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61.
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63.
The title total synthesis was achieved by employing deconjugative asymmetric α-sulfenylation of the chiral 3-(α,β,γ,δ-unsaturated acyl)oxazolidin-2-one with a 3,3-dimethoxypropyl methanethiosulfonate as a key step. From the biological activity assay carried out using the title compounds, it appeared evident that in vitro antibacterial and mammalian type I FAS inhibitory activity can be cleanly separated by changing not only the substituent at the C3-position but also the absolute configuration at the C5-position, and that unnatural (S)-(−)-3-demethylthiolactomycin and its congeners might be usable as selective mammalian type I FAS inhibitors. 相似文献
64.
Acylglycerols (=Glycerides) from the Glandular Trichome Exudate on the Leaves of Paulownia tomentosa
Teigo Asai Noriyuki Hara Sawa Kobayashi Shiro Kohshima Yoshinori Fujimoto 《Helvetica chimica acta》2009,92(8):1473-1494
Chemical investigations of the glandular trichome exudates on the leaves of Paulownia tomentosa (Scrophulariaceae) led to the identification of the thirty acylglycerols (=glycerides) 1 – 30 , including five known ones ( 2, 3, 6, 9 , and 15 ) (Fig. 1). Spectroscopic analysis combined with GC/MS studies of the glycerides and the liberated fatty acids, in the form of trimethylsilyl ether derivatives and trimethylsilylated methyl esters, respectively, established that the constituents belonged to 1,3‐di‐O‐acetyl‐2‐O‐(fatty acyl)glycerols, 1‐O‐acetyl‐2‐O‐(fatty acyl)‐sn‐glycerols, and 2‐O‐(fatty acyl)glycerols, wherein the fatty acyl moiety was either an eicosanoyl or an octadecanoyl group bearing OH and/or AcO groups at the 3‐, 3,6‐, 3,7‐, 3,8‐, or 3,9‐positions. The 1‐O‐acetyl‐2‐O‐[(3R,6S)‐3‐(acetyloxy)‐6‐hydroxyeicosanoyl]‐sn‐glycerol ( 12 ; 20% of the total glycerides), 2‐O‐[(3R,8R)‐3,8‐bis(acetyloxy)eicosanoyl]glycerol ( 17 ; 14%), 2‐O‐[(3R,9R)‐3,9‐bis(acetyloxy)eicosanoyl]glycerol ( 18 ; 12%), and 2‐O‐[(3R)‐3‐(acetyloxy)eicosanoyl]glycerol ( 10 ; 12%) were relatively abundant constituents. The configurations of the stereogenic centers of the fatty acyl moieties were determined by 1H‐NMR analysis of the monoesters obtained from (R)‐ and (S)‐2‐(naphthalen‐2‐yl)‐2‐methoxyacetic acid ((R)‐ and (S)‐2NMA? OH and the hydroxy‐substituted fatty acid methyl esters (Fig. 2). The configuration at C(2) of the glycerol moiety of the 1‐O‐acetyl‐2‐O‐(fatty acyl)glycerols was determined to be (2S) by chemical conversion of, e.g., G‐2 (= 2 / 3 1 : 10) to (+)‐3‐O‐[tert‐butyl)diphenylsilyl]‐sn glycerol of known absolute configuration. 相似文献
65.
Miyashita T Baba M Shigeta S Mori K Shinozuka K 《Chemical & pharmaceutical bulletin》2003,51(6):630-634
A series of novel 10-thiaisoalloxazine derivatives bearing an alkoxymethyl or benzyloxymethyl moiety at the N-1 position has been synthesized through the bromination of 1-substituted-5-hydroxyuracils and subsequent condensation with aminobenzenethiol in a one-pot reaction. Contrary to the previous report, the formation of intermediary 5,6-diethoxy-5-hydroxy-5,6-dihydrouracil seems to be not the necessary factor for the formation of the thiaisoalloxazines, since the reaction proceeds in tetrahydrofuran (THF) or acetonitrile far more smoothly than in ethanol. The anti-human immunodeficiency virus (HIV)-1 activity of the resulted thiaisoalloxazine derivatives was evaluated in lymphocyte cells based on the inhibitory activity against the viral-induced cytopathic activity. Among the derivatives, compounds 6, 7, and 8 bearing an alkoxymethyl moiety at the N-1 position exhibited modest inhibitory activity towards the cytotopathic effect of HIV-1. 相似文献
66.
Masahiro Sekiya Takeshi Noro Toshikatsu Koga Shiro L. Saito 《Journal of computational chemistry》2010,31(3):497-499
Developed and reported are compact yet efficient correlating basis sets for the 57La and 89Ac atoms, missing in the literature. Good performance of these correlating sets is exemplified in molecular applications to diatomic oxides and fluorides. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
67.
Prof. Dr. Munetaka Kunishima Takae Ujigawa Yoshie Nagaoka Chiho Kawachi Dr. Kazuhito Hioki Dr. Motoo Shiro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15856-15867
The reaction of 2‐chloro‐4,6‐dimethoxy‐1,3,5‐triazine (CDMT) with various nitrogen‐containing compounds, particularly tertiary amines (tert‐amines), has been studied for the preparation of 2‐(4,6‐dimethoxy‐1,3,5‐triazinyl)trialkylammonium salts [DMT‐Am(s)]. DMT‐Ams derived from aliphatic tert‐amines exhibited activity for the dehydrocondensation between a carboxylic acid and an amine to form an amide in a model reaction. Based on a conformational analysis of DMT‐Ams and tert‐amines by NMR and X‐ray diffraction methods, we concluded that a β‐alkyl group maintained in a gauche relationship with the nitrogen lone pair of tert‐amines significantly hinders the approach of CDMT to the nitrogen. Thus, trimethylamine and quinuclidine without such alkyl groups readily react with CDMT whereas triethylamine, possessing two or three such gauche β‐alkyl groups in the stable conformations, does not react at all. The theory of “gauche β‐alkyl group effect” proposed here provides useful guidelines for the preparation of DMT‐Ams possessing various tertiary amine moieties. An investigation of the dehydrocondensation activity of tert‐amines in a CDMT/tert‐amine system that involves in situ generation of DMT‐Am, showed that the gauche effect of the β‐alkyl group becomes quite pronounced; the yield of the amide decreases significantly with tert‐amines possessing an unavoidable gauche β‐alkyl group. Thus, the tert‐amine/CDMT systems are useful for judging whether tert‐amines can readily react with CDMT without isolation of DMT‐Ams. 相似文献
68.
Chiral‐Substrate‐Assisted Stereoselective Epoxidation Catalyzed by H2O2‐Dependent Cytochrome P450SPα
Dr. Takashi Fujishiro Dr. Osami Shoji Dr. Norifumi Kawakami Takahiro Watanabe Dr. Hiroshi Sugimoto Dr. Yoshitsugu Shiro Prof. Dr. Yoshihito Watanabe 《化学:亚洲杂志》2012,7(10):2286-2293
The stereoselective epoxidation of styrene was catalyzed by H2O2‐dependent cytochrome P450SPα in the presence of carboxylic acids as decoy molecules. The stereoselectivity of styrene oxide could be altered by the nature of the decoy molecules. In particular, the chirality at the α‐positions of the decoy molecules induced a clear difference in the chirality of the product: (R)‐ibuprofen enhanced the formation of (S)‐styrene oxide, whereas (S)‐ibuprofen preferentially afforded (R)‐styrene oxide. The crystal structure of an (R)‐ibuprofen‐bound cytochrome P450SPα (resolution 1.9 Å) revealed that the carboxylate group of (R)‐ibuprofen served as an acid–base catalyst to initiate the epoxidation. A docking simulation of the binding of styrene in the active site of the (R)‐ibuprofen‐bound form suggested that the orientation of the vinyl group of styrene in the active site agreed with the formation of (S)‐styrene oxide. 相似文献
69.
[structure: see text] Absolute stereochemistry of amphidinolides G (1) and H (2), potent cytotoxic 27- and 26-membered macrolides, respectively, isolated from a marine dinoflagellate Amphidinium sp., was determined by X-ray diffraction analysis, synthesis of a degradation product (3) of 2, and interconversion between 1 and 2. 相似文献
70.
A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water 总被引:1,自引:0,他引:1
Microcrystalline cellulose (avicel) was treated in supercritical waterusing batch-type and flow-type systems. The flow-type system made it possibletoshorten the heating, treating and cooling times, compared with the batch-typesystem. As a result, the flow-type system was able to liquefy avicel withoutproducing any supercritical water-insoluble residue. Although hydrolyzedproducts such as glucose and fructose, and pyrolyzed products such aslevoglucosan, 5-hydroxymethyl furfural, erythrose, methylglyoxal,glycolaldehydeand dihydroxyacetone were found in common from the water-soluble portiontreatedby both systems, the flow-type system gave a water-soluble portion with morehydrolyzed and less pyrolyzed products, together with water-solubleoligosaccharides consisting of cellobiose to cellododecaose and theirdecomposedproducts at their reducing end of glucose, such as[–glucopyranosyl]1–11 –levoglucosan,[–glucopyranosyl]1–11 –erythrose and[–glucopyranosyl]1–11 –glycolaldehyde. Inaddition, the precipitates of polysaccharides were recovered after 12h setting of the water-soluble portion. These results indicatedthat the flow-type system can hydrolyze cellulose with minimizing pyrolyzedproducts. On the other hand, the batch-type system resulted in a higher yieldof the pyrolyzed products due to the longer treatment, but a higher yield ofglucose due possibly to the higher pressure and concomitantly higher ionicproduct of water. Based on these lines of evidence, the process to increase theyield of the sugar is discussed under supercritical water treatment. 相似文献