全文获取类型
收费全文 | 3387篇 |
免费 | 119篇 |
国内免费 | 11篇 |
专业分类
化学 | 2283篇 |
晶体学 | 17篇 |
力学 | 61篇 |
数学 | 399篇 |
物理学 | 757篇 |
出版年
2023年 | 22篇 |
2022年 | 45篇 |
2021年 | 60篇 |
2020年 | 55篇 |
2019年 | 64篇 |
2018年 | 31篇 |
2017年 | 39篇 |
2016年 | 93篇 |
2015年 | 60篇 |
2014年 | 85篇 |
2013年 | 157篇 |
2012年 | 201篇 |
2011年 | 227篇 |
2010年 | 109篇 |
2009年 | 83篇 |
2008年 | 169篇 |
2007年 | 178篇 |
2006年 | 161篇 |
2005年 | 168篇 |
2004年 | 132篇 |
2003年 | 116篇 |
2002年 | 96篇 |
2001年 | 71篇 |
2000年 | 62篇 |
1999年 | 39篇 |
1998年 | 28篇 |
1997年 | 41篇 |
1996年 | 41篇 |
1995年 | 50篇 |
1994年 | 47篇 |
1993年 | 45篇 |
1992年 | 47篇 |
1991年 | 34篇 |
1990年 | 37篇 |
1989年 | 23篇 |
1988年 | 25篇 |
1987年 | 22篇 |
1985年 | 36篇 |
1984年 | 26篇 |
1982年 | 28篇 |
1981年 | 35篇 |
1980年 | 21篇 |
1979年 | 35篇 |
1978年 | 28篇 |
1977年 | 32篇 |
1976年 | 35篇 |
1975年 | 31篇 |
1974年 | 27篇 |
1973年 | 37篇 |
1972年 | 26篇 |
排序方式: 共有3517条查询结果,搜索用时 15 毫秒
1.
2.
Hansen Karin Vels Kreka Kosova Jacobsen Torben 《Journal of Solid State Electrochemistry》2019,23(3):811-822
Journal of Solid State Electrochemistry - Local cathodic polarizations of yttria-stabilized zirconia were carried out with a PtIr probe as the working electrode in a controlled atmosphere high... 相似文献
3.
Olaf Hansen 《Mathematical Methods in the Applied Sciences》2002,25(12):1075-1090
In this article we study the radiosity operator along an edge between two adjacent half‐planes. First we show that the radiosity operator is invertible in a whole scale of anisotropic Sobolev spaces. In the absence of any shadows we are able to derive regularity properties of the solution, which depend only on the angle between the half‐planes, the reflectivity coefficients and the right‐hand side. This work can be considered as a supplement to the article of Rathsfeld (Mathematical Methods in the Applied Sciences 1999; 22 : 217–241). Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
4.
5.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
6.
Marit Seifert Stephanie Hesse Vasken Kabrelian Dieter Klemm 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):463-470
For the modification of medically useful biomaterials from bacterially synthesized cellulose, fleeces of Acetobacter xylinum have been produced in the presence of 0.5, 1.0, and 2.0% (m/v) carboxymethylcellulose (CMC), methylcellulose (MC), and poly(vinyl alcohol) (PVA), respectively, in the Hestrin-Schramm culture medium. The incorporation of the water-soluble polymers into cellulose and their influence on the structure, crystal modifications, and material properties are described. With IR and solid-state 13C NMR spectroscopy of the fleeces, the presence of the cellulose ethers and an increase in the amorphous parts of the cellulose modifications (NMR results) have been detected. The incorporation is represented by a higher product yield, too. As demonstrated by scanning electron microscopy, a porelike cellulose network structure forms in the presence of CMC and MC. This modified structure increases the water retention ability (expressed as the water content), the ion absorption capacity, and the remaining nitrogen-containing residues from the culture medium or bacteria cells. The water content of bacterial cellulose (BC) in the never dried state and the freeze-dried, reswollen state can be controlled by the CMC concentration in the culture solution. The freeze-dried, reswollen BC-CMC (2.0%) contains 96% water after centrifugation, whereas standard BC has only 73%. About 98% water is included in a BC-MC composite in the wet state, and about 93% is included in the reswollen state synthesized in the presence of 0.5, 1.0, or 2.0% MC. These biomaterial composites can be stored in the dried state and reswollen before use, reaching a higher water absorption than pure, never dried BC. The copper ion capacity of BC-CMC composites increases proportionally with the added amount of CMC. BC-CMC (0.5%) can absorb 3 times more copper ions than original BC. In the case of 0.5 and 1.0% PVA additions to the culture solution, this polymer cannot be detected in the cellulose fleeces after they are washed. Nevertheless the presence of PVA in the culture medium effects a decreased product yield, a retention of nitrogen-containing residues in the material during purification, a reduced water absorption ability, and a slightly higher copper ion capacity in comparison with original BC. The water content of freeze-dried, reswollen BC-PVA (0.5%) is only 62%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 463–470, 2004 相似文献
7.
Nis Halland Tore Hansen Karl Anker Jrgensen 《Angewandte Chemie (International ed. in English)》2003,42(40):4837-4837
8.
We prove that, in Euclidean space, any nonnegatively curved, compact, smoothly immersed hypersurface lies outside the convex hull of its boundary, provided the boundary satisfies certain required conditions. This gives a convex hull property, dual to the classical one for surfaces with nonpositive curvature. A version of this result in the nonsmooth category is obtained as well. We show that our boundary conditions determine the topology of the surface up to at most two choices. The proof is based on uniform estimates for radii of convexity of these surfaces under a clipping procedure, a noncollapsing convergence theorem, and a gluing procedure. 相似文献
9.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
10.