全文获取类型
收费全文 | 77664篇 |
免费 | 548篇 |
国内免费 | 112篇 |
专业分类
化学 | 41270篇 |
晶体学 | 1261篇 |
力学 | 3278篇 |
综合类 | 1篇 |
数学 | 7828篇 |
物理学 | 24686篇 |
出版年
2022年 | 629篇 |
2021年 | 870篇 |
2020年 | 965篇 |
2019年 | 1103篇 |
2018年 | 1596篇 |
2017年 | 1686篇 |
2016年 | 2148篇 |
2015年 | 1022篇 |
2014年 | 1718篇 |
2013年 | 3269篇 |
2012年 | 2898篇 |
2011年 | 3275篇 |
2010年 | 2636篇 |
2009年 | 2634篇 |
2008年 | 2996篇 |
2007年 | 2873篇 |
2006年 | 2767篇 |
2005年 | 2432篇 |
2004年 | 2237篇 |
2003年 | 2071篇 |
2002年 | 2134篇 |
2001年 | 2233篇 |
2000年 | 1623篇 |
1999年 | 1253篇 |
1998年 | 1125篇 |
1997年 | 1036篇 |
1996年 | 891篇 |
1995年 | 831篇 |
1994年 | 812篇 |
1993年 | 811篇 |
1992年 | 864篇 |
1991年 | 933篇 |
1990年 | 877篇 |
1989年 | 905篇 |
1988年 | 816篇 |
1987年 | 767篇 |
1986年 | 739篇 |
1985年 | 864篇 |
1984年 | 961篇 |
1983年 | 818篇 |
1982年 | 835篇 |
1981年 | 746篇 |
1980年 | 702篇 |
1979年 | 768篇 |
1978年 | 890篇 |
1977年 | 913篇 |
1976年 | 808篇 |
1975年 | 775篇 |
1974年 | 790篇 |
1973年 | 760篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Wender PA Baryza JL Bennett CE Bi FC Brenner SE Clarke MO Horan JC Kan C Lacôte E Lippa B Nell PG Turner TM 《Journal of the American Chemical Society》2002,124(46):13648-13649
Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer. 相似文献
992.
The reaction of alkylpyridinium (CnH2n + 1NC5H5, hereafter Cn-Py) iodide salts in aqueous acetonitrile with a preformed palladium iodide precursor afforded two different types of organic-inorganic phases depending on the molar ratio. A 2:1 ratio yielded the phase [Cn-Py]2[PdI4] (3, n = 14, 16), which crystallized in the triclinic crystal system. The X-ray crystal structure of 3, (n = 14), refined in the space group P1 (a = 8.918(3) A, b = 9.894(3) A, c = 29.062(12) A, alpha = 93.51(3) degrees, beta = 94.17(3) degrees, gamma = 115.60(3) degrees, and Z = 2), consists of interdigitated bilayers with a basal spacing of 29.0 A. The aliphatic chains of the cations, which run almost parallel to the stacking direction, are fully stretched between polar planes built on isolated [PdI4]2- anions and cation headgroups. Changing the organic cation to palladium ratio to 1:1 led to a new phase [Cn-Py]2[Pd2I6] (4, n = 14, 16), which crystallizes in the triclinic P1 space group (a = 9.399(4) A, b = 14.264(6) A, c = 29.415(13) A, alpha = 92.11(4) degrees, beta = 90.07(4) degrees, gamma = 104.53(3) degrees, Z = 3 for 4(n = 14); a = 9.417(2) A, b = 14.215(3) A, c = 31.552(6) A, alpha = 87.96(3) degrees, beta = 87.63(3) degrees, gamma = 75.67(3) degrees, Z = 3 for 4(n = 16)). The layered structure is basically of a continuously interdigitated single-layer type, with a bilayer sublattice superimposed. Isolated [Pd2I6]2- anions contribute to the inorganic planes. A high degree of interdigitation and tilting of the aliphatic chains lead to basal spacings of 29.4 and 31.5 A for 4(n = 14) and 4(n = 16), respectively. The [Cn-Py]2[PdI4] and [Cn-Py]2[Pd2I6] phases were characterized by thermal analysis. Mesomorphic behavior was observed only for 3(n = 16), which was confirmed by variable-temperature powder XRD and optical microscopy. 相似文献
993.
For the detection of the cystic fibrosis protein (CFP) in serum of cystic fibrosis (CF) carriers, thin-layer polyacrylamide gel isoelectric focusing proved inappropriate as a diagnostic test, but was useful for screening fractions on purification of CFP by chromatofocusing on a Mono P column. On sodium dodecyl sulfate-polyacrylamide gel electrophoresis an Mr 12,000 protein (P12) was found in most CFP-positive sera, indicating good correlation between these two CF-associated proteins. Detection of the P12 protein by sodium dodecyl sulfate-polyacrylamide gel electrophoresis was well reproducible and less delicate than IEF. The technique was also used to purify P12 from serum by two successive preparative electrophoresis steps in a 7.5-15% gradient and 15% homogeneous gel. The use of silver staining revealed that P12, which was present in all sera of CF patients and carriers with variable intensities, was also present in trace amounts in normal sera. 相似文献
994.
A preparative route to cis- and trans-1,2-dibromocyclopropane () was developed via the Hunsdiecker reaction of silver cyclopropane-1,2-dicarboxylate (). Cis- and trans- gave the same ratio of cis- and trans- (1:3.2). The mechanism of this reaction is briefly discussed. 相似文献
995.
Lead is extracted from urine with ammonium pyrrolidien dithiocrbamate into methyl isobutyl ketone, and 20 μl of the extract is injected into a water carrier stream in a flow-injection/atomic absorption system. The procedure is simple, quick, accurate and reproducible. Recoveries are 96–105%. The mean urine lead contents of 20 unexposed and 20 printing-press lead exposed workers was found to be 39.0 ± 8.3 and 71.7 ± 26.3 μg Pb l?1, respectively. 相似文献
996.
997.
Xerogels containing residues of amide derivatives of phosphonic and thiophosphonic acids, ≡Si(CH2)3NHP(S, O)(OC2H5)2 (functional group concentration of 1.3–2.2 mmol/g) have been prepared by a sol-gel method. It has been shown that xerogels having a developed porous structure (with specific surface areas of 240–485 m2/g, pore volumes of 0.20–0.50 cm3/g, and pore diameters of 3.6–6.5 nm) are formed at tetraethoxysilane-to-trifunctional silane ratios of 4: 1 (and above) and 6: 1 (and above) for the derivatives of phosphonic and thiophosphonic acids, respectively. The IR and 13C CP/MAS NMR spectroscopy data have demonstrated that the surface layer of the xerogels contains not only (thio)phosphonic acid residues, but also silanol groups and water molecules participating in hydrogen bonding. The 29Si CP/MAS NMR spectroscopy data have indicated that structural groups are, for the most part, contained in structural units T3 [(≡SiO)3Si(CH2)3NHP(O, S)(OC2H5)2] and T2 [(≡SiO)2Si(OR)[(CH2)3NHP(O, S)(OC2H5)2] (R = H or C2H5). 相似文献
998.
V. P. Sheverdov O. V. Ershov A. V. Eremkin O. E. Nasakin I. N. Bardasov V. A. Tafeenko 《Russian Journal of Organic Chemistry》2005,41(12):1757-1763
β,β,γ,γ-Tetracyanoalkanones react with acrolein at a high rate to afford the corresponding 2-substituted 4-formyl-3-cyclopentene-1,1,2-tricarbonitriles in high yields. The reaction occurs under mild conditions and is quite applicable for modification of natural and biologically active compounds possessing an R′CHC(O)CR3 fragment to obtain their derivatives containing three cyano groups. 相似文献
999.
Monperrus M Tessier E Veschambre S Amouroux D Donard O 《Analytical and bioanalytical chemistry》2005,381(4):854-862
A robust method has been developed for simultaneous determination of mercury and butyltin compounds in aqueous samples. This method is capable of providing accurate results for analyte concentrations in the picogram per liter to nanogram per liter range. The simultaneous determination of the mercury and tin compounds is achieved by species-specific isotope dilution, derivatization, and gas chromatography–inductively coupled plasma mass spectrometer (GC–ICP–MS). In derivatization by ethylation and propylation, reaction conditions such as pH and the effect of chloride were carefully studied. Ethylation was found to be more sensitive to matrix effects, especially for mercury compounds. Propylation was thus the preferred derivatization method for simultaneous determination of organomercury and organotin compounds in environmental samples. The analytical method is highly accurate and precise, with RSD values of 1 and 3% for analyte concentrations in the picogram per liter to nanogram per liter range. By use of cleaning procedures and SIDMS blank measurements, detection limits in the range 10–60 pg L–1 were achieved; these are suitable for determination of background levels of these contaminants in environmental samples. This was demonstrated by using the method for analysis of real snow and seawater samples. This work illustrates the great advantage of species-specific isotope dilution for the validation of an analytical speciation method—the possibility of overcoming species transformations and non-quantitative recovery. Analysis time is saved by use of the simultaneous method, because of the use of a single sample-preparation procedure and one analysis. 相似文献
1000.
O. B. Smolii L. V. Muzychka A. N. Chernega B. S. Drach 《Russian Journal of General Chemistry》2005,75(4):527-532
The substituted vinylphosphonium salt (E)-MeSCH=C(CN)P+Ph3I− readily cyclizes under the action of benzamidine and 3-amino-s-triazole, but it does not enter cyclocondensation with 2-aminopyridine. The structure of the cyclization product with 3-amino-s-triazole was confirmed by its transformation to 7-imino-6-(triphenylphosphoranylidene)-6,7-dihydro-s-triazolo[1,5]pyrimidine which was identified by X-ray diffraction. This stabilized ylide and its analogs proved useful starting materials for regioselective syntheses of 2-R-4-alkyl-4,7-dihydro-s-triazolo[1,5-a]pyrimidin-7-ones.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 565–570.Original Russian Text Copyright © 2005 by Smolii, Muzychka, Chernega, Drach. 相似文献