全文获取类型
收费全文 | 6893篇 |
免费 | 234篇 |
国内免费 | 35篇 |
专业分类
化学 | 4796篇 |
晶体学 | 35篇 |
力学 | 287篇 |
数学 | 973篇 |
物理学 | 1071篇 |
出版年
2022年 | 84篇 |
2021年 | 85篇 |
2020年 | 98篇 |
2019年 | 97篇 |
2018年 | 82篇 |
2017年 | 73篇 |
2016年 | 149篇 |
2015年 | 150篇 |
2014年 | 176篇 |
2013年 | 372篇 |
2012年 | 380篇 |
2011年 | 450篇 |
2010年 | 246篇 |
2009年 | 254篇 |
2008年 | 385篇 |
2007年 | 363篇 |
2006年 | 379篇 |
2005年 | 388篇 |
2004年 | 323篇 |
2003年 | 275篇 |
2002年 | 267篇 |
2001年 | 111篇 |
2000年 | 96篇 |
1999年 | 85篇 |
1998年 | 66篇 |
1997年 | 93篇 |
1996年 | 97篇 |
1995年 | 70篇 |
1994年 | 62篇 |
1993年 | 67篇 |
1992年 | 63篇 |
1991年 | 58篇 |
1990年 | 40篇 |
1989年 | 46篇 |
1988年 | 41篇 |
1987年 | 35篇 |
1985年 | 81篇 |
1984年 | 65篇 |
1983年 | 50篇 |
1982年 | 68篇 |
1981年 | 75篇 |
1980年 | 54篇 |
1979年 | 67篇 |
1978年 | 70篇 |
1977年 | 81篇 |
1976年 | 54篇 |
1975年 | 54篇 |
1974年 | 51篇 |
1973年 | 38篇 |
1971年 | 37篇 |
排序方式: 共有7162条查询结果,搜索用时 15 毫秒
61.
62.
The solid-phase synthesis of the octapeptide 1 AcGly-Ala-Lys-Arg-His-Arg-Lys-ValOMe, which represents the fragment 14-21 of the amino acid sequence of the chromosomal histone H4, as well as of the structurally related nonapeptide 2 AcGly-Ala-Lys-Leu-Arg-His-Arg-Lys-ValOMe, is described using a new polyacrylic resin containing a glycolamide ester linkage(resin-NHCO-CH2-OCO-peptide) acting as a labile anchoring moiety between the resin and the peptide.After elongation of the polypeptide chain using classical protecting groups, i.e. t-butyloxycarbonyl for the α-NH2 function, benzyloxycarbonyl, nitro and 2,4-dinitrophenyl groups for the side-chains of Lys, Arg and His respectively, both peptides 1 and 2 were obtained in good yields and with a high purity as shown by high-pressure liquid chromatography, by amino-acid analysis and by high-field proton NMR spectroscopy.This work demonstrates the ability of the newly introduced polyacrylic resin to act as a convenient support for solid-phase peptide synthesis. 相似文献
63.
The chemistry of several of the Diels-Alder adducts formed by the reaction of 4,4-diethylpyrazoline-3,5-dione ( 1 ) with conjugated dienes was studied with respect to reduction (hydride and catalytic) and reaction with base. Reaction of the 2,3-dimethyl-1,3-butadiene adduct with lithium aluminum hydride followed by hydrogenation gave 1,3,5,6,7,8-hexahydro-cis-endo-6,7-dimethyl-2,2-diethylpyrazolo[1,2-a]pyridazine ( 11 ). Attempted conversion of this compound to 3,3-diethyl-cis-7,8-dimethyl-1,5-diazacyclononane ( 12 ) gave instead a compound which has been tentatively identified as N-(2,3-dimethyl-4-aminobutyl)-2-ethyl-2-methylbutanaldimine ( 14 ). Lithium aluminum hydride reduction of 4,4-diethylpyrazolidine-3,5-dione ( 22 ) or the adducts formed from 1 and cyclopentadiene or 1,3-cyclohexadiene gave good yields of 4,4-diethylpyrazolidine ( 21 ). This later reduction gave a new and efficient synthetic route to the pyrazolidine ring system. Lithium aluminum hydride reduction of 5,6,7,8-tetrahydro-5,8-ethano-2,2-diethylpyrazolo[1,2-a]pyridazine-1,3(2H)dione ( 26 ) followed by hydrogenolysis led to a high yield of 4,4-diethyl-2,6-diazabicyclo[5.2.2]undecane ( 28 ) which is the first reported example of this ring system. Reaction of several of the adducts with ethanolic potassium hydroxide resulted in the opening of the five-membered ring. 相似文献
64.
The peroxide function of artemisinin has been activated by iron(II)-heme generated in situ from iron(III)-protoporphyrin-IX and glutathione, a biologically relevant reductant. In mild conditions, this reaction produced a high yield (85%) of heme derivatives alkylated at alpha-, beta-, and delta-meso positions by a C4-centered radical derived from artemisinin. 相似文献
65.
An extended average energy (EAE) calculation of the 2s2 and 2p21S resonance state energies of two-electron atoms is carried out. We take the bare-nucleus hamiltonian as the initial approximation and treat the zeroth-order degeneracy by van Vleck perturbation theory, For both H? and He the lower state energies agree quite well with experiment while the upper state is about 1–2 eV too high. Our remits for He are comparable in accuracy to those obtained by the 1/Z Hartree—Fock perturbation method. A brief concluding discussion of ways to improve the simple EAE technique is presented. 相似文献
66.
Hanna Nagy Kovacs Alvin D. Delman Bernard B. Simms 《Journal of polymer science. Part A, Polymer chemistry》1970,8(4):869-884
The effects of incorporating a p-phenylene- (or m-phenylene)-1,3,4-oxadiazole fragment into the backbone of poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)], which was developed by the authors, was investigated. Bis[(p-carbohydrazidophenyl)]diphenylsilane was copolymerized with dipentachlorophenyl terephthalate or isophthalate to produce the prepolymers poly[N-(p-diphenylsilylbenzoyl)-N′N″-(terephthaloyl)-N″′-(p-benzoyl)dihydrazide] and poly[N-(p-diphenylsilylbenzoyl)-N′,-N″-(isophthaloyl)-N″′-p-(benzoyl) dihydrazide], respectively. The polyhydrazides were converted by thermal dehydration into poly[1,4-phenylene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,4-phenylene-2,5-(1,3,4-oxadiazole)] and poly[1,4-phenyl-ene(diphenylsilyl)-1,4-phenylene-(1,3,4-oxadiazole-2,5-diyl)-1,3,4-(oxadiazole)]. The new polymers were soluble in organic solvents. Films cast from these solutions exhibited good adhesion to glass and metal surfaces. Thermal analysis showed that the heat stability of all these polymers was about the same and that they were resistant to decomposition when heated in air to about 400°C. The results also indicated that these polymers were somewhat less heat-resistant than samples of poly-[1,4-phenylene(diphenylsilyl)-1,4-phenylene-2,5-]1,3,4-(oxadiazole) synthesized from bis(p-carbohydrazidophenyl)diphenylsilane and bis-(p-carbopentachlorophenoxy-phenyl)diphenylsilane. 相似文献
67.
[reaction: see text] The Cp(2)TiCl-mediated deoxygenation of leurosine (1) afforded anhydrovinblastine (4) in good yield. Furthermore, as the reaction proceeded via a carbon-centered radical intermediate, this transient was also trapped by a hydrogen-atom donor to afford selectively reduced alkaloid 10. 相似文献
68.
69.
70.
Franoise Arnaud-Neu Marie-Christine Almasio Bernard Spiess Marie-Jos Schwing-Weill Sally A. Sullivan Jean-Marie Lehn 《Helvetica chimica acta》1985,68(4):831-839
Nature and Stability of Some Metallic Complexes of Dinucleating Cryptands in Solution II. Polythiamacrotricycles and Related Monocyclic Subunits The stability constants of the Cu2+ and Ag+ complexes of the cylindrical macrotricycle 1a (1,7,13,19-tetraaza 4,16-dioxa 10,22,27,32-tetrathiatricyclo[17.5.5.5]tetratriacontane) have been determined by pH-metry, as well as those of the Cu2+, Co2+, Zn2+, Cd2+, Pb2+, and Ag+ complexes of the monocyclic subunit 2a (1,7-dimethyl-1,7-diaza 4,10-dithiacyclododecane), in aqueous solutions (NaClO4) at 25°. In the Cu(II) systems, equilibria were reached slowly, and the results established by pH-metry were confirmed by UV/VIS spectrophotometric studies. The tricycle 1a forms dinuclear cryptates with copper and silver, with overall stability constants log β210 (Cu2- 1a )4+ = 18.5, log β21-2 (Cu2- 1a (OH)2)2+ = 4.8, log β210(Ag2- 1a )2+ = 23.0. Ag+ also forms a mononuclear (Ag- 1a )+ complex, with log β110 = 13.1, but no mononuclear species were detected in the Cu- 1a system. The absorption spectra of the bis-Cu(II) complexes of 1a and 2a in aqueous medium, MeOH and propylene carbonate (PC) are given, as well as those, in MeOH and PC, of the bis-copper complexes of the related monocycles 3 and 4 (1,7-diaza-4,10,13-trithiacyclopentadecane and 1.10-diaza 4,7,13,16-tetrathiacyclooctadecane, respectively), and tricycle 5 with two benzyl groups in the lateral chains. The complexing properties of the polyoxa- and polythia macrotricycles (Parts I and II of this series) are compared to those of other bis-chelating ligands, the bicyclic bis-tren and the monocyclic bis-dien. 相似文献