全文获取类型
收费全文 | 13012篇 |
免费 | 382篇 |
国内免费 | 49篇 |
专业分类
化学 | 8930篇 |
晶体学 | 57篇 |
力学 | 423篇 |
数学 | 1721篇 |
物理学 | 2312篇 |
出版年
2023年 | 97篇 |
2022年 | 128篇 |
2021年 | 182篇 |
2020年 | 199篇 |
2019年 | 228篇 |
2018年 | 194篇 |
2017年 | 151篇 |
2016年 | 336篇 |
2015年 | 343篇 |
2014年 | 365篇 |
2013年 | 702篇 |
2012年 | 864篇 |
2011年 | 890篇 |
2010年 | 537篇 |
2009年 | 416篇 |
2008年 | 825篇 |
2007年 | 788篇 |
2006年 | 728篇 |
2005年 | 677篇 |
2004年 | 632篇 |
2003年 | 570篇 |
2002年 | 458篇 |
2001年 | 221篇 |
2000年 | 228篇 |
1999年 | 132篇 |
1998年 | 153篇 |
1997年 | 130篇 |
1996年 | 169篇 |
1995年 | 97篇 |
1994年 | 97篇 |
1993年 | 91篇 |
1992年 | 92篇 |
1991年 | 67篇 |
1990年 | 77篇 |
1989年 | 61篇 |
1988年 | 65篇 |
1986年 | 54篇 |
1985年 | 83篇 |
1984年 | 106篇 |
1983年 | 67篇 |
1982年 | 79篇 |
1981年 | 82篇 |
1980年 | 88篇 |
1979年 | 65篇 |
1978年 | 79篇 |
1977年 | 83篇 |
1976年 | 89篇 |
1975年 | 66篇 |
1974年 | 43篇 |
1973年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Guilard R Gryko DT Canard G Barbe JM Koszarna B Brandès S Tasior M 《Organic letters》2002,4(25):4491-4494
[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure. 相似文献
102.
Phenyl-substituted ethenes react with iodine and xenon difluoride to provide difluorinated products. Iodofluoro intermediates react with xenon difluoride to produce transient iodine difluoride species that lose IF and F(-) and produce carbocations. 相似文献
103.
The identification of acyclic isoprenoid hydrocarbons in organic extracts of geological samples and particularly in petroleum deserves a great interest from the biological origin of the sedimentary organic matter and the understanding of geochemical processes. 相似文献
104.
The interaction of 4-hydroxy metabolites of estrogens with DNA leads to the formation of DNA adducts. These adducts are believed to play an important role in the incidence of breast and endometrial cancer. In order to be able to analyze these adducts in in vivo samples a method based upon the coupling of miniaturized liquid chromatography (LC) to electrospray tandem mass spectrometry (ES-MS/MS) was developed for the analysis of the adducts formed with 4-hydroxyequilenin. In vitro synthesized adducts obtained by the reaction of 4-hydroxyequilenin with the main 2'-deoxynucleosides were separated on a Hypersyl C(18) BDS nano-HPLC column (15 cm x 75 microm i.d.) at a flow-rate of 300 nl min(-1) using gradient elution with CH(3)OH--0.2% CH(3)COOH in H(2)O. The column was coupled, in combination with a column switching system, to a nano-electrospray interface. Analysis of the low- and high-resolution low-energy collision-activated dissociation product ion spectra of normal and deuterated adducts supported earlier data demonstrating equilenin to form different isomeric adducts, except with thymidine, for which no adducts were found. The nano-HPLC column-switching ES-MS system was tested for its sensitivity on a triple-quadrupole instrument, and detection limits down to 197 fg in the single reaction monitoring mode were obtained for semi-preparatively isolated equilenin--2'-deoxyguanosine adduct. 相似文献
105.
A commercial cation exchange resin Amberlite 200 has been modified after immersion in solutions of polyethyleneimine (PEI). The kinetic of fixation of the metallic ions have been determined. The modification of the surface of the resin deals with a change in the order of the affinities of the resins towards cations. The retention is the function of the formation and the stability of the complex. The conditions of modification (pH, PEI concentration and time of immersion) have been examined and the modification was confirmed by the determination of the exchange capacities, the distribution coefficient (P) and the selectivity factors (S). The obtained results revealed the effect of PEI on the exchange properties of the resin. The pH range selected (6-8) permitted a good adherence of PEI onto the resin surface. The quantity of the adsorbed PEI was increased by raising the initial concentration and the immersion period. The exchange capacity for copper ion passed from 2.6 mmol g−1, in the case of unmodified resin, to 3.9 mmol g−1 for the modified one. 相似文献
106.
Didier Bruyère 《Journal of organometallic chemistry》2003,687(2):466-472
The results of our preliminary investigations directed toward asymmetric catalysis of the cyclocarbopalladation of alkenes bearing a proximate nucleophile with organic halides (or triflates) are disclosed. A series of bidentate phosphine ligands were evaluated in intramolecular versions of this reaction using (E)-2-[7-(2-bromophenyl)-hept-4-enyl]-malonic acid dimethyl ester (1) and (Z)-2-[7-(2-trifluoromethanesulfonyloxy-phenyl)-hept-4-enyl]-malonic acid dimethyl ester (9) as model substrates. The highest enantioselective induction was obtained with aryl triflate 9 which produced the corresponding cyclopentylindane as a single diastereomer in 54% chemical yield and 43% ee by using PdCl2[S-(−)-TolBINAP] as chiral catalyst and K2CO3 as base. 相似文献
107.
Catalytic enantioselective synthesis of beta-amino acid derivatives is an area of intense interest, due to the importance of these compounds as components in pharmaceutical agents and peptidomimetics. In this report, we present the first catalytic enantioselective method for the synthesis of gamma-unsaturated beta-amino acids and their corresponding 1,3-amino alcohol derivatives. This methodology takes advantage of a highly enantioselective vinylzinc addition to an aldehyde to set chirality. The resulting allylic alcohols are then transformed into the corresponding allylic amines via Overman's [3,3]-sigmatropic imidate rearrangement, and subsequent one-pot deprotection-oxidation of a pendant oxygen leads to the gamma-unsaturated beta-amino acid derivatives of high enantiopurity. 相似文献
108.
Waterman PR Overhaus M Heckenkamp J Nigri GR Fungaloi PF Landis ME Kossodo SC LaMuraglia GM 《Photochemistry and photobiology》2002,75(1):46-50
Restenosis results from intimal hyperplasia and constrictive remodeling following cardiovascular interventions. Photodynamic therapy (PDT) has been shown to inhibit intimal hyperplasia in vivo by preventing neointimal repopulation of the treated vessel. This study was undertaken in an attempt to further dissect the mechanisms by which PDT acts on secreted and extracellular matrix proteins to inhibit migration of cultured human vascular cells. PDT of three-dimensional collagen gels inhibited invasive human smooth muscle cell (SMC) migration, whereas cell-derived matrix metalloproteinase production remained unaltered. Additionally, PDT generated cross-links in the collagen gels, a result substantiated in an ex vivo model whereby PDT rendered the treated vessels resistant to pepsin digestion and inhibited invasive migration of SMC and fibroblasts. These data support the premise that by inducing matrix protein cross-links, rendering the vessel resistant to degradation, in vivo PDT inhibits repopulation of the vessel and therefore intimal hyperplasia. 相似文献
109.
Studies of the preparation of 1,8-dihydroazocines and transannular cyclization of hydroazocines to produce functionalized pyrrolizidines are described. Results are presented which demonstrate that unsymmetrically substituted acetylenes bearing at least one electron withdrawing groups undergo efficient cycloaddition to 1 - β - styryl - 1,2 - dihydropyridine producing in a regio-selective fashion 3,4 - disubstituted - 1,8 - dihydroazocines. The dihydroazocines generated in this manner can be converted to 1 - formyl - Δ4,5 - epoxyazocines which undergo interesting rearrangement reactions to form pyrrolizidines when subjected to methoxide deformylation followed by acid treatment. In addition, 1,6,7,8 - tetrahydroazocines can be converted to pyrrolizidines under bromination conditions. The intriguing chemical process which occur under the conditions outlined above are described. 相似文献
110.
The sequences of 13 tryptic peptides of cow ?A-casein (accounting for about one half of the amino acid residues present in the protein) were established. The rennin sensitive linkage could be located in a large fragment (36 residues). ?-casein consists of a hydrophilic part (?-caseino-glycopeptide) and of a hydrophobic moiety (para-?-casein); in this latter, however, several quite hydrophilic sequences were characterized. Another feature of the ?-casein structure is the frequent duplication or triplication of certain amino acids (Pro-Pro; Phe-Phe; Gln-Gln-Gln-Asn-Glu-Glu-Glu; Pro-Pro-Lys-Lys-Asn-Gln-; etc. …). 相似文献