全文获取类型
收费全文 | 2366篇 |
免费 | 69篇 |
国内免费 | 6篇 |
专业分类
化学 | 1582篇 |
晶体学 | 16篇 |
力学 | 78篇 |
数学 | 363篇 |
物理学 | 279篇 |
无线电 | 123篇 |
出版年
2023年 | 20篇 |
2022年 | 21篇 |
2021年 | 33篇 |
2020年 | 36篇 |
2019年 | 32篇 |
2018年 | 26篇 |
2017年 | 26篇 |
2016年 | 65篇 |
2015年 | 45篇 |
2014年 | 48篇 |
2013年 | 119篇 |
2012年 | 102篇 |
2011年 | 150篇 |
2010年 | 86篇 |
2009年 | 65篇 |
2008年 | 118篇 |
2007年 | 131篇 |
2006年 | 120篇 |
2005年 | 116篇 |
2004年 | 101篇 |
2003年 | 105篇 |
2002年 | 84篇 |
2001年 | 28篇 |
2000年 | 29篇 |
1999年 | 28篇 |
1998年 | 20篇 |
1997年 | 20篇 |
1996年 | 36篇 |
1995年 | 30篇 |
1994年 | 25篇 |
1993年 | 25篇 |
1992年 | 29篇 |
1991年 | 26篇 |
1990年 | 22篇 |
1989年 | 28篇 |
1988年 | 29篇 |
1987年 | 19篇 |
1986年 | 17篇 |
1985年 | 37篇 |
1984年 | 41篇 |
1983年 | 22篇 |
1982年 | 35篇 |
1981年 | 28篇 |
1980年 | 23篇 |
1979年 | 27篇 |
1978年 | 26篇 |
1977年 | 20篇 |
1976年 | 22篇 |
1975年 | 16篇 |
1974年 | 21篇 |
排序方式: 共有2441条查询结果,搜索用时 15 毫秒
31.
Bolm C Verrucci M Simic O Cozzi PG Raabe G Okamura H 《Chemical communications (Cambridge, England)》2003,(22):2826-2827
Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee. 相似文献
32.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
33.
Correa NM Zorzan DH D'Anteo L Lasta E Chiarini M Cerichelli G 《The Journal of organic chemistry》2004,69(24):8231-8238
Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface. 相似文献
34.
The synthesis and structure analysis of the unknown 1H-imidazo[1,2-a]imidazole ( 1 ) is described. The preparation involves alkylation of 2-aminoimidazole with bromoacetaldehyde diethyl acetal and subsequent hydrolysis and cyclization with hydrochloric acid. The structure was characterized by mass spectrometry and by 1H-, 15N- and 13C-nmr of 1 and by 1H-nmr of its 1-benzyl derivative 8 . An independent synthesis of 8 was accomplished via cyclization of 2-(N-dichloroethyl-N-benzyl)aminoimidazole ( 11 ). 相似文献
35.
The results of Fenske-Hall molecular orbital calculations are reported for the trigonal prismatic complexes Mo(S(2)C(2)H(2))(3) and Mo(S(2)C(6)H(4))(3). Both complexes exhibit a bend of the S-C-C-S ligand plane away from the S-Mo-S plane. A series of calculations which systematically follow the changes in electronic structure as the bend angle alpha is varied between 0 and 30 degrees indicates that the bend can be attributed to a second order Jahn-Teller distortion. The driving force for this distortion, which allows mixing between a set of ligand pi orbitals and the metal d(z)()()2 orbital, should be greatest for d(0) systems. In these systems the bent geometry leads to the stabilization of the doubly occupied HOMO. The driving force for ligand bending should be lower in systems having more or fewer electrons (e.g. Re(S(2)C(2)Ph(2))(3) or V(S(2)C(2)Ph(2))(3), respectively). While the steric bulk of the dithiolate ligands in the latter complexes may also influence the degree of ligand bending, this is probably a secondary effect. 相似文献
36.
Depecker G Patino N Di Giorgio C Terreux R Cabrol-Bass D Bailly C Aubertin AM Condom R 《Organic & biomolecular chemistry》2004,2(1):74-79
A cyclic molecule including a hexameric PNA sequence has been designed and synthesized in order to target the TAR RNA loop of HIV-1 through the formation of a "kissing complex". For comparison, its linear analogue has also been investigated. The synthesis of the cyclic and linear PNA has been accomplished following a liquid-phase strategy using mixed PNA and fully N-protected (aminoethylglycinamide) fragments. The interactions of this cyclic PNA and its linear analogue with TAR RNA have been studied and the results indicate clearly that no interaction occurs between the cyclic antisense PNA and TAR RNA, whereas a tenuous interaction has been detected with its linear PNA analogue. 相似文献
37.
Mario Giuffrida Pietro Maravigna Giorgio Montaudo Emo Chiellini 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1643-1656
Some bipolyesters consisting of 1,2-propene glycol residue (P) and symmetric aromatic diacid residue constituted by two p-oxybenzoyl groups coupled by a terephthaloyl (HTH), phthaloyl (HOH) and isophthaloyl (HIH) group, and a nonsymmetric diacid residue constituted by a p-oxybenzoyl and a terephthaloyl group (HT), have been investigated by direct pyrolysis–mass spectrometry. The results show that intramolecular exchange reactions occurring at the pyrolysis stage cause a reorganization of the copolymer sequences. Sequential bipolyesters I–IV are ideal materials for the investigation of the extent of thermal reorganization induced in the bipolymer sequences by the pyrolytic process. 相似文献
38.
Cesarino Balsamini Gilberto Spadoni Annalida Bedini Giorgio Tarzia Maurizio Lanfranchi Maria Angela Pellinghelli 《Journal of heterocyclic chemistry》1992,29(6):1593-1598
The alkyl N-(diphenylmethylene)-α,β-dehydroamino acids 1 have been submitted to 1,3-dipolar cycloadditions with nitrile oxides. The reactivity of these compounds depends on the type and on the stereochemistry of the β-substituents. With the unsubstituted terms 1a,b the reaction occurs on the C,C double bond, providing a good method for the synthesis of the 4,5-dihydroisoxazole derivatives 3a,b,c and for the gem-functionalized 4,5-dihydroisoxazoles amino carboxylic ester 5. The β-substituted compounds 1c,d,e , inert to 1,1-dimethylethylnitrile oxide, undergo the reaction to the N,C double bond, thus giving with 2a,b the 4,5-dihydro-1,2,4-oxadiazole derivatives 4. All the reactions occur with high site- and regioselectivity. 相似文献
39.
2-Arylidene-3-oxo-2,3,4,5,6,7-hexahydrobenzo[b]furans 2 react with hydrazine hydrate to afford 5,6,7,8-tetrahydro-4-cinnolones. By methylation, these compounds gave the corresponding N-1 and N-2 methyl derivatives. The mesoionic compounds are obtained, accompanied by 3-arylacetyl-4,5,6,7-tetrahydroindazoles upon reaction of 2 with methylhydrazine. 相似文献
40.
Giorgio Favini Demetrio Pitea Manuela Sottocornola Roberto Todeschini 《Journal of Molecular Structure》1982,87(1):53-64
The conformational geometries and possible interconversion paths for some oxa derivatives of bicyclo[5.1.0] octane have been studied by the molecular mechanics method. The theoretical results are compared with the experimental data for the molecular geometry of bicyclo[5.1.0] octane and 3,5,8-trioxabicyclo[5.1.0] octane, the free energy of activation for cycloheptene epoxide and 3,5-dioxabicyclo[5.1.0] octane, the dipole moments and molar Kerr constants in solution for cycloheptene epoxide, 3,5-dioxa- and 3,5,8-trioxabicyclo[5.1.0] octane. 相似文献