), C4H6N4·C5H9NO, (IV), one salt of barbituric acid, viz. 2,4‐diaminopyrimidinium barbiturate (barbiturate is 2,4,6‐trioxopyrimidin‐5‐ide), C4H7N4+·C4H3N2O3−, (V), and two solvated salts of 2‐thiobarbituric acid, viz. 2,4‐diaminopyrimidinium 2‐thiobarbiturate–N,N‐dimethylformamide (1/2) (2‐thiobarbiturate is 4,6‐dioxo‐2‐sulfanylidenepyrimidin‐5‐ide), C4H7N4+·C4H3N2O2S−·2C3H7NO, (VI), and 2,4‐diaminopyrimidinium 2‐thiobarbiturate–N,N‐dimethylacetamide (1/2), C4H7N4+·C4H3N2O2S−·2C4H9NO, (VII). The ADA/DAD synthon was succesfully formed in the salt of barbituric acid, i.e. (V), as well as in the salts of 2‐thiobarbituric acid, i.e. (VI) and (VII). In the crystal structures of 2,4‐diaminopyrimidine, i.e. (I)–(IV), R22(8) N—H…N hydrogen‐bond motifs are preferred and, in two structures, additional R32(8) patterns were observed. 相似文献
85.
Andrew J. Parnell Ashley J. Cadby Alan D. F. Dunbar George L. Roberts Alex Plumridge Robert M. Dalgliesh Maximilian W. A. Skoda Richard A. L. Jones 《Journal of polymer science. Part A, Polymer chemistry》2016,54(2):141-146
We show that [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) at the surface of thin film blends of poly(3-hexylthiophene) (P3HT):PC61BM can be patterned by water. Using a series of heating and cooling steps, water droplets condense onto the blend film surface. This is possible due to the liquid-like, water swollen layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Breath pattern water deformation and subsequent drying on the film surface results in isolated PC61BM structures, showing that migration of PC61BM takes place. This was confirmed by selective wavelength illumination to spatially map the photoluminescence from the P3HT and PC61BM. Within a device, redistribution of the surface PC61BM into aggregates would be catastrophic, as it would markedly alter device performance. We also postulate that repeated volume change of the poly(3,4-ethylenedioxythiophene) polystyrene sulfonate layer by water swelling may be, in part, responsible for the delamination failure mechanism in thin film solar cells devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 141–146 相似文献
86.
87.
88.
Ohne Zusammenfassung 相似文献
89.
Markus Clemens Moritz HeliasThorsten Steinmetz Georg Wimmer 《Journal of Computational and Applied Mathematics》2008
The simulation of slowly varying transient electric high-voltage fields and magnetic fields requires the repeated and successive solution of high-dimensional linear algebraic systems of equations with identical or near-identical system matrices and different right-hand side vectors. For these solution processes which are required within implicit time integration schemes and nonlinear (quasi-)Newton–Raphson methods an iterative multiple right-hand side (mrhs) scheme is used which recycles vector subspaces resulting from previous preconditioned conjugate gradient iteration runs. The combination of this scheme with a subspace projection extrapolation start value generation scheme is discussed. Numerical results for three-dimensional electric and magnetic field simulations are presented and the efficiency of the new schemes re-using eigenvector information from previous iteration processes with different tolerance criteria are compared to those of standard conjugate gradient iterations. 相似文献
90.
J. Kunze S. Koelling M. Reich M. A. Wimmer 《Analytical and bioanalytical chemistry》2000,366(2):165-166
A technique for the determination of titanium and zirconium in human blood serum, after pressurized digestion utilizing ICP-MS coupled to an ultrasonic nebulizer (USN) and desolvating membrane is described. As no CRM for titanium is available, zirconium has been determined in order to demonstrate the accuracy of the technique, as the limits in blood are well known. Bone cement consists basically of a polymer, namely polymethylmethacrylate (PMMA). For better X-ray contrast some manufacturers use incorporated ZrO2 with a volume fraction of 10 to 15%. Thus, the zirconium present in the PMMA matrix can be used as an indicator for the PMMA particulate debris. 相似文献