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131.
生物小分子与铜锌超氧化物歧化酶相互作用的波谱学研究及其应用 总被引:1,自引:0,他引:1
本工作以ESR和NMR为主要手段,并结合其它生化方法,考察了氨基酸、核酸碱基、糖等生命基本物质,和抗坏血酸等生命必需物质与钢锌超氧化物歧化酶的相互作用,实验观测到氨基酸、核酸碱基和抗坏血酸在水溶液中可以与酶中的Cu2+作用而使其脱离活性部位,以小分子络合物形式游离在溶液中,同时使酶失活,脱离活性部位的Cu2+的比例和酶的失活程度取决于小分子配体的加入量及其与Cu2+的络合能力。此外,首次尝试使用ESR方法,并借助氨基酸与酶的作用,考察了铜锌超氧化物歧化酶在盐酸胍变性和热变性过程中的构象变化行为,结果表明这一方法是直观而有效的。 相似文献
132.
Supersemiprime Rings and Supersemiprime Radical 总被引:4,自引:1,他引:3
§1. IntroductionInthisrecentyears,theprimeringswithspecialpropertieshavebeenstudiedsomeau-thors,forexample,N.T.Groenewaldintroducedthecompletelyprimeringsandthecompletelyrimeradicalin[1].D.HandelmanandJ.Lawrencediscussedthestronglyprimeringsandthestronglyprimeradicalin[2].S.Veldsmanstudiedthesuperprimeringsandthesuperprimeradicalin[3].ZhangXianjunintroducedtheAbsolutelysemiprimeringsandtheabsolutelysemiprimeradicalandsoon.Theaimofthispaperistostudythesemiprimeringswithspecialpropertiesan… 相似文献
133.
Hiroshi Ito Masaki Okazaki Dolores C. Miller 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1478-1505
Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with 1H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004 相似文献
134.
135.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
136.
137.
Ke Sha Dongshuang Li Yapeng Li Xiaotian Liu Shuwei Wang Jingqi Guan Jingyuan Wang 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5037-5049
Amphiphilic diblock copolymer polycaprolactone‐block‐poly(glycidyl methacrylate) (PCL‐b‐PGMA) was synthesized via enzymatic ring‐opening polymerization (eROP) and atom transfer radical polymerization (ATRP). Methanol first initiated eROP of ?‐caprolactone (?‐CL) in the presence of biocatalyst Novozyme‐435 under anhydrous conditions. The resulting monohydroxyl‐terminated polycaprolactone (PCL–OH) was subsequently converted to a bromine‐ended macroinitiator (PCL–Br) for ATRP by esterification with α‐bromopropionyl bromide. PCL‐b‐PGMA diblock copolymers were synthesized in a subsequent ATRP of glycidyl methacrylate (GMA). A kinetic analysis of ATRP indicated a living/controlled radical process. The macromolecular structures were characterized for PCL–OH, PCL–Br, and the block copolymers by means of nuclear magnetic resonance, gel permeation chromatography, and infrared spectroscopy. Differential scanning calorimetry and wide‐angle X‐ray diffraction analyses indicated that the copolymer composition (?‐CL/GMA) had a great influence on the thermal properties. The well‐defined, amphiphilic diblock copolymer PCL‐b‐PGMA self‐assembled into nanoscale micelles in aqueous solutions, as investigated by dynamic light scattering and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5037–5049, 2007 相似文献
138.
A. V. Sokolov 《Russian Chemical Bulletin》1992,41(10):1750-1755
The concept of the apparent electronegativity of a reaction site has been introduced. This has been used to develop a new scheme for calculating the relative rate constants of addition of radicals with different structures to vinyl monomers. The parameters of the scheme are given for 40 reagents. The results of a comparison of calculated and literature rate constants of addition are presented.Institute of Nonaqueous Solution Chemistry, Russian Academy of Sciences, 150003 Ivanovo. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2238–2245, October, 1992. 相似文献
139.
Yozo Miura Hiroyuki Dote Hiroyuki Kubonishi Kenichi Fukuda Tomoko Saka 《Journal of polymer science. Part A, Polymer chemistry》2007,45(6):1159-1169
A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB8 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB8 9‐miktoarm star copolymers were cleaved by treating with Me3SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007. 相似文献
140.
Reaction of arenesulfonylimines of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-sulfonylated fluorine-containing heterocycles, including the fused ones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2171–2175, November, 2007. 相似文献