全文获取类型
收费全文 | 67785篇 |
免费 | 14500篇 |
国内免费 | 4874篇 |
专业分类
化学 | 62721篇 |
晶体学 | 644篇 |
力学 | 2586篇 |
综合类 | 241篇 |
数学 | 5987篇 |
物理学 | 14980篇 |
出版年
2024年 | 71篇 |
2023年 | 738篇 |
2022年 | 1021篇 |
2021年 | 1394篇 |
2020年 | 2491篇 |
2019年 | 3661篇 |
2018年 | 2025篇 |
2017年 | 1619篇 |
2016年 | 4703篇 |
2015年 | 4817篇 |
2014年 | 5137篇 |
2013年 | 6222篇 |
2012年 | 5872篇 |
2011年 | 5104篇 |
2010年 | 4793篇 |
2009年 | 4627篇 |
2008年 | 4305篇 |
2007年 | 3506篇 |
2006年 | 3091篇 |
2005年 | 2971篇 |
2004年 | 2564篇 |
2003年 | 2144篇 |
2002年 | 2741篇 |
2001年 | 2011篇 |
2000年 | 1898篇 |
1999年 | 1153篇 |
1998年 | 719篇 |
1997年 | 655篇 |
1996年 | 705篇 |
1995年 | 601篇 |
1994年 | 550篇 |
1993年 | 470篇 |
1992年 | 449篇 |
1991年 | 364篇 |
1990年 | 324篇 |
1989年 | 236篇 |
1988年 | 216篇 |
1987年 | 198篇 |
1986年 | 141篇 |
1985年 | 156篇 |
1984年 | 135篇 |
1983年 | 116篇 |
1982年 | 80篇 |
1981年 | 59篇 |
1980年 | 49篇 |
1979年 | 32篇 |
1978年 | 26篇 |
1976年 | 27篇 |
1975年 | 31篇 |
1974年 | 23篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Jin-Ming Lin Tatsuro Nakagama Hitoshi Okazawa Xing-Zheng Wu Toshiyuki Hobo 《Fresenius' Journal of Analytical Chemistry》1996,354(4):451-454
Capillary gel electrophoresis (CGE) was successfully applied to the separation of optically active isomers and position isomers by incorporating a suitable cyclodextrin chiral selector in polyacrylamide gel. A commercially available ß-cyclodextrin (ß-CD) was used for enantioselectivity towards o-, m- and p-nitrobenzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-toluic acid and the optical isomers of dansyl-D,L-leucine and R,S-1,1-binaphthyl-2,2-dihydrogenphosphate. Especially the effect of organic solvents, such as acetonitrile, methanol, dimethylsulphoxide and others were examined in detail. The resolution varied to some extent with the addition of the organic solvent to the polyacrylamide gel and the running buffer solution. The possible mechanism has also been discussed. In addition, quantitative aspects of the separation of stereoisomers using CGE have been studied, showing that both the resolution and accuracy of the determinations were affected by the ratio of the enantiomers. 相似文献
992.
在氩气氛中,合成子SrMgF4:xEu,yTb复合氟化物磷光体,该体系中Eu^3+和Eu^2+共存,随共掺入Tb浓度的增加,Eu^3+的荧光发射强度降低,Eu^3+的发光增强,并且Eu^2+的ESR信号增强,认为Eu^3+和Tb3+之间存在的电荷迁移,即Eu^3+Tb^3+→Eu^2++Tb^4+,通过半量手段研究了这一电荷迁移反应的平衡常数。 相似文献
993.
痕量Au Bi和Cd的萃取浮选及原子吸收光谱法测定 总被引:1,自引:0,他引:1
浮选法分离痕量金属离子,由于灵敏度高、选择性强已得到广泛应用。本文利用浮选法使Au~(3 )、Bi~(3 )和Cd~(2 )同KBr反应生成的络合阴离子与碱性染料罗丹明B(RB)生成既疏水又疏有机溶剂的三元离子缔合物,后者经甲苯浮选分出,用二甲基甲酰胺(DMF)溶解后,可用原子吸收法测定Au、Bi和Cd的含量。本方法用于海水,锌片和矿样中上述三种元素的微量测定,可提高检测灵敏度,而且K、Na、Ca、Mg等共存离子不生干扰。具体实验方法如下: 相似文献
994.
995.
Controlling chemical reactivity has been the central theme in chemistry. Herein, we review the recent progress on the development of genetically encoded protein coupling reactions and their potential applications. The chemical reactivity is encoded in the protein sequences. The information is read out by folding and molecular recognition between two reactive components and subsequently translated into chemical bonding via autocatalysis. It has emerged as a unique way to tune the chemical reactivity and is regarded as one type of information‐coded reactions. Not only has it received many applications such as protein topology engineering, bioconjugation, biomaterials and synthetic biology, but also its principle may be extended beyond protein chemistry to enable new modes of supramolecular interactions that promote chemical bonding and that are simultaneously reinforced by covalent bonds. 相似文献
996.
Equilibrium geometries, interaction energies, and charge transfer for the intermolecular interactions between BrF and HnX (HF, H2O, and NH3) were studied at the MP2/6-311++G(3d,3p) level. The halogen-bonded geometry and hydrogen-bonded geometry are observed in these interactions. The calculated interaction energies show that the halogen-bonded structures are more stable than the corresponding hydrogen-bonded structures. To study the nature of the intermolecular interactions, symmetry-adapted perturbation theory (SAPT) calculations were carried out and the results indicate that the halogen bonding interactions are dominantly inductive energy in nature, while electrostatic energy governs the hydrogen bonding interactions. 相似文献
997.
Densities have been measured as a function of composition for ternary-pseudobinary mixtures of [(benzene + toluene or methylcyclohexane)
+ (cyclohexane + toluene or methylcyclohexane)] by means of a vibrating-tube densimeter at atmospheric pressure and the temperature
298.15 K. The excess molar volumes, VmE, were calculated from the densities and correlated using the Redlich–Kister equation to estimate the coefficients and standard
errors. The experimental and calculated quantities are used to discuss the mixing behavior of the components. The results
show the third component, toluene and methylcyclohexane, influences the interaction between benzene and cyclohexane. 相似文献
998.
四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构 总被引:1,自引:0,他引:1
The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands. 相似文献
999.
1000.
铑(Ⅲ)与2—(3,5—二氯—2—吡啶偶氮)—5—二甲氨基苯胺络合物的催化氢波 总被引:2,自引:0,他引:2
本文提出一种新的测定铑的催化氢波体系.先使Rh(Ⅲ)与3,5-diCl-PADMA在HAc-NaAc缓冲溶液中生成稳定的络合物,再以适量HclO_4将溶液酸化后进行极谱测定。利用正交试验法确定体系的最佳分析条件为:0.05 mol/L pH5.0的HAc-NaAc,1.6×10~(-5)mol/L3,5-diCl-PADMA,沸水浴加热15min.,4.4 mol/L HCIO4酸化。在此条件下的线性范围为1.9×10~(-11)~3.9×10~(-9)mol/L,检出限达5.8×10~(-12)mol/L。大量Cu(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)及Co(Ⅱ)对体系的干扰可用EDTA消除。研究了催化波的性质,表明该波为Rh(Ⅲ)与3,5-diClPADMA络合物的催化氢波。 相似文献