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101.
Rheological models of complex fluids with a physically restricted microstructure are analyzed to obtain general classes of
dynamical evolution equations for these materials. These classes insure that the appropriate mathematical constraints, associated
with each type of physical restriction, are consistently incorporated into the corresponding model development. Describing
the microstructure of the complex fluid with a second-rank tensor variable, a general class of dynamical evolution equations
is derived for three physically meaningful constraints associated with constancy of the invariants of this microstructural
tensor. The physical rationale for each of these constraints is discussed, and a corresponding set of constrained dynamical
evolution equations is derived in general terms.
Abdellatif Ait-Kadi passed away suddenly during the course of this research. The surviving authors express their gratitude
to Abdellatif for our many hours of productive work and companionship. 相似文献
102.
Dr. Yongjun Zhou Prof. Patrícia Prediger Prof. Luiz Carlos Dias Dr. Annabel C. Murphy Prof. Peter F. Leadlay 《Angewandte Chemie (International ed. in English)》2015,54(17):5232-5235
Elaiophylin is an unusual C2‐symmetric antibiotic macrodiolide produced on a bacterial modular polyketide synthase assembly line. To probe the mechanism and selectivity of diolide formation, we sought to reconstitute ring formation in vitro by using a non‐natural substrate. Incubation of recombinant elaiophylin thioesterase/cyclase with a synthetic pentaketide analogue of the presumed monomeric polyketide precursor of elaiophylin, specifically its N‐acetylcysteamine thioester, produced a novel 16‐membered C2‐symmetric macrodiolide. A linear dimeric thioester is an intermediate in ring formation, which indicates iterative use of the thioesterase active site in ligation and subsequent cyclization. Furthermore, the elaiophylin thioesterase acts on a mixture of pentaketide and tetraketide thioesters to give both the symmetric decaketide diolide and the novel asymmetric hybrid nonaketide diolide. Such thioesterases have potential as tools for the in vitro construction of novel diolides. 相似文献
103.
Influence of the Solvent on the “Casting” Methodology for MWCNT‐Modified Glassy Carbon and Platinum Electrodes 下载免费PDF全文
Ana Carolina Ângelo Dorim Herbert Aleixo Edilton de Souza Barcellos Leonardo Luiz Okumura 《Electroanalysis》2015,27(11):2663-2669
The choice of electrode material and surface preparation method are usually dictated by the suitability of the electrode to observe an electrochemical parameter, such as heterogeneous electron transfer rate, surface coverage, or redox potential. Thus, the glassy carbon (GC) and platinum (Pt) electrodes were modified with multiwalled carbon nanotubes (MWCNT) by direct “casting” modification using nine different aliquots of solvents. After drying at room temperature, the modified electrode showed distinct redox peaks corresponding to ferrocyanide oxidation/reduction. Using chemometrics, the cyclic voltammograms with higher current intensity were obtained for those in which ethanol, water and acetone as dispersing agents were used for GCE and dimethylformamide, water and acetone for Pt electrode modification. 相似文献
104.
Formulation of Aluminum Chloride Phthalocyanine in Pluronic™ P‐123 and F‐127 Block Copolymer Micelles: Photophysical properties and Photodynamic Inactivation of Microorganisms 下载免费PDF全文
Bruno Henrique Vilsinski Adriana Passarella Gerola Junior Adalberto Enumo Katieli da Silva Souza Campanholi Paulo Cesar de Souza Pereira Gustavo Braga Noboru Hioka Elza Kimura André Luiz Tessaro Wilker Caetano 《Photochemistry and photobiology》2015,91(3):518-525
Aluminum Chloride Phthalocyanine (AlPcCl) can be used as a photosensitizer (PS) for Photodynamic Inactivation of Microorganisms (PDI). The AlPcCl showed favorable characteristics for PDI due to high quantum yield of singlet oxygen (ΦΔ) and photostability. Physicochemical properties and photodynamic inactivation of AlPcCl incorporated in polymeric micelles of tri‐block copolymer (P‐123 and F‐127) against microorganisms Staphylococcus aureus, Escherichia coli and Candida albicans were investigated in this work. Previously, it was observed that the AlPcCl undergoes self‐aggregation in F‐127, while in P‐123 the PS is in a monomeric form suitable for PDI. Due to the self‐aggregation of AlPcCl in F‐127, this formulation did not show any effect on these microorganisms. On the other hand, AlPcCl formulated in P‐123 was effective against S. aureus and C. albicans and the death of microorganisms was dependent on the PS concentration and illumination time. Additionally, it was found that the values of PS concentration and illumination time to eradicate 90% of the initial population of microorganisms (IC90 and D90, respectively) were small for the AlPcCl in P‐123, showing the effectiveness of this formulation for PDI. 相似文献
105.
Dominik Grtner Andr Luiz Stein Sabine Grupe Johannes Arp Axel JacobivonWangelin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(36):10691-10695
Stable C O linkages are generally unreactive in cross‐coupling reactions which mostly employ more electrophilic halides or activated esters (triflates, tosylates). Acetates are cheap and easily accessible electrophiles but have not been used in cross‐couplings because the strong C O bond and high propensity to engage in unwanted acetylation and deprotonation. Reported herein is a selective iron‐catalyzed cross‐coupling of diverse alkenyl acetates, and it operates under mild reaction conditions (0 °C, 2 h) with a ligand‐free catalyst (1–2 mol %). 相似文献
106.
Gabriela Furlan Giordano Luis Carlos Silveira Vieira Angelo Luiz Gobbi Renato Sousa Lima Lauro Tatsuo Kubota 《Analytica chimica acta》2015
An integrated platform was developed for point-of-use determination of ethanol in sugar cane fermentation broths. Such analysis is important because ethanol reduces its fuel production efficiency by altering the alcoholic fermentation step when in excess. The custom-designed platform integrates gas diffusion separation with voltammetric detection in a single analysis module. The detector relied on a Ni(OH)2-modified electrode. It was stabilized by uniformly depositing cobalt and cadmium hydroxides as shown by XPS measurements. Such tests were in accordance with the hypothesis related to stabilization of the Ni(OH)2 structure by insertion of Co2+ and Cd2+ ions in this structure. The separation step, in turn, was based on a hydrophobic PTFE membrane, which separates the sample from receptor solution (electrolyte) where the electrodes were placed. Parameters of limit of detection and analytical sensitivity were estimated to be 0.2% v/v and 2.90 μA % (v/v)−1, respectively. Samples of fermentation broth were analyzed by both standard addition method and direct interpolation in saline medium based-analytical curve. In this case, the saline solution exhibited ionic strength similar to those of the samples intended to surpass the tonometry colligative effect of the samples over analyte concentration data by attributing the reduction in quantity of diffused ethanol vapor majorly to the electrolyte. The approach of analytical curve provided rapid, simple and accurate analysis, thus contributing for deployment of point-of-use technologies. All of the results were accurate with respect to those obtained by FTIR method at 95% confidence level. 相似文献
107.
108.
Neyva M. L. Romeiro Rigoberto G. S. Castro Sandra M. C. Malta Luiz Landau 《Transport in Porous Media》2007,70(1):1-10
We study a one-dimensional multi-species system of dispersive-advective contaminant transport equations coupled by nonlinear
biological (kinetic reactions) and physical (adsorption) processes. To deal with the nonlinearities and the coupling, and
to avoid additional computational costs, we propose a linearization technique based on first-order Taylor’s series expansions.
A stabilized finite element in space, combined with an Euler implicit finite difference discretization in time, is used to
approximate the dispersive-advective transport problem. Three computational tests are performed with different boundary conditions,
retardation factors and kinetic parameters for a nonlinear reactive multi-species transport model. The proposed methodology
is shown to be accurate and decrease computational costs in the numerical implementation of nonlinear reactive transport problems. 相似文献
109.
110.
The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations, HPS presented a smaller effect at concentrations above 1.5mM. At 10mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. 相似文献