全文获取类型
收费全文 | 23245篇 |
免费 | 2306篇 |
国内免费 | 5110篇 |
专业分类
化学 | 27027篇 |
晶体学 | 151篇 |
力学 | 285篇 |
综合类 | 126篇 |
数学 | 426篇 |
物理学 | 2646篇 |
出版年
2024年 | 47篇 |
2023年 | 347篇 |
2022年 | 521篇 |
2021年 | 810篇 |
2020年 | 1189篇 |
2019年 | 1006篇 |
2018年 | 1031篇 |
2017年 | 943篇 |
2016年 | 1020篇 |
2015年 | 981篇 |
2014年 | 1462篇 |
2013年 | 2281篇 |
2012年 | 1283篇 |
2011年 | 1570篇 |
2010年 | 1204篇 |
2009年 | 1339篇 |
2008年 | 1430篇 |
2007年 | 1560篇 |
2006年 | 1466篇 |
2005年 | 1346篇 |
2004年 | 1342篇 |
2003年 | 1038篇 |
2002年 | 641篇 |
2001年 | 535篇 |
2000年 | 536篇 |
1999年 | 459篇 |
1998年 | 419篇 |
1997年 | 370篇 |
1996年 | 332篇 |
1995年 | 334篇 |
1994年 | 280篇 |
1993年 | 217篇 |
1992年 | 210篇 |
1991年 | 158篇 |
1990年 | 124篇 |
1989年 | 111篇 |
1988年 | 91篇 |
1987年 | 64篇 |
1986年 | 64篇 |
1985年 | 59篇 |
1984年 | 54篇 |
1983年 | 26篇 |
1982年 | 40篇 |
1981年 | 44篇 |
1980年 | 34篇 |
1979年 | 29篇 |
1978年 | 32篇 |
1977年 | 31篇 |
1976年 | 38篇 |
1974年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
在B3LYP/6-31G(d, p)(Rh和P采用LANL2DZ + Polar)水平下,利用自洽反应场(SCRF)的Onsager模型,系统研究了C6H12、C6H6、THF、CH2Cl2、CH3OH和H2O(相对介电常数ε分别为2.02、2.25、7.58、8.93、32.63和78.39)六种溶剂对乙烯氢甲酰化反应中各驻点的结构和反应机理的影响.分别在上述溶剂中优化了反应物、产物、中间体和过渡态的结构,并计算了自由能和活化自由能.计算结果表明,不同溶剂对反应势能面上各驻点的结构和能量均有一定的影响,而且随着相对介电常数ε的增加,反应的活化自由能下降.水是以上六种溶剂中最佳的溶剂,这与大量的实验研究结果一致. 相似文献
992.
993.
Schlegel HB 《Journal of computational chemistry》2003,24(12):1514-1527
Potential energy surfaces form a central concept in the application of electronic structure methods to the study of molecular structures, properties, and reactivities. Recent advances in tools for exploring potential energy surfaces are surveyed. Methods for geometry optimization of equilibrium structures, searching for transition states, following reaction paths and ab initio molecular dynamics are discussed. For geometry optimization, topics include methods for large molecules, QM/MM calculations, and simultaneous optimization of the wave function and the geometry. Path optimization methods and dynamics based techniques for transition state searching and reaction path following are outlined. Developments in the calculation of ab initio classical trajectories in the Born-Oppenheimer and Car-Parrinello approaches are described. 相似文献
994.
1-(偶氮苯基)-3-(3,5-二溴-2-吡啶)-三氮烯的合成及其与镉的显色反应 总被引:10,自引:0,他引:10
报道了 1 (偶氮苯基 ) 3 ( 3,5 二溴 2 吡啶 ) 三氮烯的合成及其与镉的显色反应。在TritonX 1 0 0存在下 ,于pH 1 0 .9的Na2 B4O7 NaOH缓冲介质中 ,镉与ABDBPDT形成摩尔比 1∶3型红色配合物。试剂及配合物的最大吸收波长分别为 430nm和 5 30nm。表观摩尔吸光系数为 1 .75× 1 0 5L·mol- 1 ·cm- 1 。镉含量在 0 μg/2 5mL~ 1 2 μg/2 5mL范围内符合比耳定律 相似文献
995.
J. N. Spencer S. K. Berger C. R. Powell B. D. Henning G. S. Furman W. M. Loffredo E. M. Rydberg R. A. Neubert C. E. Shoop D. N. Blauch 《Journal of solution chemistry》1981,10(7):501-509
Enthalpies of solution and of transfer of amides for the solvents chloroform (CHCl3), methylenechloride (CH2Cl2), carbontetrachloride (CCl4), cyclohexane (C6H12), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and ethylacetate (EtOAc) have been used to isolate and quantify the solvation interactions of amides in chlorinated solvents. Specific interactions at the aminde carbonyl and N–H groups have been identified. An analysis of the transfer enthalpies of pyrrole and methylpyrrole from cyclohexane to the chlorinated solvents shows that specific interactions between the pyrroles and these solvents are similar in nature. A means of calculating differences in the transfers of different solutes between the same solvent pair is given.Work done at Lebanon Valley College. 相似文献
996.
The hydration of the lipid 1-palmitoyl-2-oleoylphosphatidylcholine (POPC) and of the cationic detergent dodecyltrimethylammonium bromide (DTAB) has been studied by means of isothermal titration calorimetry (ITC), gravimetry, and infrared (IR) spectroscopy. During the experiments films of the amphiphiles are perfused by an inert gas of variable relative humidity. The measurement of adsorption heats using ITC represents a new adaptation of adsorption calorimetry which has been called the humidity titration technique. This method yields the partial molar enthalpy of water upon adsorption. It is found to be endothermic with respect to the molar enthalpy of water on condensation for the water molecules which interact directly with the headgroups of POPC and DTAB. Consequently, the spontaneous hydration of the amphiphiles is entropy driven in an aqueous environment. IR spectroscopy shows that hydration is accompanied by the increase in the conformational and/or motional freedom of the amphiphilic molecules upon water binding. In particular, a lyotropic chain melting transition is induced at a certain characteristic relative humidity. This event is paralleled by the adsorption of water. The corresponding exothermic adsorption heat is consumed completely (POPC) or partially (DTAB) by the hydrocarbon chains upon melting. Differential scanning calorimetry was used as an independent method to determine transition enthalpies of the amphiphiles at a definite hydration degree. Water binding onto the headgroups is discussed in terms of hydrogen bonding and polar interactions. The adsorption isotherms yield a number of 2.6 tightly bound water molecules per POPC and DTAB molecule. 相似文献
997.
Kedong Xia Junpo Guo Cuijuan Xuan Ting Huang Zhiping Deng Lingxuan Chen Deli Wang 《中国化学快报》2019,30(1):192-196
Nitrogen doped carbon nanosheets supported molybdenum carbides nanoparticles (MoxC/NCS) have been synthesized by tuning the mass ratio of melamine and ammonia molybdate. The Mo2C/NCS-10 exhibits superior electrocatalytic performance and stability for HER, which was attributed to N-doped carbon nanosheets, small particle size, mesoporous structure, and large electrochemical active surface area. 相似文献
998.
Kazuo Mukai Kanae Nagai Aya Ouchi Tomomi Suzuki Katsuhiro Izumisawa Shin-Ichi Nagaoka 《国际化学动力学杂志》2019,51(9):643-656
Measurements of aroxyl radical (ArO•)-scavenging rate constants () of antioxidants (AOHs) (α-tocopherol (α-TocH) and three catechins (CatHs) (ie, epicatechin (EC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG)) were performed in ethanol solution, using stopped-flow spectrophotometry. values were measured not only for each AOH, but also for the mixtures of two AOHs (α-TocH and CatH). A notable synergistic effect that the value of α-TocH increases 1.29, 1.84, and 1.65 times under the coexistence of constant concentrations of EC, EGC, and EGCG, respectively, was observed for the solutions including α-TocH and CatH. Similarly, values of CatHs (EC, EGC, and EGCG) increased 1.72, 2.25, and 2.34 times under the coexistence of constant concentrations of α-TocH, respectively. UV-Vis absorption of α-tocopheroxyl radical (α-Toc•) (λmax = 428 nm), which had been produced by reaction of α-TocH with ArO•, decreased remarkably under the coexistence of α-TocH and CatHs due to the fast α-TocH-regeneration reaction by CatHs. The result suggests that the prooxidant reaction due to α-Toc• is suppressed by the coexistence of CatHs. By analyzing the formation and decay curves of α-Toc•, it has been ascertained that one molecule of EGCG having three OH groups at B-ring may rapidly regenerate three molecules of α-Toc• to α-TocH. 相似文献
999.
1000.
Apparent equilibrium constants and calorimetric enthalpies of reaction have been measured for the reaction L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate(aq) + ammonia(aq) which is catalyzed by L-tryptophanase. High-pressure liquid-chromatography and microcalorimetery were used to perform these measurements. The equilibrium measurements were performed as a function of pH, temperature, and ionic strength. The results have been interpreted with a chemical equilibrium model to obtain thermodynamic quantities for the reference reaction: L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate–(aq) + NH
4
+
(aq). At T=25°C and Im=O the results for this reaction are: Ko=(1.05±0.13)×10–4,
G°=(22.71±0.33) kJ-mol–1,
H°=(62.0±2.3) kJ-mol–1, and
S°=(132±8) J-K–1-mol–1. These results have been used together with thermodynamic results from the literature to calculate standard Gibbs energies of formation, standard enthalpies of formation, standard molar entropies, standard molar heat capacities, and standard transformed formation properties for the substances participating in this reaction.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday. 相似文献