全文获取类型
收费全文 | 34822篇 |
免费 | 6474篇 |
国内免费 | 4606篇 |
专业分类
化学 | 20611篇 |
晶体学 | 394篇 |
力学 | 3136篇 |
综合类 | 387篇 |
数学 | 5141篇 |
物理学 | 16233篇 |
出版年
2024年 | 94篇 |
2023年 | 357篇 |
2022年 | 901篇 |
2021年 | 1039篇 |
2020年 | 1398篇 |
2019年 | 1221篇 |
2018年 | 1195篇 |
2017年 | 1357篇 |
2016年 | 1547篇 |
2015年 | 1387篇 |
2014年 | 1883篇 |
2013年 | 3008篇 |
2012年 | 2083篇 |
2011年 | 2165篇 |
2010年 | 1879篇 |
2009年 | 2165篇 |
2008年 | 2203篇 |
2007年 | 2276篇 |
2006年 | 2162篇 |
2005年 | 1806篇 |
2004年 | 1605篇 |
2003年 | 1476篇 |
2002年 | 1448篇 |
2001年 | 1212篇 |
2000年 | 1102篇 |
1999年 | 961篇 |
1998年 | 907篇 |
1997年 | 723篇 |
1996年 | 667篇 |
1995年 | 582篇 |
1994年 | 487篇 |
1993年 | 394篇 |
1992年 | 326篇 |
1991年 | 287篇 |
1990年 | 188篇 |
1989年 | 190篇 |
1988年 | 185篇 |
1987年 | 143篇 |
1986年 | 140篇 |
1985年 | 121篇 |
1984年 | 101篇 |
1983年 | 49篇 |
1982年 | 91篇 |
1981年 | 95篇 |
1980年 | 58篇 |
1979年 | 70篇 |
1978年 | 36篇 |
1977年 | 32篇 |
1976年 | 26篇 |
1974年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
951.
Luigi R. Nassimbeni Sevi Papanicolaou Madeleine H. Moore 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(1):31-42
The structures of Ni(NCS)2(4-PhPy)4·4DMSO and Ni(NCS)2(3-MePy)4·CHCl3 have been elucidated. Movement of guest molecules through channels in the host structure was simulated by potential energy calculations. Ni(NCS)2(3,5-diMePy)4 does not form inclusion compounds. An intra-molecular potential energy study shows that theortho-hydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. The same result is obtained with the 4-methylpyridine ligand, which suggests that the extent of rotation of substituted pyridines about the Ni–N bounds is not a factor governing clathrate formation.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82030 (43 pages). 相似文献
952.
Maksymilian Ignaczak Andrzej Grzejdziak 《Monatshefte für Chemie / Chemical Monthly》1988,119(1):71-81
Predominance areas of various equilibria were identified and complex formation constants of Ag(I) with 1,10-phenanthroline were determined as well as the solubility product of the complex salt for Ag(phen)2ClO4 in propylene carbonate. The solubility product of AgNO3 in propylene carbonate was estimated. The value of the formal potential of the system Ag(phen)
2
2+
/Ag(phen)
2
+
inPC was determined by chronovoltammetry. Differences in the stability of analogous complexes in water andPC are discussed.
Die Gleichgewichtskonstante der Komplexierung und die Redoxpotentiale im System Ag(II)/Ag(I)-1,10-Phenantrolin in Propylencarbonat
Zusammenfassung Die Gebiete der Dominanz der einzelnen Gleichgewichte, die Bildungskonstanten 1 und 2 der Komplexe Ag(I) mit 1,10-Phenantrolin und der Wert des Löslichkeitsproduktes Ag(phen)2ClO4 in Propylencarbonat wurden bestimmt. Das Löslichkeitsprodukt von AgNO3 in Propylencarbonat wurde abgeschätzt. Die Werte des formalen Potentials des Systems Ag(phen) 2 2+ /Ag(phen) 2 + inPC wurden mit Hilfe cyclischer Voltametrie ermittelt. Es wurden weiterhin die Unterschiede in der Stabilität analoger Komplexe in Wasser und in Propylencarbonat diskutiert.相似文献
953.
用Suzuki偶合反应合成了一系列以咔唑为主链,与不同的芳香环和杂环化合物 共聚的新型电致发光无规共聚物.这些共聚物溶于普通的有机溶剂,发较强的荧光 .咔唑链段为共聚物提供了很好的空穴传输和空穴注入性能.与咔唑共聚的窄能隙 单体,如蒽(ANT)、噻吩(Th)、2,1,3-苯并噻二唑(BTDZ)、2,1,3—苯并硒二唑 (BseDZ)和4,7—二噻吩—2,1,3—苯并噻二唑(DBT)在聚合物中含量小于50%时 成为陷阱中心.还观察到极为有效的分子内能量转移.由于共聚单体的能隙不同, 这些电致发光共聚物的发光范围可覆盖整个可见光谱区.研究结果表明,用咔唑作 为宽带主体,与少量低带隙单体共聚,有可能成为一种合成同时兼有优异空穴注入 特性,又能广泛调节发光颜色的新的发光聚合物体系. 相似文献
954.
铜(Ⅱ)-邻菲咯啉-(邻菲咯啉-5,6-二酮)络合物的合成及其同脱氧核糖核酸的作用 总被引:9,自引:0,他引:9
以邻菲咯啉(phen)、邻菲咯啉-5,6-二酮(dione)为配体首次合成了高氯酸邻菲咯啉-邻菲咯啉-5,6-二酮(Ⅱ)。用荧光光谱,摩尔比,粘度,MLCT减色效应,平衡常数以及荧光能量转移研究了各合物与鱼精子DNA的结合情况,证实了该络合物与DNA存在插入作用。基于络合物对DNA能量转移造成荧光量子产率比值(Φλ/Φ320)的降低,解释了不同波长激发光下,荧光发射峰在加入DNA后产生猝灭和增强两种绝然不同的现象。 相似文献
955.
以Al2O3为基质,添加ZrO2和La2O3,制成La2O3-ZrO2-Al2O3复合载体,然后采用SO42-进行改性,再负载上Cu2+,制备了铜基SO42-改性的复合载体催化剂(Cu/SO42-/La2O3-ZrO2-Al2O3)。考察了它在富氧条件下对丙烯选择还原NO的催化性能,并借助XRD、SEM、TG、Py-IR、NH3-TPD、FTIR和TPR等方法研究了Cu/SO42-/La2O3-ZrO2-Al2O3的结构和性能的关系。结果表明,ZrO2的加入主要有利于提高催化剂的低温活性;La2O3的加入则主要有利于提高催化剂的热稳定性和还原性能;SO42-能够与Zr形成螯合双配位结构,大幅度促使催化剂表面酸量增加并且酸性增强;因此,有效地提高了Cu/SO42-/La2O3-ZrO2-Al2O3在富氧条件下对丙烯选择还原NO的催化活性和水热稳定性。在无水条件下,Cu/SO42-/La2O3-ZrO2-Al2O3能使NO的最大转化率高达84.3%,即使在275 ℃ 10%水蒸气存在的情况下,仍能使NO的转化率高达81.2%。 相似文献
956.
957.
INTRODUCTIONThe wicking technique has been used to determine the surface energy components of solids[1-7]. Generally, thereare two wicking processes in practice, i.e. thin layer wicking and column wicking. A comparison of the twowicking techniques made by van Oss et al.[2], shows that column wicking has a problem of showing differentpacking density due to some kinds of powder materials, i.e. clay can not give good repacking reproducibility[2].But thin layer wicking has a problem in sample… 相似文献
958.
M. Yakup Arca Meltem Ylmaz Emine Yaln Gülay Bayramo
lu 《Journal of membrane science》2004,240(1-2):167-178
Poly(hydroxyethyl methacrylate), pHEMA, and a composite pHEMA/chitosan networks were synthesized in the membrane form via UV initiated photo-polymerisation in the presence of an initiator ,′-azoisobutyronitrile. Reactive Yellow 2 (RY-2) was covalently immobilised as a dye–ligand onto both membranes. The polarity and surface energy of the investigated membranes were determined by contact angle measurement. The incorporation of chitosan in the pHEMA networks produced more hydrophilic surface, as indicated by contact angle analysis. The binding characteristics of lysozyme, γ-globulins, human serum albumin (HSA) and bovine serum albumin (BSA) to pHEMA-RY-2 and pHEMA/chitosan-RY-2 affinity membranes have been investigated from aqueous solution and their dye–ligand free forms were used as control systems. When chitosan was incorporated in the pHEMA network as a cationic polymer led to higher adsorption capacity for the lysozyme. Selective adsorption behaviour was also observed in the case of pHEMA/chitosan-RY-2 membrane for the lysozyme. The non-specific adsorptions of the lysozyme on the pHEMA and pHEMA/chitosan membranes were about 1.9 and 7.2 mg/ml, respectively. These were negligible for all others investigated proteins. The lysozyme adsorption data was analysed using the first-order and the second-order models. The first-order equation in both affinity membrane systems is the most appropriate equation to predict the adsorption capacities of the adsorbents. The adsorption isotherms well fitted the combined Langmuir–Freundlich model. A theoretical analysis has been conducted to estimate the thermodynamic contributions (changes in enthalpy, entropy and Gibbs free energy) for the adsorption of lysozyme to both dye–ligand immobilised membranes. The adsorption capacities of both dye–ligand immobilised membranes increased with increasing the temperature while decreased with increasing the NaCl concentration. Both affinity membranes are stable when subjected to sanitization with sodium hydroxide after repeated separation–elution cycles. 相似文献
959.
Potential energy functions suitable for the (Cs1–xNaxT2O4)-A type zeolite family were obtained from the known crystal structure of Cs7Na5-A zeolite. Using these potential functions, several other crystal structures in these family were obtained by molecular mechanical calculations. The activation energy - to -cage transmission of the H2 molecule and the void volume of Cs3Na9-A zeolite were calculated. 相似文献
960.
Isolated polyfluorobenzene (PFB) molecules and their protonated forms are investigated by the AM1 method with full geometry optimization. The proton affinities of PFB are estimated for different protonated positions. The proton affinity of PFB averaged over all isomers is shown to decrease monotonically as the number of fluorine atoms in the molecule increases. The relative populations of different isomers of arenonium ions (AI) formed by PFB protonation are determined. From the calculated data, the value of + for the F atom in theipso-position is estimated as 1.00. The activation energies of the 1,2-hydrogen shifts in AI are calculated. The dependences of the proton affinity and the activation energies of 1,2-hydrogen shifts on the number of halogen atoms are found to have distinct characters for PFB and polychlorobenzenes. The physical reasons for these difference are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1878–1882, November, 1993. 相似文献