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71.
Normen Szesni 《Inorganica chimica acta》2006,359(2):617-632
Bis(alkoxy)allenylidene complexes, [(CO)5MCCC(OR′)OR], as well as mono(alkoxy)allenylidene complexes, [(CO)5MCCC(OR′)Ph], of chromium and tungsten are accessible from propynones [HCCC(O)Ph] or propynoic acid esters [HCCC(O)OR; R = Et, (−)-menthyl, endo-bornyl] by the following reaction sequence: (a) deprotonation of the alkynes, (b) reaction with [(CO)5M-THF] (M = Cr, W), and (c) alkylation of the resulting alkynyl metallate, [(CO)5MCCC(O)R], with Meerwein salts. Vinylidene complexes, [(CO)5MCC(R′)C(O)OR], are formed as a by-product by Cβ-alkylation of the alkynyl metallate. Dimethylamine displaces one alkoxy substituent of the bis(alkoxy)allenylidene complexes to give dimethylamino(alkoxy)allenylidene complexes, [(CO)5MCCC(OR)NMe2]. The analogous reaction of dimethylamine with a mono(alkoxy)-substituted allenylidene complex affords the aminoallenylidene complex [(CO)5CrCCC(NMe2)Ph]. When the amine is used in large excess, the α,β-unsaturated aminocarbene complex [(CO)5CrC(NMe2)C(H)C(NMe2)Ph] is additionally formed by addition of the amine across the CαCβ-bond of the allenylidene ligand. The reaction of [(CO)5MCCC(OEt)2] with dimethyl ethylenediamine offers access to bis(amino)allenylidene complexes, in which Cγ is part of a five-membered heterocycle. Photolysis of bis(alkoxy)allenylidene complexes in the presence of triphenylphosphine yields tetracarbonyl- and tricarbonyl{bis(phosphine)}allenylidene complexes. Diethylaminopropyne inserts into the CβCγ bond of [(CO)5MCCC(OEt)OMethyl] to give alkenylallenylidene complexes. Subsequent acid-catalyzed intramolecular cyclization affords a pyranylidene complex. 相似文献
72.
The striking change in the circular dichroism (CD) of bradykinin (BK) occasioned by its interaction with sodium dodecyl sulfate (SDS) is evidently due in large part to a change in the conformation of the C-terminal tetrapeptide moiety of the hormone. The full change in CD is induced by the binding of two molecules of monomeric SDS per peptide molecule, the complex being aggregated. Formation of the 1:2 BK-SDS complex apparently proceeds via intermediates of stoichiometry 1:1 and 2:1. The cooperative nature of the interaction is attributed to the SDS-promoted aggregation of BK. Electrostatic interactions with the Arg residues appear important for the binding reaction per se. CD reveals that BK also interacts with acidic lipids which bear a net electrical charge (e.g., cerebroside sulfate and phosphatidyl inositol) but not with lipids bearing no net charge (e.g., cerebroside and phosphatidyl choline). The interactions are with particular mixed micelles of the lipid and the nonionic surfactant used for their solubilization, micellar size and structure being examined by surface tensiometry and electron microscopy. 相似文献
73.
Deepika Sharma Rupam Kapoor Ashok K. Bhatnagar 《World journal of microbiology & biotechnology》2008,24(3):395-400
Curculigo orchioides Gaertn. (family Hypoxidaceae) is an endangered anticarcinogenic and aphrodisiac herb, native of India. This study reports
the effect of three arbuscular mycorrhizal (AM) fungal inocula on post-transplanting performance of ‘in vitro’ raised C. orchioides plantlets. The three AM fungal inocula consisted of two monospecific cultures of Glomus geosporum and G. microcarpum and one crude consortium of AM fungal spores isolated from rhizosphere soil of C. orchioides growing in natural habitat. Complete plantlets of C. orchioides were raised by direct organogenesis of leaf explants on half strength Murashige and Skoog’s medium devoid of any growth hormone.
C. orchioides plantlets responded significantly different to all three mycorrhizal treatments. Mycorrhization enhanced the survival rate
of C. orchioides plantlets to 100%. The inoculated plantlets fared significantly better than the uninoculated ones in terms of biomass production
and number of leaves and roots per plant. Mycorrhizal plantlets exhibited higher concentrations of photosynthetic pigments
as well as minerals P, Mg, Cu, Zn, Mn and Fe in both shoots and roots. Among the three inocula tested, plantlets inoculated
with the mixed consortium of AM fungi consistently performed better in terms of the parameters evaluated. The study suggests
use of mixed consortium of AM fungi over monospecific cultures for the sustainable cultivation and conservation of endangered
medicinal plant: Curculigo orchioides. 相似文献
74.
Casini A Hartinger C Gabbiani C Mini E Dyson PJ Keppler BK Messori L 《Journal of inorganic biochemistry》2008,102(3):564-575
Gold(III) compounds constitute an emerging class of biologically active substances, of special interest as potential anticancer agents. During the past decade a number of structurally diverse gold(III) complexes were reported to be acceptably stable under physiological-like conditions and to manifest very promising cytotoxic effects against selected human tumour cell lines, making them good candidates as anti-tumour drugs. Some representative examples will be described in detail. There is considerable interest in understanding the precise biochemical mechanisms of these novel cytotoxic agents. Based on experimental evidence collected so far we hypothesize that these metallodrugs, at variance with classical platinum(II) drugs, produce in most cases their growth inhibition effects through a variety of "DNA-independent" mechanisms. Notably, strong inhibition of the selenoenzyme thioredoxin reductase and associated disregulation of mitochondrial functions were clearly documented in some selected cases, thus providing a solid biochemical basis for the pronounced proapoptotic effects. These observations led us to investigate in detail the reactions of gold(III) compounds with a few model proteins in order to gain molecular-level information on the possible interaction modes with possible protein targets. Valuable insight on the formation and the nature of gold-protein adducts was gained through ESI MS (electrospray ionization mass spectrometry) and spectrophotometric studies of appropriate model systems as it is exemplified here by the reactions of two representative gold(III) compounds with cytochrome c and ubiquitin. The mechanistic relevance of gold(III)-induced oxidative protein damage and of direct gold coordination to protein sidechains is specifically assessed. Perspectives for the future of this topics are briefly outlined. 相似文献
75.
James M. Caffrey Harry A. Smith John C. Schmitz Andrea Merchant Earl Frieden 《Biological trace element research》1990,25(1):11-19
The hemolysis of red blood cells (RBC) induced by Cu(II) is modified by ceruloplasmin (Cp) and albumin. The time course of hemolysis for rabbit RBC by Cu(II) consisted of two parts, an induction period followed by a catastrophic lysis period. The induction period decreased and the lysis rate increased with increasing Cu(II) concentration. Cp or albumin, modified Cu(II) induced hemolysis, by increasing the duration of the induction period and decreasing the overall rate of hemolysis of RBC. The catastrophic lysis period coincided with a sharp increase in the formation of metHb within the cell and in a rapid uptake of Cu(II). The presence of Cp led to an increase in the induction period prior to the rapid increase in metHb formation and in Cu(II) uptake. Porcine Cp was prepared with either two or three nonprosthetic copper binding sites (sites where Cu(II) is easily removed by passing over Chelex-100). Cp with three nonprosthetic binding sites gave more protection than Cp with two. Likewise, albumin can be prepared with three and five nonprosthetic copper binding sites. The albumin with five sites gave more protection than the albumin with three sites. 相似文献
76.
77.
78.
Maurizio Zandomeneghi 《Chirality》1995,7(6):446-451
Complexation of 2-(3′-benzoylphenyl)propionic acid (ketoprofen), 1 , to bovine serum albumin (BSA) results in an intense negative circular dichroism in the ketonic n → π* band of the benzoylphenyl moiety. This high CD contrasts with the weak CD of 1 -enantiomers dissolved in common solvents. Furthermore, a number of chiral and achiral molecules containing the benzophenone moiety are easily complexed to BSA: all these complexes show an intense CD at the same transition. To account for the observed CD intensities of the above molecules, it appears that BSA complexation markedly shifts the equilibrium between strongly asymmetric, antipodic conformers. Dissymmetry of these conformers is connected to the instability of a structure with phenyl rings coplanar to the carbonyl chromophore, as also indicated by molecular mechanics calculations. The magnification of the Cotton effects of the 1 -antipodes, due to the protein, can be used to measure the optical purity of 1 -samples with excellent precision. In contrast with BSA, human SA is unable to recognize the chirality of 1 -antipodes; oleic acid cocomplexation modifies this fact as well as other features of the binding. © 1995 Wiley-Liss, Inc. 相似文献
79.
I. Hoeschele 《TAG. Theoretical and applied genetics. Theoretische und angewandte Genetik》1988,76(2):311-319
Summary Statistical techniques for detection of major loci and for making inferences about major locus parameters such as genotypic frequencies, effects and gene action from field-collected data are presented. In field data, major genotypic effects are likely to be masked by a large number of environmental differences in addition to additive and nonadditive polygenic effects. A graphical technique and a procedure for discriminating among genetic hypotheses based on a mixed model accounting for all these factors are proposed. The methods are illustrated by using simulated data.Journal Paper No. J-12733 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Project No. 1901 相似文献
80.
Raj Kumar Koiri Surendra Kumar Trigun Santosh Kumar Dubey Santosh Singh Lallan Mishra 《Biometals》2008,21(2):117-126
Metal complex–protein interaction is an evolving concept for determining cellular targets of metallodrugs. Lacatate dehydrogenase
(LDH) is critically implicated in tumor growth and therefore, considered to be an important target protein for anti-tumor
metal complexes. Due to efficient biocompatibility of copper (Cu2+) and zinc (Zn2+), we synthesized CubpyAc2 · H2O (Cu-bpy) and ZnbpyAc2 · H2O (Zn-bpy; where bpy = 2,2′ bipyridine, Ac = CH3COO−) complexes and evaluated their interaction with and modulation of LDH in mouse tissues. The increasing concentration of both
the complexes showed a significant shift in UV–Vis spectra of LDH. The binding constant data (Kc = 1 × 103 M−1 for Cu-bpy and 7 × 106 M−1 for Zn-bpy) suggested that Zn-bpy-LDH interaction is stronger than that of Cu-bpy-LDH. LDH modulating potential of the complexes
were monitored by perfusing the mice tissues with non-toxic doses of Cu-bpy and Zn-bpy followed by activity measurement and
analysis of LDH isozymes on non-denaturing polyacrylamide gel electrophoresis (PAGE). As compared to the control sets, Cu-bpy
caused a significant decline (P < 0.05–0.001) in the activity of LDH in all the tissues studied. However, Zn-bpy showed inhibition of LDH only in liver (P < 0.01), kidney (P < 0.001) and heart (P < 0.01), but with no effect in spleen, brain and skeletal muscle tissues. PAGE analysis suggested that all the five LDH isozymes
are equally sensitive to both the complexes in the respective tissues. The results suggest that Cu- and Zn-bpy are able to
interact with and inhibit LDH, a tumor growth supportive target protein at tissue level. 相似文献