全文获取类型
收费全文 | 66761篇 |
免费 | 18381篇 |
国内免费 | 198篇 |
专业分类
化学 | 70781篇 |
晶体学 | 170篇 |
力学 | 2619篇 |
数学 | 7060篇 |
物理学 | 4710篇 |
出版年
2023年 | 4109篇 |
2022年 | 1513篇 |
2021年 | 2695篇 |
2020年 | 4837篇 |
2019年 | 2580篇 |
2018年 | 2461篇 |
2017年 | 776篇 |
2016年 | 5933篇 |
2015年 | 5854篇 |
2014年 | 5320篇 |
2013年 | 6314篇 |
2012年 | 4274篇 |
2011年 | 2436篇 |
2010年 | 4051篇 |
2009年 | 3988篇 |
2008年 | 2275篇 |
2007年 | 2032篇 |
2006年 | 1361篇 |
2005年 | 1294篇 |
2004年 | 1122篇 |
2003年 | 963篇 |
2002年 | 879篇 |
2001年 | 402篇 |
2000年 | 316篇 |
1997年 | 400篇 |
1996年 | 442篇 |
1995年 | 387篇 |
1994年 | 368篇 |
1993年 | 475篇 |
1992年 | 339篇 |
1989年 | 314篇 |
1988年 | 356篇 |
1985年 | 406篇 |
1984年 | 446篇 |
1983年 | 328篇 |
1982年 | 506篇 |
1981年 | 501篇 |
1980年 | 521篇 |
1979年 | 510篇 |
1978年 | 525篇 |
1977年 | 611篇 |
1976年 | 653篇 |
1975年 | 714篇 |
1974年 | 725篇 |
1973年 | 524篇 |
1972年 | 498篇 |
1971年 | 440篇 |
1970年 | 640篇 |
1969年 | 493篇 |
1968年 | 519篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Basicities of the series of complexes CpIr(CO)(PR(3)) [PR(3) = P(p-C(6)H(4)CF(3))(3), P(p-C(6)H(4)F)(3), P(p-C(6)H(4)Cl)(3), PPh(3), P(p-C(6)H(4)CH(3))(3), P(p-C(6)H(4)OCH(3))(3), PPh(2)Me, PPhMe(2), PMe(3), PEt(3), PCy(3)] have been measured by the heat evolved (DeltaH(HM)) when the complex is protonated by CF(3)SO(3)H in 1,2-dichloroethane (DCE) at 25.0 degrees C. The -DeltaH(HM) values range from 28.0 kcal/mol for CpIr(CO)[P(p-C(6)H(4)CF(3))(3)] to 33.2 kcal/mol for CpIr(CO)(PMe(3)) and are directly related to the basicities of the PR(3) ligands in the complexes. For the more basic pentamethylcyclopentadienyl analogs, the -DeltaH(HM) values range from 33.8 kcal/mol for the weakest base CpIr(CO)[P(p-C(6)H(4)CF(3))(3)] to 38.0 kcal/mol for the strongest CpIr(CO)(PMe(3)). The nucleophilicities of the Cp'Ir(CO)(PR(3)) complexes were established from second-order rate constants (k) for their reactions with CH(3)I to give [Cp'Ir(CO)(PR(3))(CH(3))](+)I(-) in CD(2)Cl(2) at 25.0 degrees C. There is an excellent linear correlation between the basicities (DeltaH(HM)) and nucleophilicities (log k) of the CpIr(CO)(PR(3)) complexes. Only the complex CpIr(CO)(PCy(3)) with the bulky tricyclohexylphosphine ligand deviates dramatically from the trend. In general, the pentamethylcyclopentadienyl complexes react 40 times faster than the cyclopentadienyl analogs. However, they do not react as fast as predicted from electronic properties of the complexes, which suggests that the steric size of the Cp ligand reduces the nucleophilicities of the CpIr(CO)(PR(3)) complexes. In addition, heats of protonation (DeltaH(HP)) of tris(2-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, and tris(2,4,6-trimethylphenyl)phosphine were measured and used to estimate pK(a) values for these highly basic phosphines. 相似文献
992.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献
993.
Wolfgang Stadlbauer Otto Schmut Prof. Dr. Thomas Kappe 《Monatshefte für Chemie / Chemical Monthly》1977,108(2):367-379
The reaction of N-(2-pyridyl)-carbaminates (3), 1-phenyl-3-(2-pyridyl)-urea (5 a) or alkyl and aryl substituted pyridopyrimidinediones (2) synthesized from 2-amino-pyridine with arylisocyanates (4 a, b) yields 3-aryl substituted pyrido-[1,2-a]-s-triazine-2,4-diones (1). 2-Aminopyridine and azamalonic derivatives (ethoxycarbonyl isocyanate, ethyl iminodicarboxylate) react to give the 3-unsubstituted triazine system (1 c). The isolation of monocyclic triazinediones obtained from the reaction of N-phenylbenzamidine (9) with aryl isocyanate (4 a) or ethoxycarbonyl isocyanate failed because of hydrolytic ring opening. The mechanism of the reaction of 3-substituted pyrido-pyrimidinediones (2) and phenyl isocyanate (4 a) is discussed. 相似文献
994.
This article outlines some of the factors influencing the choice of a suitable reactor for using immobilized biocatalysts.
We have concentrated on biochemical engineering parameters of immobilized biocatalysts, which are important with respect to
their application in industrial processes. 相似文献
995.
Applied Biochemistry and Biotechnology - The capacity of polystyrene microspheres with immobilized antibodies against type 1 pili ofE. coli was measured. Using pure IgG-type monoclonal antibodies... 相似文献
996.
Jia Hui Xu Ting Ting Zhuang Yi Cao Dr. Jing Yang Jing Jia Wen Zheng Ying Wu Dr. Chun Fang Zhou Dr. Li Huang Ying Wang Prof. Dr. Ming Bo Yue Dr. Jian Hua Zhu Prof. Dr. 《化学:亚洲杂志》2007,2(8):996-1006
Copper oxide was incorporated into MCM‐41 by a one‐pot synthesis under acidic conditions to prepare a new mesoporous nitrosamines trap for protection of the environment. The resulting composites were characterized by XRD, N2 adsorption–desorption, and H2 temperature‐programmed reduction techniques, and their adsorption capabilities were assessed in the gaseous adsorption of N‐nitrosopyrrolidine (NPYR). The adsorption isotherms were consistent with the Freundlich equation. The copper salt was deposited onto MCM‐41 during the evaporation stage and was fixed on the host in the calcination process that followed. MCM‐41 was able to capture NPYR in air below 373 K but not at 453 K. Loading of copper oxide on MCM‐41 greatly improved its adsorption capability at elevated temperatures. The influence of the incorporation of copper into MCM‐41 samples and the adsorption behavior of these samples are discussed in detail. 相似文献
997.
Reza Dabesrani Robert H. Sik Donald G. Davis George Dubay Colin F. Chignell 《Photochemistry and photobiology》1993,58(3):367-373
Abstract— The photochemistry, photophysics, and photosensitization (Type I and II) of indomethacin (IN) (N-[p-chlorobenzoyl]-5-methoxy-2-methylindole-3-acetic acid) has been studied in a variety of solvents using NMR, high performance liquid chromatography-mass spectroscopy, transient spectroscopy, electron paramagnetic resonance in conjunction with the spin trapping technique, and the direct detection of singlet molecular oxygen (l O2) luminescence. Photodecomposition of IN (λex > 330 nm) in degassed or air-saturated benzene proceeds rapidly to yield a major (2; N-[p-chlorobenzoyl]-5-methoxy-2-methyl-3-methylene-indoline) and a minor (3; N-[p-chlorobenzoyl]-5-methoxy-2, 3-dimethyl-indole) decarboxylated product and a minor indoline (5; 1-en-5-methoxy-2-methyl-3-methylene-in-doline), which is formed by loss of the p-chlorobenzoyl moiety. In air-saturated solvents two minor oxidized products 4 (N-[p-chlorobenzoyl]-5-methoxy-2-methylindol-3-aldehyde) and 6 (5-methoxy-2-methyl-indole-3-aldehyde) are also formed. When photolysis was carried out in 18O2-saturated benzene, the oxidized products 4 and 6 contained 18O, indicating that oxidation was mediated by dissolved oxygen in the solvent. In more polar solvents such as acetonitrile or ethanol, photodecomposition is extremely slow and inefficient. Phosphorescence of IN at 77 K shows strong solvent dependence and its emission is greatly reduced as polarity of solvent is increased. Flash excitation of IN in degassed ethanol or acetonitrile produces no transients. A weak transient is observed at 375 nm in degassed benzene, which is not quenched by oxygen. Irradiation of IN (λex > 325 nm) in N2-gassed C6H6 in the presence of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) results in the trapping of two carbon-centered radicals by DMPO. One adduct was identified as DMPO/.COC6H4-p-CI, while the other was probably derived from a radical formed during IN decarboxylation. In air-saturated benzene, (hydro) peroxyl and alkoxyl radical adducts of DMPO are observed. A very weak luminescence signal from 1O2 at 1268 nm is observed initially upon irradiation (λex= 325 nm) of IN in air-saturated benzene or chloroform. The intensity of this 1O2 signal increases as irradiation is continued suggesting that the enhancement in 1O2 yield is due to photoproduct(s). Accordingly, when 2 and 3 were tested directly, 2 was found to be a much better sensitizer of 1O2 than IN. In air-saturated ethanol or acetonitrile no IN 1O2 luminescence is detected even on continuous irradiation. The inability of IN to cause phototoxicity may be related to its photo stability in polar solvents, coupled with the low yield of active oxygen species (1O2, O2?-) upon UV irradiation. 相似文献
998.
999.
Acid-catalyzed isomerization of the petrosterol side chain () proceeds stereospecifically to yield the naturally occurring 26-dehydro-25-epiaplysterol side chain (); in addition, a 1.5-hydride shift leading to 22-dehydro-25-epiaplysteryl acetate () has also been observed. 相似文献
1000.
Douglas X. West Robert D. Profilet John C. Severns Roger K. Bunting 《Transition Metal Chemistry》1988,13(1):29-34
Summary A series of cobalt(II), nickel(II) and copper(II) complexes of 2-picolinamineN-oxide, HA, has been prepared. Solids of formula [M(HA)3](BF4)2 (M=cobalt(II) or nickel(II); [Cu(HA)2]X2 (X=BF
4
–
, NO
3
–
); [Co(HA)2X2] (X=Cl– or Br–); [Ni(HA)2Cl2] and [Cu(HA)X2] (X=Cl– or Br–] have been isolated and characterized by partial elemental analyses, molar conductivities, magnetic susceptibilities, DSC-TGA, and spectral methods. All complexes were found to be monomeric, and their spectral parameters are compared with those of the metal ion complexes ofN-alkyl-2-picolinamineN-oxides, 2-dialkylaminopyridineN-oxides and 2-picolinamine. The cobalt(II) and nickel(II) halide complexes spectrally show a mixture of octahedral and tetrahedral centres. 相似文献