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991.
Boot CM Amagata T Tenney K Compton JE Pietraszkiewicz H Valeriote FA Crews P 《Tetrahedron》2007,63(39):9903-9914
The structures and biological properties of peptides produced by two genera of marine-derived fungi, an atypical Acremonium sp., and a Metarrhizium sp., were explored. The Acremonium strain was isolated from a marine sponge and has previously been shown by our group to produce peptides from the efrapeptin and RHM families. The isolation and structural elucidation of the new linear pentadecapeptides efrapeptins Eα (1) and H (2) and N-methylated octapeptides RHM3 (3) and RHM4 (4) were carried out through a combination of 1D and 2D NMR techniques and tandem MS. Additional known efrapeptins E, F, and G and the known syctalidamides A and B were also isolated. The absolute configurations of 1-4 are proposed to be the same as the original compound families. The marine sponge-derived Metarrhizium sp. was shown to produce destruxin cyclic depsipeptides including A, B, B2, desmethyl B, E chlorohydrin, and E2 chlorohydrin. Efrapeptins Eα (1), F, and G each displayed IC50s of 1.3 nM against H125 cells, and destruxin E2 chlorohydrin displayed an IC50 of 160 nM against HCT-116 cells. An initial therapeutic assessment suggested a continuous (168 h) exposure of at least 2 ng/mL, or a daily (24 h) exposure of at least 300 ng/mL for H125 cells treated with efrapeptin G, and a continuous (168 h) exposure of at least 190 ng/mL for HCT-116 cells treated with destruxin E2 chlorohydrin, will cause 90% tumor cell death in vitro. 相似文献
992.
Substituted bicyclic 2-pyridones, termed pilicides, prevent pilus assembly in uropathogenic Escherichia coli. Based on the bioactive methyl ester protected 2-pyridone 4, further functionalization at C-6 has yielded a set of new compounds, which have been evaluated for their ability to inhibit pilus formation in uropathogenic E. coli. The key intermediate in the synthesis was formylated 2-pyridone 5, which could be obtained via a Vilsmeier reaction. This versatile intermediate was converted into secondary and tertiary amines via reductive amination and could also be converted to other interesting functionalities using simple chemical transformations. 相似文献
993.
Xia X Busser W Strunk J Muhler M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(22):11063-11066
The adsorption of CO on polycrystalline TiO2 was investigated by static adsorption microcalorimetry. The initial differential heat of adsorption (qdiff,0) of CO on polycrystalline titania is 40 kJ/mol, and the standard adsorption entropy (Deltas0) is -104 J mol(-1) K(-1). These results are consistent with those derived from temperature-programmed desorption and FTIR results in the literature. The good reproducibility of the isotherms and the stable qdiff indicate that the lattice oxygen and hydroxyl groups on titania surface are basically not reactive to adsorbed CO. 相似文献
994.
Sardar R Park JW Shumaker-Parry JS 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11883-11889
A simple, inexpensive, single-step synthesis of gold and silver nanoparticles using poly(allylamine) (PAAm) as a reducing and stabilizing agent is reported. The synthetic process was carried out in aqueous solution, making the method versatile and environmentally friendly. The synthesized polymer-stabilized nanoparticles are stable in water without particle aggregation at room temperature for at least a month. We demonstrate successful ligand exchange on the polymer-stabilized gold nanoparticles (AuNPs) with a variety of omega-functionalized acid-, alcohol-, amine-, and biotin-terminated alkylthiols. The methodologies, including ligand exchange, also are applicable for the generation of finely dispersed silver nanoparticles. The synthesized gold and silver nanoparticles are characterized by UV-visible absorption spectroscopy and transmission electron microscopy (TEM). The different ligand-stabilized AuNPs are also analyzed by Fourier transform infrared (FTIR) spectroscopy. 相似文献
995.
Ratnayake R Lacey E Tennant S Gill JH Capon RJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(5):1610-1619
The kibdelones are a novel family of bioactive heterocyclic polyketides produced by a rare soil actinomycete, Kibdelosporangium sp. (MST-108465). Complete relative stereostructures were assigned to kibdelones A-C (1-3), kibdelone B rhamnoside (5), 13-oxokibdelone A (7), and 25-methoxy-24-oxokibdelone C (8) on the basis of detailed spectroscopic analysis and chemical interconversion, as well as mechanistic and biosynthetic considerations. Under mild conditions, kibdelones B (2) and C (3) undergo a facile equilibration to kibdelones A-C (1-3), while kibdelone B rhamnoside (5) equilibrates to a mixture of kibdelone A-C rhamnosides (4-6). A plausible mechanism for this equilibration is proposed and involves air oxidation, quinone/hydroquinone redox transformations, and a choreographed sequence of keto/enol tautomerizations that aromatize ring C via a quinone methide intermediate. Kibdelones exhibit potent and selective cytotoxicity against a panel of human tumor cell lines and display significant antibacterial and nematocidal activity. 相似文献
996.
Geske GD O'Neill JC Miller DM Mattmann ME Blackwell HE 《Journal of the American Chemical Society》2007,129(44):13613-13625
Bacteria use a language of low molecular weight ligands to assess their population densities in a process called quorum sensing. This chemical signaling process plays a pivotal role both in the pathogenesis of infectious disease and in beneficial symbioses. There is intense interest in the development of synthetic ligands that can intercept quorum-sensing signals and attenuate these divergent outcomes. Both broad-spectrum and species-selective modulators of quorum sensing hold significant value as small-molecule tools for fundamental studies of this complex cell-cell signaling process and for future biomedical and environmental applications. Here, we report the design and synthesis of focused collections of non-native N-acylated homoserine lactones and the systematic evaluation of these approximately 90 ligands across three Gram-negative bacterial species: the pathogens Agrobacterium tumefaciens and Pseudomonas aeruginosa; the model symbiont Vibrio fischeri. This study is the first to report and compare the activities of a set of ligands across multiple species and has revealed some of the most potent synthetic modulators of quorum sensing to date. Moreover, several of these ligands exhibit agonistic or antagonistic activity in all three species, while other ligands are only active in one or two species. Analysis of the screening data revealed that at least a subset of these ligands modulate quorum sensing via a partial agonism mechanism. We also demonstrate that selected ligands can either inhibit or promote the production of elastase B, a key virulence factor in wild-type P. aeruginosa, depending on their concentrations. Overall, this work provides broad insights into the molecular features required for small-molecule inhibition or activation of quorum sensing in Gram-negative bacteria. In addition, this study has supplied an expansive set of chemical tools for the further investigation of quorum-sensing pathways and responses. 相似文献
997.
998.
This paper presents methods for calculating confidence intervals for estimates of sampling uncertainty (s(samp)) and analytical uncertainty (s(anal)) using the chi-squared distribution. These uncertainty estimates are derived from application of the duplicate method, which recommends a minimum of eight duplicate samples. The methods are applied to two case studies--moisture in butter and nitrate in lettuce. Use of the recommended minimum of eight duplicate samples is justified for both case studies as the confidence intervals calculated using greater than eight duplicates did not show any appreciable reduction in width. It is considered that eight duplicates provide estimates of uncertainty that are both acceptably accurate and cost effective. 相似文献
999.
Holland JP Aigbirhio FI Betts HM Bonnitcha PD Burke P Christlieb M Churchill GC Cowley AR Dilworth JR Donnelly PS Green JC Peach JM Vasudevan SR Warren JE 《Inorganic chemistry》2007,46(2):465-485
Two new types of unsymmetrical bis(thiosemicarbazone) proligands and their neutral zinc(II) and copper(II) complexes have been synthesized. These bifunctional ligands both chelate the metal ions and provide pendent amino groups that can be readily functionalized with biologically active molecules. Functionalization has been demonstrated by the synthesis of three water-soluble glucose conjugates of the new zinc(II) bis(thiosemicarbazonato) complexes, and their copper(II) analogues have been prepared in aqueous solution via transmetalation. A range of techniques including NMR, electron paramagnetic resonance, cyclic voltammetry, high-performance liquid chromatography (HPLC), UV/vis, and fluorescence emission spectroscopy have been used to characterize the complexes. Four compounds, including two zinc(II) complexes, have been characterized by X-ray crystallography. The connectivity and conformation of the glucose conjugates have been assigned by NMR spectroscopy. Time-dependent density functional theory calculations have been used to assign the electronic transitions of the copper(II) bis(thiosemicarbazonato) chromophore. Two copper-64-radiolabeled complexes, including one glucose conjugate, have been prepared and characterized using radio-HPLC, and transmetalation is shown to be a viable method for radiolabeling compounds with copper radionuclides. Preliminary cell washout studies have been performed under normoxic conditions, and the uptake and intracellular distribution have been studied using confocal fluorescence microscopy. 相似文献
1000.
McDonald S Pringle JM Bishop AG Prenzler PD Robards K 《Journal of chromatography. A》2007,1153(1-2):203-213
Fulvic acids from an Australian floodplain river and billabong were isolated using DEAE and DAX-8 resins, and characterised with the use of size exclusion chromatography and solid-state CP-MAS (13)C NMR spectroscopy. Differences between the two resin isolates were evident. Fulvic acids isolated using DEAE-cellulose had higher apparent M(n) and M(w) values, while the DAX-8 resin showed a slight preference for aliphatic components. Fulvic acids from the river and billabong had the same functional groups present, however, the river fulvic acids had higher apparent M(n) (number average molecular weight) and M(w) values (weight average molecular weight), and were more polydisperse than the billabong fulvic acid. There were no significant changes in the characteristics of the fulvic acid isolated from the river at four sampling times: summer, autumn, winter and spring. In contrast, fulvic acids isolated from a billabong displayed seasonal variation in molecular weights. This work emphasizes the importance in ecological studies of isolation procedure for the operationally defined fulvic acids. 相似文献