全文获取类型
收费全文 | 123159篇 |
免费 | 6484篇 |
国内免费 | 14281篇 |
专业分类
化学 | 70850篇 |
晶体学 | 1153篇 |
力学 | 2420篇 |
综合类 | 861篇 |
数学 | 12812篇 |
物理学 | 19265篇 |
综合类 | 36563篇 |
出版年
2024年 | 195篇 |
2023年 | 915篇 |
2022年 | 2310篇 |
2021年 | 2404篇 |
2020年 | 2740篇 |
2019年 | 2673篇 |
2018年 | 2377篇 |
2017年 | 3357篇 |
2016年 | 3577篇 |
2015年 | 3476篇 |
2014年 | 4354篇 |
2013年 | 7580篇 |
2012年 | 7992篇 |
2011年 | 6832篇 |
2010年 | 5561篇 |
2009年 | 7124篇 |
2008年 | 7561篇 |
2007年 | 8796篇 |
2006年 | 8177篇 |
2005年 | 7082篇 |
2004年 | 6558篇 |
2003年 | 5395篇 |
2002年 | 6273篇 |
2001年 | 3971篇 |
2000年 | 3679篇 |
1999年 | 3386篇 |
1998年 | 2775篇 |
1997年 | 2319篇 |
1996年 | 2006篇 |
1995年 | 1844篇 |
1994年 | 1695篇 |
1993年 | 1433篇 |
1992年 | 1339篇 |
1991年 | 1031篇 |
1990年 | 844篇 |
1989年 | 824篇 |
1988年 | 626篇 |
1987年 | 453篇 |
1986年 | 347篇 |
1985年 | 245篇 |
1984年 | 244篇 |
1983年 | 137篇 |
1982年 | 211篇 |
1981年 | 174篇 |
1980年 | 195篇 |
1979年 | 182篇 |
1978年 | 169篇 |
1977年 | 122篇 |
1976年 | 108篇 |
1973年 | 67篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
891.
Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pKa1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pKa2 and pKa3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group. 相似文献
892.
893.
Lorenzo CaggianoDamiano Castoldi Raphael BeumerPau Bayón Joachim TelserCesare Gennari 《Tetrahedron letters》2003,44(43):7913-7919
During the course of our synthetic studies towards simplified eleuthesides, we have found that p-methoxyphenyl (PMP) protected allylic alcohols are compatible with the RCM reaction and can give better yields than the corresponding free allylic alcohols. 相似文献
894.
IntroductionInthepastseveralyears ,considerableprogresshasbeenachievedincontrollingtheassemblyofindividualbuildingblocksintostructureswithspecifictopologiesandinterestingpropertiessuchasmolecularrecognition ,ionexchangeandselectiveguestinclusion .1 3 Itis… 相似文献
895.
896.
A method combining the techniques of liquid – solid disk extraction (LSDE) and supercritical fluid elution (SFE) has been developed for the phenols regulated by the Clean Water Act. LSDE uses a disk or membrane made of polytetrafluoroethylene (PTFE) fibrils impregnated with small particles, e.g. styrene divinylbenzene (SDB) resin, to extract phenols from water. After disk extraction the retained analytes are eluted from the disk using SFE. SFE is used as an alternative to liquid solvent elution with an organic solvent. Analytes are separated, identified, and quantified using gas chromatography – ion trap detector mass spectrometry (GC-ITDMS). The method is capable of sub parts per billion detection limits, and precision of 5–28% RSD. Evaluation of various disks or membranes, such as C18-silica disks, SDB disks, and ion exchange membranes, has also been performed for the extraction of phenols from water. The results obtained from the in-situ aqueous acetylation of phenols and extraction of their acetates are quantitative. The utilization of LSDE and SFE techniques has proven to be a more effective approach than liquid – liquid extraction in minimizing air pollution and solvent waste. 相似文献
897.
The permeability of copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane for twelve gases (0_2, N_2, CO_2, H_2, D_2, He, At, CH_4, C_2H_4, C_2H_6, C_3H_6 and C_3H_8) was examined. The basic laws of solution and diffusion of the gases in the membrane were expounded preliminarily. It was found that a linear relationship between logarithm of diffusion coefficient (D) and critical molar volume (V_c) of the gases. The permeation characteristics of the gases in the copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane was also discussed. 相似文献
898.
Alternative Ligands. XXIII Rhodium(I) Complexes with Donor/Acceptor Ligands of the Type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) Donor/acceptor ligands of the type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) react with [Rh(CO)2Cl]2 (1) to give the mononuclear complexes RhCl(CO)(Me2PCH2CH2)2SiX2 [X = F( 4 ), Cl ( 5 )] and RhCl(CO)[2-Me2PC6H4)SixMe2]2 [X = F ( 8 ), Cl ( 9 )], respectively. In case of the ligands (Me2PCH2CH2)2SiCl2 ( 3 ) and (2-Me2PC6H6)SiClMe2 ( 7 ) the Rh(I) complexes formed in the first step partly undergo oxidative addition reactions of SiCl bonds yielding rhodium(III) compounds of low solubility. Only for 8 the coordination shifts Δδ = δ(complex)?δ(ligand) and coupling constants give some indication to possible Rh→Si interactions. However, the molecular structure of 8 determined by X-ray diffraction does not show RhSi or RhF bonding contacts. The new compounds were characterized by analytical (C, H) and spectroscopic investigations (MS, IR,-NMR). 相似文献
899.
The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1–aminopyrene and pmpa=N–(2–pyridylmethylene)–1–pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, esták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
900.
Polyol Metal Complexes. 27. Bis-Diolato Antimonates(III ) with Guanosine as the Diol The complex anions of K3[SbIII(Guo1,2′,3′H?3)2] · 10 H2O ( 1 ) and [Co(NH3)6][SbIII(Guo1,2′,3′H?3)2] · 9 H2O ( 2 ) are four-coordinate homoleptic bis(diolato)antimonate(III ) species. The guanosine trianions act as carbohydrate ligands through their cis-furanoidic ribosyl moiety, thus forming no nucleobase–metal bonds. 相似文献