全文获取类型
收费全文 | 3456篇 |
免费 | 432篇 |
国内免费 | 237篇 |
专业分类
化学 | 1774篇 |
晶体学 | 25篇 |
力学 | 331篇 |
综合类 | 101篇 |
数学 | 473篇 |
物理学 | 1421篇 |
出版年
2024年 | 8篇 |
2023年 | 25篇 |
2022年 | 76篇 |
2021年 | 76篇 |
2020年 | 73篇 |
2019年 | 71篇 |
2018年 | 79篇 |
2017年 | 120篇 |
2016年 | 161篇 |
2015年 | 120篇 |
2014年 | 162篇 |
2013年 | 256篇 |
2012年 | 169篇 |
2011年 | 217篇 |
2010年 | 184篇 |
2009年 | 216篇 |
2008年 | 248篇 |
2007年 | 260篇 |
2006年 | 261篇 |
2005年 | 212篇 |
2004年 | 168篇 |
2003年 | 146篇 |
2002年 | 127篇 |
2001年 | 110篇 |
2000年 | 83篇 |
1999年 | 70篇 |
1998年 | 76篇 |
1997年 | 51篇 |
1996年 | 43篇 |
1995年 | 46篇 |
1994年 | 35篇 |
1993年 | 31篇 |
1992年 | 22篇 |
1991年 | 25篇 |
1990年 | 20篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 7篇 |
1986年 | 10篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1967年 | 1篇 |
1959年 | 2篇 |
排序方式: 共有4125条查询结果,搜索用时 15 毫秒
51.
Slow pyrolysis of walnut shell which is a cheap and abundantly available solid waste was carried out using thermogravimetric
analysis. The effects of raw material heating rate on the pyrolysis properties and kinetic parameters were investigated. A
two-step consecutive reaction model were used to simulate the pyrolysis process. The kinetic parameters were established by
using the pattern search method. Comparison between experimental data and the model prediction indicated that the two-step
consecutive reaction model can better describe the slow pyrolysis of walnut shell as the formation of an intermediate during
the pyrolysis process was taken into account. 相似文献
52.
János?W?lfling Angéla?Magyar Gyula?SchneiderEmail author 《Monatshefte für Chemie / Chemical Monthly》2003,134(10):1387-1393
Summary. A new synthetic route was developed for the preparation of trans-3-hydroxy-16,17-seco-pregna-5,17(20)-dien-16-al, using Grob fragmentation as the key step. This seco-steroid contains a formyl group and an unsaturated side-chain in a sterically favourable position, and is therefore a promising starting material for the synthesis of novel condensed steroid heterocycles.Received March 22, 2003; accepted April 22, 2003
Published online September 25, 2003 相似文献
53.
Bossée A Afonso C Fournier F Tasseau O Pepe C Bellier B Tabet JC 《Journal of mass spectrometry : JMS》2004,39(8):903-912
Peptide metallation with Cu2+ was explored in the negative ESI mode using an ion trap mass spectrometer. Under these conditions, the [(M-3H) + CuII]- species formed were investigated under low-energy collision-induced dissociation conditions. MS2 experiments indicate a very different behavior of CuII metallated complexes compared with [M-H]- species. CuII induces an easy loss of CO2 and specific side-chain cleavages (by radical losses) at the C-terminal residue, as observed previously by prompt 'in source' dissociation experiments. The loss of CO2 yields an unstable carbylide that leads to further dissociations involving the migration of a proton or a hydrogen radical (through the reduction of CuII). Multistage MS3 experiments were carried out to rationalize this behavior. Fragmentation pathways are proposed in order to explain the product ions observed. The side-chain radical loss at the C-terminus was demonstrated to be a consecutive process. Finally, evidence is provided that the specific side-chain cleavages can be used for the differentiation of Leu/Ile and Gln/Lys residues when they are located at the C-terminus. The existence of a zwitterionic form in the case of the anionic YGGFK-CuII complex is proposed. 相似文献
54.
Chemical and physical analyses of malt, the main ingredient of beer, have been used to predict the concentration of certain volatile compounds in the finished beer.The prediction was done by means of the partial least squares regression (PLS2) in SIMCA. The total data set as well as individual malt clusters were submitted to PLS analysis. Best prediction was obtained by separating the total object matrix in classes according to similarity found by fuzzy pattern recognition (FCV). FCV was also used to separate the beer variables in classes and to select the subset of variables to be predicted.A joint approach of fuzzy pattern recognition to identify groups of samples and SIMCA-PLS2 to predict several dependent variables is suggested as a powerful tool in process-analytical chemistry. 相似文献
55.
E. Yu. Mikhteeva E. G. Savchuk E. A. Tararako E. B. Merkulov V. K. Goncharuk 《Journal of Structural Chemistry》2005,46(6):1082-1085
Images of cleaved surfaces were obtained for 53ZrF4-20BaF2-4LaF3-3AlF3-20NaF (ZBLAN) glasses and fused quartz using an NTMDT atomic force microscope. It is shown that the scatter of particle size depends on the cooling rate and is 21–48.5 Å for the cleaved surface of ZBLAN glass obtained by very fast cooling and 68–172 Å for the cleaved surface of ZBLAN after slow cooling. For cleaved fused quartz, the range is 25-18 Å. 相似文献
56.
Davor Margeti? 《Tetrahedron》2007,63(20):4338-4346
Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1,3-dienes. The versatility of parity reversal, in conjunction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the N,O-sesquinorbornadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclization of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products); further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the fragmentation and cycloaddition processes using DFT calculations (B3LYP/6-31G∗) and these calculations correctly predict, which reaction can be intercepted at the norbornadienomaleic anhydride stage and preferred stereochemistry of cycloadducts. 相似文献
57.
Filip Fratev Gottfried Olbrich Oskar E. Polansky 《Monatshefte für Chemie / Chemical Monthly》1979,110(3):505-515
UsingGleason's theorem the pars orbital concept is developed for excited states of conjugated systems described by CI-methods. A significance index is introduced to evaluate different patterns of fragmentation. The usefulness of this approach is illustrated for butadiene, biphenyl, naphthalene, and azulene.
11. Mitt.:H. Karpf, O. E. Polansky undM. Zander, Tetrahedron Lett.1978, 2069. 相似文献
58.
1,2,4-三嗪类化合物具有抗癌、抗病毒、杀虫、抑制中枢神经系统等多种作用。前文用苯甲酰基硫代甲酰胺直接与氨基脲反应,制备了8种新的4,6-二取代-3-酮-5-硫酮-1,2,4-三嗪类化合物(a—h),本文测定了其电子轰击质谱、高分辨质谱及联动扫描质谱,以了解其质谱裂解途径。 相似文献
59.
Tsuneo Okubo 《Colloid and polymer science》2006,284(12):1395-1401
Sedimentation and drying dissipative structural patterns formed in the course of drying colloidal silica spheres (1.2 μm in diameter) in aqueous suspension have been studied in a glass dish and a polystyrene dish. The broad ring patterns are formed within a short time in suspension state by the convection flow of water and colloidal spheres. The broad ring patterns are not formed when a dish is covered with a cap, which demonstrates the important role of the convectional flow of silica spheres and water accompanied with the evaporation of water on the air-suspension interface. The sedimentary spheres always move by the convectional flow of water, and the broad ring patterns became sharp with time. Broad ring and microscopic fine structures are formed in the solidification processes on the bases of the convectional and sedimentation patterns. Drying patterns of the colloidal suspensions containing sodium chloride are star-like ones, which strongly supports the synchronous cooperative interactions between the salt and colloidal spheres. 相似文献
60.
Cellular networks were constructed based on PEG modification and soft lithography, in which cell numbers and spatial distributions can be controlled. A micro-injector was combined with cellular networks to fix virus induced plaque and virus spread direction, by which virus cell-to-cell spread can be distinguished from cell-free spread. 相似文献