全文获取类型
收费全文 | 5116篇 |
免费 | 138篇 |
国内免费 | 19篇 |
专业分类
化学 | 3621篇 |
晶体学 | 55篇 |
力学 | 114篇 |
数学 | 295篇 |
物理学 | 1188篇 |
出版年
2022年 | 24篇 |
2021年 | 55篇 |
2020年 | 43篇 |
2019年 | 63篇 |
2018年 | 42篇 |
2017年 | 41篇 |
2016年 | 92篇 |
2015年 | 84篇 |
2014年 | 96篇 |
2013年 | 238篇 |
2012年 | 271篇 |
2011年 | 299篇 |
2010年 | 161篇 |
2009年 | 155篇 |
2008年 | 268篇 |
2007年 | 264篇 |
2006年 | 279篇 |
2005年 | 243篇 |
2004年 | 243篇 |
2003年 | 224篇 |
2002年 | 222篇 |
2001年 | 141篇 |
2000年 | 116篇 |
1999年 | 84篇 |
1998年 | 64篇 |
1997年 | 61篇 |
1996年 | 71篇 |
1995年 | 53篇 |
1994年 | 71篇 |
1993年 | 67篇 |
1992年 | 75篇 |
1991年 | 45篇 |
1990年 | 49篇 |
1989年 | 57篇 |
1988年 | 51篇 |
1987年 | 47篇 |
1986年 | 50篇 |
1985年 | 92篇 |
1984年 | 92篇 |
1983年 | 28篇 |
1982年 | 45篇 |
1981年 | 45篇 |
1980年 | 48篇 |
1979年 | 74篇 |
1978年 | 49篇 |
1977年 | 59篇 |
1976年 | 51篇 |
1975年 | 35篇 |
1974年 | 28篇 |
1973年 | 21篇 |
排序方式: 共有5273条查询结果,搜索用时 31 毫秒
71.
[structure: see text] Absolute stereochemistry of amphidinolides G (1) and H (2), potent cytotoxic 27- and 26-membered macrolides, respectively, isolated from a marine dinoflagellate Amphidinium sp., was determined by X-ray diffraction analysis, synthesis of a degradation product (3) of 2, and interconversion between 1 and 2. 相似文献
72.
Ivanova SM Nolan BG Kobayashi Y Miller SM Anderson OP Strauss SH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(2):503-510
The relative Lewis basicities of six Al(ORF)4- ions, Al[OC(CH3)(CF3)2]4-, Al(OC(CF3)3]4-, Al(OCPh(CF3)2]4-, Al[OC[4-C6H4(tBu)](CF3)2]4-, Al(OC(Cy)(CF3)2]4-, and Al(OCPh2(CF3)]4-, have been determined by measuring their relative coordinating abilities towards Li+ in dichloromethane. The relative Li- Lewis basicities of the Al(ORF)4- ions are linearly related to the aqueous pKa values of the corresponding parent HORF fluoroalcohols. The Lewis basicity of Al[OCH(CF3)2]4- could not be measured because two of these anions can coordinate to one Li+ cation. The structures of LiAl[OCH(CF3)2]4 and [1-Et-3-Me-1,3-C3H3N2][Li[Al[OCH(CF3)2)4]2] were determined. 相似文献
73.
Scale-up of wet granulation in a vertical high shear mixer was conducted. Pharmaceutical excipient powders composed of lactose, cornstarch and micro-crystallinecellulose, and hydroxypropylcellulose as a binder were mixed together and then granulated with purified water under various operating conditions and vessel scales. A novel internal stress measurement system was developed and stress of normal and tangential directions that granules received from the agitator blade during the granulation was continuously measured. The results indicated that granules received stress mainly from the tangential direction, which also showed the largest value near at the vessel wall. The effects of the agitator tip speed and the centrifugal acceleration on the measured stress was investigated. It was found that the tip speed of the agitator blade could be the main factor for the granule growth. The physical properties such as strength, size distribution and compressibility of granules prepared by changing the operating conditions and the vessel scales were evaluated and the scale-up characteristics of high shear granulation were investigated experimentally. The results showed that these physical properties had linear correlations with the tip speed. It was finally concluded that the scale-up of high shear granulation could be well conducted by means of the tip speed of the agitator blade. 相似文献
74.
Joaquim I. GOES Nobuhiko Handa Satoru Taguchi Takeo Hama 《Photochemistry and photobiology》1995,62(4):703-710
Abstract— The impact of ultraviolet-B radiation (UVBR) on the biosynthesis and the composition of intracellular dissolved free and combined amino acids was examined in nitrate-replete and nitrate-deficient cultures of Tetraselmis sp. Several similarities were observed in the response of Tetraselmis sp. to nitrogen deficiency and exposure to UVBR, in support of a view that UVBR affects amino acid synthesis in phytoplankton via its inhibitory effects on nitrogen assimilation into the cells. At levels that still permitted the uptake of carbon into the cells, both nitrogen deficiency and UVBR exposure resulted in a reduction in the overall rates of carbon incorporated into amino acids, an increase in the absolute concentrations of amino acids within the intracellular dissolved free amino acid (INDFAA) pool and a decrease in the total cellular amino acid (TCAA) pool. An examination of the patterns of carbon assimilation into individual amino acids in cells exposed to UVBR revealed similarities with the patterns in cells subject to nitrogen deficiency. The most conspicuous changes from the controls included an increased incorporation of 13 C into glutamic' acid (glutamic acid + glutamine) and aspartic acid and a marked reduction into alanine and valine. Changes in the concentrations of amino acids within the INDFAA and TCAA pools were also similar in nitrate-deficient and UVBR-exposed cells and resembled the carbon assimilation patterns. These results strongly suggest that UVBR-induced changes in the biosynthesis and composition of amino acids are probably via its suppression of nitrogen assimilation into the cells. 相似文献
75.
Matsuda R Kitaura R Kitagawa S Kubota Y Kobayashi TC Horike S Takata M 《Journal of the American Chemical Society》2004,126(43):14063-14070
In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds. 相似文献
76.
Masao Tomoi Satoru Ishigaki Yasushi Arita Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(8):2251-2261
Polystyrene-bound 4-(1-pyrrolidino)pyridine moieties were prepared by the reaction of chloromethylated polystyrene resins with pyrrolidinopyridine derivatives containing hydroxyl groups. The supported amines were effective catalysts for acylations of tert-alcohols or enols, acylrearrangements, and diester synthesis from epoxides and anhydrides. Some of the low ring-substituted (8–15%) catalysts exhibited high activity comparable to that of 4-(N,N-dimethylamino)pyridine, though the activity was a little lower than that of 4-(1-pyrrolidino)pyridine. The recovered catalysts can be re-used, except for acyl rearrangements, without significant decrease in activity. 相似文献
77.
A novel fine particle removal system composed of a corona-discharge neutralizer, a pulse-jet air unit and an image processing system has been developed. First of all, adhesion force between particle and film was directly measured and effect of electrostatic force on the adhesion force was calculated experimentally and theoretically. The electrostatic force was found to be significant, leading to the suggestion that the countermeasure for the electrostatic force was required to effectively remove fine particles. This system was then applied to the removal of fine particles from surface of a gelatin film used for conventional capsule material. The number of particles removed by the system was calculated by an image processing system and number base removal efficiency was computed with and without the elimination of electrostatic charge by the neutralizer. It was found that the difference between the removal efficiency of particles with elimination of electrostatic charge and that of without the elimination showed linear relationship with the electrostatic adhesion force. The data confirmed the necessity of electrostatic charge elimination for the effective removal of fine particles. 相似文献
78.
T. Kobayashi I. Endo A. Fukumi T. Horiguchi Y. Ishida T. Kondo T. Kuwamoto N. Minamoto T. Nakamura T. Takahasi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,39(3):209-216
Atomic-beam laser spectroscopy with fluorescence detection is applied to investigate the hyperfine structure (hfs), Stark and Zeeman effects of the electric dipole transitions of Sm i. The measurements are performed for the four transitions of 0 → 15650.55, 292.58 → 15650.55, 292.58 → 15567.32, and 1489.55 → 16890.59 cm-1. The hfs constants of the upper and lower levels and the isotope shifts of the transitions are determined. The tensor polarizability of the 15650.55 cm-1 level is found to be α2 = -556.2 ± 11.8 kHz/(kV/cm)2. Thanks to the accurate g values of the lower levels [Childs, W.J., Goodman, L.S.: Phys. Rev. A 6, 2011 (1972)], the g values of the upper levels are obtained from the observed Zeeman splittings. The values are found to be -0.115907(79), 2.22259(20) and 1.599968(51) for the 15650.55 cm-1 .1, 15567.32 cm-1 and 16890.59.cm-1 levels, respectively. 相似文献
79.
Takashima H Mimura N Ohkubo T Yoshida T Tamaoki H Kobayashi Y 《Journal of the American Chemical Society》2004,126(14):4504-4505
Distributed computing has been implemented to the solution structure determination of endothelin-1 to evaluate efficiency of the method for NMR constraint-based structure calculations. A key target of the investigation was determination of the C-terminal folding of the peptide, which had been dispersed in previous studies of NMR, despite its pharmacological significances. With use of tens of thousands of random initial structures to explore the conformational space comprehensively, we determined high-resolution structures with good convergences of C-terminal as well as previously defined N-terminal structures. The previous studies had missed the C-terminal convergence because of initial structure dependencies trapped in localized folding of the N-terminal region, which are strongly constricted by two disulfide bonds. 相似文献
80.
Thermolysis of 2,5-diphenyl-1,4-dithiin-1-oxide afforded 2-formyl-2,4-diphenyl-1,3-dithiole, which was obtained also in photolysis along with another rearranged product, 2-benzoyl-4-phenyl-1,3-dithiole. 相似文献