全文获取类型
收费全文 | 4666篇 |
免费 | 231篇 |
国内免费 | 35篇 |
专业分类
化学 | 3515篇 |
晶体学 | 25篇 |
力学 | 130篇 |
数学 | 323篇 |
物理学 | 939篇 |
出版年
2023年 | 21篇 |
2022年 | 23篇 |
2021年 | 119篇 |
2020年 | 108篇 |
2019年 | 106篇 |
2018年 | 66篇 |
2017年 | 62篇 |
2016年 | 167篇 |
2015年 | 136篇 |
2014年 | 175篇 |
2013年 | 291篇 |
2012年 | 341篇 |
2011年 | 385篇 |
2010年 | 252篇 |
2009年 | 198篇 |
2008年 | 307篇 |
2007年 | 250篇 |
2006年 | 240篇 |
2005年 | 223篇 |
2004年 | 195篇 |
2003年 | 171篇 |
2002年 | 189篇 |
2001年 | 98篇 |
2000年 | 93篇 |
1999年 | 79篇 |
1998年 | 39篇 |
1997年 | 41篇 |
1996年 | 45篇 |
1995年 | 34篇 |
1994年 | 48篇 |
1993年 | 40篇 |
1992年 | 26篇 |
1991年 | 26篇 |
1990年 | 18篇 |
1989年 | 25篇 |
1988年 | 16篇 |
1987年 | 14篇 |
1986年 | 12篇 |
1985年 | 26篇 |
1984年 | 22篇 |
1983年 | 16篇 |
1982年 | 14篇 |
1981年 | 11篇 |
1980年 | 15篇 |
1979年 | 11篇 |
1978年 | 10篇 |
1976年 | 16篇 |
1975年 | 12篇 |
1974年 | 11篇 |
1972年 | 10篇 |
排序方式: 共有4932条查询结果,搜索用时 15 毫秒
91.
Silver ions dissolved in a polymer matrix are additionally coordinated by carbonyl oxygens of asparagines and their counter anions interact with cationic sites, resulting in the enhanced activity of the silver ion as an olefin carrier for facilitated olefin transport. 相似文献
92.
93.
两种结构钼磷酸的催化氧化行为 总被引:11,自引:0,他引:11
考察了Dawson与Keggin结构钼磷酸的催化氧化行为,并与结构特性进行了关联,结果发现,Dawson结构的杂多酸对氧化脱氢及插入氧反应均有更高的活性。 相似文献
94.
Won Sick Woo Sam Sik Kang Otto Seligmann V. Mohan Chari Hildebert Wagner 《Tetrahedron letters》1980,21(44):4255-4258
From the seeds of Phytolacca americana two new lignans, Americanin B and D, have been isolated and their structures elucidated mainly by spectroscopic methods 相似文献
95.
We apply the master equation and non-linear Fokker-Planck techniques to a model with autocatalysis and (Michaelis-Menten, Langmuir-Hinshelwood) saturation law and the minimal set of reactive steps for a well posed problem is given. 相似文献
96.
Hwang JY Choi HS Seo JS La HJ Kim DS Jeon HS Jeon MK Lee DH Gong YD 《The Journal of organic chemistry》2005,70(24):10151-10154
[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14. 相似文献
97.
Kang EJ Cho EJ Ji MK Lee YE Shin DM Choi SY Chung YK Kim JS Kim HJ Lee SG Lah MS Lee E 《The Journal of organic chemistry》2005,70(16):6321-6329
(+)-SCH 351448 (Na+ salt A) was synthesized employing ring-closing olefin metathesis reaction of an open diene diester intermediate for construction of the 28-membered macrodiolide structure. The open diene diester was prepared from the monomeric hydroxy carboxylic acid and two different olefin fragments. The monomeric hydroxy acid was synthesized via Julia-Julia coupling reaction of intermediates derived from the same olefinic fragments. Oxane units in these fragments were prepared by radical cyclization reactions of beta-alkoxyacrylates. Analogous SCH 351448 salts incorporating other mono- and divalent cations may be prepared. Under acidic conditions, SCH 351448 (Na+ salt A) was the most stable complex, but SCH 351448 (Ca2+ salt) and (Na+ salt B) appear to be physiologically important species. 相似文献
98.
Won Ok Choi Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1990,28(11):2923-2935
In the living cationic polymerization of isobutyl vinyl ether (IBVE) initiated by the hydrogen iodide/zinc halide (HI/ZnX2; X = I, Br, Cl) systems, the concentration ([P*]) of the living propagating species was determined by quenching with sodiomalonic ester ( 1 ). The quenching reaction was shown to be clean, instantaneous, and quantitative to give poly (IBVE) with a terminal malonate group from which [P*] was obtained by 1H-NMR spectroscopy. In the polymerizations in toluene below +25°C, [P*] was constant and equal to the initial concentration ([HI]0) of hydrogen iodide, independent of the type and concentrations of ZnX2 as well as monomer conversion. At 0 and +25°C, however, the living species started decaying immediately after the complete consumption of monomer. In contrast, such a decay process was absent at ?15°C even in the absence of monomer until about an hour (depending on the conditions) after the end of polymerization. The deactivation reaction was first order in [P*], and the lifetime (half-life) of the living species was longer at lower temperature and at lower ZnX2 concentration. On the basis of these [P*] and lifetime measurements, the HI/ZnX2 systems were also compared with the HI/I2 counterpart. 相似文献
99.
M. C. Mahedero A. Muñoz De La Peña A. Bautista J.J. Aaron 《Journal of inclusion phenomena and macrocyclic chemistry》2002,42(1-2):61-70
The effect of -cyclodextrin (-CD) and hydroxypropyl--cyclodextrin (HP--CD) upon the photochemically-induced fluorescence (PIF) properties of four phenylurea herbicides, including linuron, diuron, isoproturon and neburon has been studied. Photochemical conversion of these nonfluorescent herbicides into strongly fluorescent photoproducts was shown to occur in -CD and HP--CD aqueous media. The influence of pH, UV irradiation time and photoproduct stability on the fluorescence intensity was also investigated. In addition, the stoichiometry and formation constants of the complexes formed between herbicides and -cyclodextrin (-CD) or 2-hydroxypropyl--cyclodextrin (HP--CD) were determined. The formation constant values, ranging from 184 ± 40 to 1498 ± 245 M-1, were calculated by applying the iterative nonlinear regression (NLR) approach to the PIF data. Linear calibrations graphs were established in the interval 1–12 g/mL, for diuron, linuron and neburon. The IUPAC limits of detection ranged between 580 and 700 ng/mL, according to the compound. Application to the analysis of phenylurea herbicides in spiked river water was also described. 相似文献
100.
Ema I García De La Vega JM Ramírez G López R Fernández Rico J Meissner H Paldus J 《Journal of computational chemistry》2003,24(7):859-868
We present three Slater-type atomic orbital (STO) valence basis (VB) sets for the first and second row atoms, referred to as the VB1, VB2, and VB3 bases. The smallest VB1 basis has the following structure: [3, 1] for the H and He atoms, [5, 1] for Li and Be, and [5, 3, 1] for the B to Ne series. For the VB2 and VB3 bases, both the number of shells and the number of functions per shell are successively increased by one with respect to VB1. With the exception of the H and Li atoms, the exponents for the VB1 bases were obtained by minimizing the sum of the Hartree-Fock (HF) and frozen-core singles and doubles configuration interaction (CISD FC) energies of the respective atoms in their ground state. For H and Li, we minimized the sum of the HF and CISD FC energies of the corresponding diatoms (i.e., of H(2) or Li(2)) plus the ground-state energy of the atom. In the case of the VB2 basis sets, the sum that was minimized also included the energies of the positive and negative ions, and for the VB3 bases, the energies of a few lowest lying excited states of the atom. To account for the core correlations, the VBx (x = 1, 2, and 3) basis sets for the Li to Ne series were enlarged by one function per shell. The exponents of these extended (core-valence, CV) basis sets, referred to, respectively, as the CVBx (x = 1, 2, and 3) bases, were optimized by relying on the same criteria as in the case of the VBx (x = 1, 2, and 3) bases, except that the full CISD rather than CISD FC energies were employed. We show that these polarized STO basis sets provide good HF and CI energies for the ground and excited states of the atoms considered, as well as for the corresponding ions. 相似文献