全文获取类型
收费全文 | 5812篇 |
免费 | 1221篇 |
国内免费 | 1107篇 |
专业分类
化学 | 2576篇 |
晶体学 | 147篇 |
力学 | 229篇 |
综合类 | 93篇 |
数学 | 500篇 |
物理学 | 1861篇 |
无线电 | 2734篇 |
出版年
2024年 | 37篇 |
2023年 | 158篇 |
2022年 | 200篇 |
2021年 | 268篇 |
2020年 | 234篇 |
2019年 | 216篇 |
2018年 | 206篇 |
2017年 | 240篇 |
2016年 | 243篇 |
2015年 | 336篇 |
2014年 | 418篇 |
2013年 | 482篇 |
2012年 | 557篇 |
2011年 | 567篇 |
2010年 | 429篇 |
2009年 | 455篇 |
2008年 | 501篇 |
2007年 | 458篇 |
2006年 | 383篇 |
2005年 | 376篇 |
2004年 | 269篇 |
2003年 | 184篇 |
2002年 | 171篇 |
2001年 | 179篇 |
2000年 | 120篇 |
1999年 | 87篇 |
1998年 | 59篇 |
1997年 | 48篇 |
1996年 | 30篇 |
1995年 | 26篇 |
1994年 | 30篇 |
1993年 | 23篇 |
1992年 | 32篇 |
1991年 | 12篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 3篇 |
1987年 | 18篇 |
1986年 | 5篇 |
1985年 | 9篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 7篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1971年 | 4篇 |
1964年 | 2篇 |
1963年 | 2篇 |
排序方式: 共有8140条查询结果,搜索用时 343 毫秒
91.
92.
Thecurrentsurgeofinterestinthefield0fnon-linearoptics(NL0)isderivedbothfromaquestforafundamentalunderstanding0fthenon-linearprocess,anditSimPortanceinthetechn0logyofphotonics.Amongnon-linearphen0mena,thethird-ordernon-linearophcsoccuPyanimPortantp0sihonbecauseitprovidesthemechanicsforophcalswitching,ophcallogic,andreal-hmeholograPhy"'.0rganicmaterialwithextendednconjugahonsandlargeRdelocalizahonsarewellknownastheimPortantmaterialsofachievinglargethird-ordernonlinearihes3.ForexamPle,thiosen… 相似文献
93.
合成了通过N-N键桥联的不对称的N2O3席夫碱配体(H3L)的镍(Ⅱ)配合物[Ni2(HL)2]2(DMF)8(H2O)2 (1)。配合物晶体属于三斜晶系,空间群为P1,a=1.273 5(2) nm,b=1.360 4(3) nm,c=1.427 6(3) nm,α=85.358(4)°,β=63.513(3)°,γ=79.545(4)°,V=2.176 8(7) nm3,Z=1,F(000)=980,R1=0.073 6。配合物1的不对称单元中含有两个双核结构Ni2(HL)2(DMF)2(H2O)2 (Ⅰ)和Ni2(HL)2(DMF)4 (Ⅱ)以及两个DMF溶剂分子。通过酚基氧原子桥联的镍-镍距离分别为:Ni(1)-Ni(1A),0.308 4 nm;Ni(2)-Ni(2B),0.310 3 nm(对称操作:A:1-x,2-y,-z;B:1-x,1-y,1-z)。金属镍(Ⅱ)离子采取扭曲的八面体配位构型,一个配体的NO2三齿配位单元和另一个配体的酚基氧原子位于赤道面位置,两个溶剂分子占据轴向位置。晶体中存在着分子内以及分子与溶剂分子间的两种氢键作用。配合物1的变温磁化率测定表明,Ni(Ⅱ)离子之间的反铁磁耦合作用在它的磁性质中起主导作用。 相似文献
94.
95.
WeiHuaHAN HaoRanLI 《中国化学快报》2005,16(1):15-16
(-)-cis-1, 3-Dibenzyl-hexahydrofuro[3, 4-d]imidazole-2, 4-dione was prepared by a new synthesis method from meso dicarboxylic acid and dehydroabietylamine by asymmetric reduction in good yield with up to 91.6% e.e. value. 相似文献
96.
97.
Nian Yun YANG Shi Hui QIAN Jin Ao DUAN Ping LI Li Juan TIAN Jiangsu Academy of Traditional Chinese Medicine Nanjing China Pharmaceutical University Nanjing Jinling Pharmaceutical Company Limited Nanjing 《中国化学快报》2005,16(9)
Various germacrane sesquiterpenes have been isolated from many species of the Eupatorium.In recent years these compounds have been increasing interest due to their insecticidal,cytotoxic,antitumor-promoting and insect-antifeedant activities1.In our present study,we have investigated the chemical constituents of Eupatorium lindleyanum DC.,which is a geo-authentic medicine of Jiangsu province.It is used as a antipyretic drug.Two novel germacrane sesquiterpenes(Figure1)were found by us from th… 相似文献
98.
Mezer A Friedman R Noivirt O Nachliel E Gutman M 《The journal of physical chemistry. B》2005,109(22):11379-11388
The surface of a protein, or a membrane, is spotted with a multitude of proton-binding sites, some of which are only a few angstroms apart. When a proton is released from one site, it propagates through the water by a random walk under the bias of the local electrostatic potential determined by the distribution of the charges on the protein. Some of the released protons disperse into the bulk, but during the first few nanoseconds, the released protons can be trapped by encounter with nearby acceptor sites. This process resembles a scenario which corresponds with the time-dependent Debye-Smoluchowski equation. In the present study, we investigated the mechanism of proton transfer between sites that are only a few angstroms apart, using as a model the proton exchange between sites on a small molecule, fluorescein, having two, spectrally distinguishable, proton-binding sites. The first site is the oxyanion on the chromophore ring structure. The second site is the carboxylate moiety on the benzene ring of the molecule. Through our experiments, we were able to reconstruct the state of protonation at each site and the velocity of proton transfer between them. The fluorescein was protonated by a few nanosecond long proton pulse under specific conditions that ensured that the dye molecules would be protonated only by a single proton. The dynamics of the protonation of the chromophore were measured under varying initial conditions (temperature, ionic strength, and different solvents (H(2)O or D(2)O)), and the velocity of the proton transfer between the two sites was extracted from the overall global analysis of the signals. The dynamics of the proton transfer between the two proton-binding sites of the fluorescein indicated that the efficiency of the site-to-site proton transfer is very sensitive to the presence of the screening electrolyte and has a very high kinetic isotope effect (KIE = 55). These two parameters clearly distinguish the mechanism from proton diffusion in bulk water. The activation energy of the reaction (E(a) = 11 kcal mol(-1)) is also significantly higher than the activation energy for proton dissociation in bulk water (E(a) approximately 2.5 kcal mol(-1)). These observations are discussed with respect to the effect of the solute on the water molecules located within the solvation layer. 相似文献
99.
Poly(acrylp-aminobenzenesulfonamideamidine-p-aminobenzenesulfonylamide) chelating fiber containing "S", "N", and "O" elements was synthesized from polyacrylonitrile fiber and p-aminobenzene sulfonamide and used to enrich and separate trace Bi(III), Hg(III), Au(III), and Pd(IV) ions from wastewater and ore sample solution. The enrichment acidity, flow rate, elution conditions, reuse, interference ions, saturated adsorption capacity, constant of adsorption rate, analytical accuracy, and actual samples on chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES) with satisfactory results. Solutions of 100 ng mL–1 of Bi(III), Hg(III), Au(III), and Pd(IV) ions can be enriched quantitatively by this chelating fiber at a rate of 1.0 mL min–1 at pH 4 and desorbed quantitatively with 20 mL of 0.25 M HCl and 2% CS(NH2)2 solution at 50 °C (with recovery 97%). When the chelating fiber was reused for 20 times, the recoveries of the analyzed ions enriched by the fiber were still over 95% (except for Hg(III)). One thousand-fold excesses of Mn2+, Ca2+, Zn2+, Mg2+, Fe3+, Cu2+, Ni2+, Al3+, and Ba2+ ions and thousands-fold excesses of Na+ and K+ cause little interference in the pre-concentration and determination of the analyzed ions. The saturated adsorption capacity of Bi(III), Hg(III), Au(III), and Pd(IV) was 4.850×10–4, 3.235×10–4, 2.807×10–4, and 3.386×10–4 mol g–1, respectively. The constants of adsorption rate were 0.409 min–1 for Bi, 0.122 min–1 for Hg, 0.039 min–1 for Au, and 0.080 min–1 for Pd. The relative standard deviations (RSDs) for the enrichment and determination of 10 ng mL–1 Bi(III), Hg(III), Au(III), and Pd(IV) were lower than 2.3%. The results obtained for these ions in actual samples by this method were basically in agreement with the given values with average errors of less than 1.0%. FT-IR spectra shows that the existence of –SO2–Ar, –H2N–Ar, O=C–NH–, HN=C–NH–, and –HN–SO2 functional groups are verified in the chelating fiber. From the FT-IR spectroscopy, we can see that Hg(III), Au(III), and Pd(IV) are mainly combined with nitrogen and sulfur (or oxygen), and Bi(III) is mainly combined with nitrogen (or oxygen) of the groups to form a chelating complex. 相似文献
100.
The development of broadly applicable and practical catalytic approaches for the enantioselective creation of quaternary stereocenters remains a highly desirable yet challenging goal. In this Communication, we describe a highly enantioselective cyanosilylation of acetal ketones (alpha,alpha-dialkoxy ketones) catalyzed by modified cinchona alkaloids. This reaction is the first highly enantioselective cyanosilylation of ketones catalyzed by an organic chiral Lewis base and is found to be highly efficient with acetal ketones bearing a broad range of alkyl, aryl, alkenyl, and alkynyl substituents. This new catalytic asymmetric reaction, coupled with the versatility of the acetal functionality, provides a broadly useful synthetic method for chiral building blocks bearing quaternary stereocenters. Acetal ketones, readily accessible but previously unexplored in asymmetric synthesis, demonstrate unusual reactivity and selectivity toward the nucleophilic cyanosilylation, thereby suggesting that they may be interesting substrates for other catalytic enantioselective reactions. 相似文献