全文获取类型
收费全文 | 1167篇 |
免费 | 41篇 |
国内免费 | 6篇 |
专业分类
化学 | 979篇 |
晶体学 | 12篇 |
力学 | 18篇 |
数学 | 50篇 |
物理学 | 155篇 |
出版年
2023年 | 3篇 |
2021年 | 15篇 |
2020年 | 22篇 |
2019年 | 16篇 |
2018年 | 9篇 |
2017年 | 9篇 |
2016年 | 20篇 |
2015年 | 16篇 |
2014年 | 26篇 |
2013年 | 45篇 |
2012年 | 67篇 |
2011年 | 84篇 |
2010年 | 39篇 |
2009年 | 48篇 |
2008年 | 66篇 |
2007年 | 63篇 |
2006年 | 72篇 |
2005年 | 79篇 |
2004年 | 62篇 |
2003年 | 61篇 |
2002年 | 57篇 |
2001年 | 23篇 |
2000年 | 15篇 |
1999年 | 9篇 |
1998年 | 19篇 |
1997年 | 20篇 |
1996年 | 14篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 14篇 |
1983年 | 6篇 |
1982年 | 19篇 |
1981年 | 18篇 |
1980年 | 20篇 |
1979年 | 13篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 8篇 |
1974年 | 5篇 |
1973年 | 6篇 |
排序方式: 共有1214条查询结果,搜索用时 265 毫秒
51.
Shoji Asano Keiji Itano Kohfuku Kohda Yuriko Yamagata 《Journal of heterocyclic chemistry》1996,33(4):1115-1121
Reaction of 9-substituted (methyl or benzyl) 1-aminoadenines 1 with hydrazine afforded 9-substituted 6-hydrazinopurines 2 and 1-substituted 5-ammo-4-(4-amino-1,2,4-triazol-3-yl)imidazole ( 4 ). The product ratio of 2 to 4 rose with increasing amounts of methanol used as the solvent. When the same reaction was carried out using 1,9-dimethyladenine instead of 1 , compounds 2 and 4 were also obtained with N6,9-dimethyladenine. A possible mechanism for formation of 2 and 4 is discussed. 相似文献
52.
The recently proposed electron-hole potential (EHP) method for excited states is extended to the multi-configurational case. The variation equation is solved using the quadratic convergence method. The EHP methods are shown to be approximations to the complete singly excited configuration interaction (CSECI) in the variational sense. Extended Brillouin theorems are proved for the EHP methods. The excitation energies and wave functions obtained by one and two configurational EHP methods agree well with those of the CSECI method. The EHP methods have clear advantage in the computer time requirement over the CI method and are especially suited for a calculation of approximate excited states of large molecules. The EHP methods are applicable to excited states which belong to the same irreducible representation as the ground state. 相似文献
53.
Ilieva S Galabov B Musaev DG Morokuma K Schaefer HF 《The Journal of organic chemistry》2003,68(4):1496-1502
The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process. 相似文献
54.
A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein-Ponndorf-Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2'-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6(R = Ph), prepared in situ from Me(3)Al, 2,2'-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH(2)Cl(2) at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1[prime or minute]-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity. 相似文献
55.
Steven L. Richardson Joseph S. Francisco Alexander M. Mebel Keiji Morokuma 《Chemical physics letters》1997,270(5-6):395-398
The reaction of HOCl + HCl → Cl2 + H2O in the presence of chlorine anion Cl− has been studied using ab initio methods. The overall exothermicity is 15.5 kcal mol−1 and this reaction has been shown to have a high activation barrier of 46.5 kcal mol−1. Cl− is found to catalyze the reaction via the formation of HOCl·Cl−, ClH·HOCl·Cl− and Cl−·H2) intermediate ion-molecule complexes or by interacting with a concerted four-center transition state of the reaction of HOCl + HCl. 相似文献
56.
cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH(3) to generate cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C(13.5)H(13)N(3)O(6.5)Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) A; beta = 99.07(1) degrees; V = 1536.7(2) A(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I) in water and alcohol (ROH, R = CH(3), C(2)H(5)) to form [[trans-Ru(NO)(pyca)(2)](2)(H(3)O(2))](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H(2)O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH(3))(pyca)(2)] (type V), with Cl(-) in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n)(+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C(2)H(5))(4)N[Ru(NO)Cl(3)(pyca)] was synthesized by the reaction of [Ru(NO)Cl(5)](2)(-) with Hpyca and characterized by X-ray structural analysis: C(14)H(24)N(3)O(3)Cl(3)Ru; triclinic, Ponemacr;, a = 7.631(1), b = 9.669(1), c = 13.627(1) A; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1) degrees; V = 981.1(1) A(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl(3)(pyca)](-) or [Ru(NO)Cl(5)](2)(-) with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C(12)H(8)N(3)O(5)ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) A; beta = 113.45(1) degrees; V = 1382.4(2) A(3); Z = 4. 相似文献
57.
Shintani Y Hirako K Motokawa M Iwano T Zhou X Takano Y Furuno M Minakuchi H Ueda M 《Journal of chromatography. A》2005,1073(1-2):17-23
We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry. 相似文献
58.
Metal-ion-assisted hydrolysis of dipeptides involving a serine residue in a neutral aqueous solution
Yashiro M Sonobe Y Yamamura A Takarada T Komiyama M Fujii Y 《Organic & biomolecular chemistry》2003,1(4):629-632
Dipeptides having a serine residue at the C-terminus, X-Ser, where X is an appropriate amino acid residue, were efficiently hydrolyzed in the presence of ZnCl2 at pH 7.0. The rapid hydrolysis of X-Ser is due to an autocatalysis of the hydroxy group in the serine residue, and is found to be accelerated by a metal ion, in particular by ZnCl2. Roles of the metal ion in the hydrolysis of peptides involving a serine residue, in relation to the recently reported protein cleavages, are discussed. 相似文献
59.