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11.
Tsugikazu Tomono Etsuo Hasegawa Eishun Tsuchida 《Journal of polymer science. Part A, Polymer chemistry》1974,12(5):953-965
Active hydrogen compounds such as hydroquinone (HQ), cyclohexanone (CH), acetophenone (AP), and 4,4′-methylene bis-N-methylaniline (MNA) polymerized with formaldehyde (F) and secondary diamines to produce Mannich base polyamine polymers. The HQ-containing polymers were oxidized to benzoquinone (BQ)-containing polymers and their redox properties were investigated in the desulfurization of hydrogen sulfide. 相似文献
12.
13.
The SCCC MO method has been used to calculate the electronic structure and spectrum of Mo(CN)
8
4–
and Mo(CN)
8
3–
ions of a D
4d
symmetry. All metal-ligand and ligand-ligand interactions and all overlap integrals (over products of HF atomic orbitals) have been included within the SCCC MO scheme. Basing on these calculations a new assignment of some absorption bands is proposed. The overall agreement between the calculated and observed electronic spectrum is satisfactory.
The authors are grateful to Prof. W. Jakób, Dr. Z. Stasicka and Dr. A. Samotus for many interesting discussions, to Prof. J. Chojnacki for providing us with new X-ray results before publication and to Dr. A. J. Sadlej for a help in dealing with the computer. 相似文献
Zusammenfassung Elektronenstruktur und Spektrum der [Mo(CN)8]–4- und [Mo(CN)8]–3-Ionen in D 4d -Symmetrie wurden mit der SCCC-MO-Methode berechnet. Alle Metall-Ligand- und Ligand-Ligand-Wechsel-wirkungen und Überlappungsintegrale wurden berücksichtigt. Die Bandenzuordnung wurde neu vorgenommen. Die Übereinstimmung der berechneten und gemessenen Spektren ist befriedigend.
Résumé Application à Mo(CN) 8 4– et Mo(CN) 8 3– de la méthode SCCC MO basée sur des orbitales atomiques HF approchées, en tenant compte du recouvrement et de toutes les interactions ligand-ligand. Dans la partie I on discute le cas de la symétrie D 4d . L'accord global avec l'expérience est satisfaisant en ce qui concerne les spectres. On montre aussi que toutes les attributions antérieures basées sur la théorie du champ cristallin semblent inadéquates.
The authors are grateful to Prof. W. Jakób, Dr. Z. Stasicka and Dr. A. Samotus for many interesting discussions, to Prof. J. Chojnacki for providing us with new X-ray results before publication and to Dr. A. J. Sadlej for a help in dealing with the computer. 相似文献
14.
This paper is concerned with the comparison between mechanical properties of polymer composite system and those of each individual constituent. The comparison is mainly performed with respect to the viscoelastic Young's modulus and the relaxation Young's modulus. These mechanical constants may be obtained from the correspondence principle by applying the Laplace transform to the constitutive equation. The calculated results exhibit that the mechanical property of polymer composite system strongly depends on that of matrix with respect to frequency- and time-dependences. That is, as for the vibration and dynamic response in the steady state, the frequency-dependence of peak position about imaginary part of dynamic modulus of composite system is similar to that of matrix, while the magnitude of dynamic modulus depends on volume fraction of dispersed particles to total volume. As for the stress relaxation, the time-dependence of the relaxation Young's modulus of composite system resemble that of matrix each other, while the magnitude depends on the volume fraction of dispersed particles to total volume. This is due to the calculating condition that particle is assumed to be very rigid in comparison with matrix in this paper. 相似文献
15.
Go Takikawa 《Tetrahedron letters》2006,47(37):6509-6511
Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl β,β-difluoro-α-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl β-substituted-β,β-difluoropyruvate in good yields. 相似文献
16.
T Kawaguchi T Hasegawa T Seki K Juni Y Morimoto A Miyakawa M Saneyoshi 《Chemical & pharmaceutical bulletin》1992,40(5):1338-1340
Five ester prodrugs of 2'3'-dideoxyinosine (DDI) were synthesized for the purpose of improving oral bioavailability. The prodrugs, acetate (C2-DDI), octanoate (C8-DDI), stearate (C18-DDI), benzoate (Bz-DDI), and hemisuccinate (Suc-DDI) were proved to quantitatively regenerate their parent drug by enzymatic hydrolysis. Though the chemical stability of the prodrugs under acidic conditions was not improved, their solubility in water was significantly decreased by esterification, except for Suc-DDI. Bioavailability was evaluated by oral administration to rats. Two hydrophobic prodrugs (C8-DDI and Bz-DDI) showed higher absolute bioavailability (23.5% and 31.0%, respectively) than did DDI (15.2%), though that of C2-DDI (11.5%) and Suc-DDI (4.5%) was poor. 相似文献
17.
PULSE RADIOLYSIS STUDIES IN MODEL LIPID SYSTEMS: FORMATION AND BEHAVIOR OF PEROXY RADICALS IN FATTY ACIDS 总被引:1,自引:0,他引:1
Abstract— Radiolytic formation and peroxidation of fatty acid radicals have been investigated by pulse radiolysis techniques in oleate, linoleate, linolenate and arachidonate systems. A strong absorption band at 280 nm associated with conjugated radicals, Rconj , formed in polyunsaturated fatty acid moieties has been used as a probe for kinetic processes occurring at doubly allylic sites in the hydrocarbon chain. Formation of Rconj by O- has been found to be more efficient than the less selective OH radical. Peroxidation of Rconj is shown to be somewhat slower, ( k R + O2 ˜ 3 × 108 M -1 s-1 ), than O2 reactions with radicals in oleate ( k R + O2 = 1 × 109 M -1 s-1 ). Peroxy radicals generated in these reactions disappear slowly by essentially second order processes (2 k RO1 ˜ 107 M -1 s-1 ). The superoxide radical, O- 2 , shows little if any reactivity towards 0.01 M linolenate or arachidonate over periods of 20 s. 相似文献
18.
Akihiko Kameyama Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(4):549-560
ABSTRACT The first total synthesis of tumor-associated glycolipid antigen, sialyl Lewis X is described. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (1) with methyl 2,3,4-tri-O-benzyl-1-thio-β-L-fuco-pyranoside (4) gave the α-glycoside (5), which was converted by reductive ring-opening of the benzylidene acetal into the glycosyl acceptor (6). Dimethyl(methylthio)sulfonium triflate-promoted coupling of 6 with methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside (7) afforded the desired hexasaccharide 8 in good yield. Compound 8 was converted into the α-trichloroacetimidate 11, via reductive removal of the benzyl groups, O-acetylation, removal of the 2-(trimethylsilyl)ethyl group, and treatment with trichloroacetonitrile, which, on coupling with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octa-decene-1,3-diol (12), gave the β-glycoside 13. Finally, 13 was transformed, via selective reduction of the azide group, condensation with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester group, into the title compound 16. 相似文献
19.
Hyejin Hyeon Ho Bong Hyun Boram Go Sung Chun Kim Yong-Hwan Jung Young-Min Ham 《Molecules (Basel, Switzerland)》2022,27(1)
Magnolia flower buds are a source of herbal medicines with various active compounds. In this study, differences in the distribution and abundance of major essential oils, phenolic acids, and primary metabolites between white flower buds of Magnolia heptapeta and violet flower buds of Magnolia denudata var. purpurascens were characterised. A multivariate analysis revealed clear separation between the white and violet flower buds with respect to primary and secondary metabolites closely related to metabolic systems. White flower buds contained large amounts of monoterpene hydrocarbons (MH), phenolic acids, aromatic amino acids, and monosaccharides, related to the production of isoprenes, as MH precursors, and the activity of MH synthase. However, concentrations of β-myrcene, a major MH compound, were higher in violet flower buds than in white flower buds, possibly due to higher threonine levels and low acidic conditions induced by comparatively low levels of some organic acids. Moreover, levels of stress-related metabolites, such as oxygenated monoterpenes, proline, and glutamic acid, were higher in violet flower buds than in white flower buds. Our results support the feasibility of metabolic profiling for the identification of phytochemical differences and improve our understanding of the correlated biological pathways for primary and secondary metabolites. 相似文献
20.
Shigeyoshí Nishino Yasuhiro Nagato Yoshihiro Hasegawa Hisanao Yamamoto Kazuo Kamaike Yoshiharu Ishido 《Heteroatom Chemistry》1991,2(1):187-196
Reagent systems of sodium– and tetrabutylammonium nitrite–acetic anhydride were proved to be extremely efficient for the deanilidation of nucleoside 3′-phosphoranilidates, whose reactions were rapid with the former and instant with the latter. It was further found that the reagent system is applicable to oligonucleotide synthesis provided that the exocyclic amino groups of 2′-deoxyadenosine, 2′-deoxyguanosine, and 2′-deoxycytidine were protected by succinylation. 相似文献