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101.
Garcia Jarem R. Peres Laura O. Fernandes Mauro R. Gruber Jonas Nart Francisco C. 《Journal of Solid State Electrochemistry》2004,8(2):122-126
In this communication we describe the electrochemical synthesis of poly(2,5-dicyano-p-phenylenevinylene) (DCNPPV) polymer films on indium tin oxide substrates. We investigate the purity, morphology, absorption and emission properties of the film. The purity was checked by infrared spectroscopy. The film formed presented spectroscopic purity equivalent to the chemically prepared PPV that was dialyzed for one week. Scanning electron microscopy of the surface revealed a grain-like morphology. The absorption and emission spectra showed absorption and emission bands at 420 nm and 575 nm, respectively, with the absorption onset at 422 nm, which corresponds to an energy gap of 2.25 eV. The electrochemical determination of the energy gap gives 2.05 eV, thus quite close to the optical energy gap at the onset of absorption. The EA and IP were determined by electrochemical measurements and are 3.46 eV and 5.51 eV, respectively.
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Francisco C. NartEmail: |
102.
The various forms of chromatography are primarily determined by differences in the physical state of the mobile phases. The main chromatographic categories include gas chromatography (GC), liquid chromatography, and supercritical fluid chromatography. Adjusting a temperature and pressure will change the mobile phase from liquid to supercritical fluid to gas, with concomitant changes in their physical properties. In this paper, the technique transition-phase chromatography (TPC) is described. In TPC, different mobile phase conditions exist inside the column. This phase transformation within the column results in huge differences in density, solvating power, viscosity, diffusivity, and, as a consequence, in the chromatographic properties of the mobile phase. TPC experiments using capillary columns packed in our laboratory have shown that when the mobile phase is transformed from supercritical fluid to gas, high column efficiencies can be achieved. The transition from supercritical fluid to gas (also called solvating GC), a particular case of the TPC, is evaluated for the separation of complex real samples (environmental, food, and fuels). 相似文献
103.
Several catalyzed alkylation reactions of 9-methyladenine by a model [CPI, cyclopropa[c]pyrrolo[3,2-e]indol-4(5H)-one (1)] of duocarmycin anticancer drugs have been compared to the uncatalyzed reaction in gas phase and in water solvent bulk, using density functional theory at the B3LYP level with the 6-31+G(d,p) basis set and C-PCM solvation model. The effect on the CPI reactivity induced by water, formic and phosphoric acids (general acid catalysis), H3O+ (specific acid catalysis), sodium, and ammonium cation complexation (cationic catalysis) has been investigated. The calculations indicate that the specific acid catalysis and the catalysis induced by sodium cation complexation are strong in the gas phase, but solvation reduces them dramatically by electrostatic effects. The specific acid catalysis is still operative, but strongly reduced in water solution, where the reaction barrier is reduced by 8.6 kcal mol(-1) in comparison to the uncatalyzed reaction. The general acid catalysis induced by phosphoric acid (-7.3 kcal mol(-1)) and the catalysis induced by Na+ and NH4+ complexation become competitive, with a catalytic effect of -3.6 and -4.1 kcal mol(-1) in water, respectively. With the specific acid catalysis, the high acidity (low pK(a) value) of the conjugated acid of CPI (CPIH+), computed in water solution using both C-PCM (pK(a) = +2.6) and PCM-B3LYP/6-31+G(d,p) (pK(a) = +2.4) solvation models, suggests that the catalytic effects induced by NH4+ complexation could become more important than the specific acid catalysis and the general catalysis by H3PO4 under physiological conditions, due to concentration effects of the catalysts. 相似文献
104.
Bonini BF Comes-Franchini M Mazzanti G Ricci A Sala M 《The Journal of organic chemistry》1996,61(21):7242-7243
105.
Geisberger G Paulus S Carraro M Bonchio M Patzke GR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4619-4625
Chitosan and its derivates continue to attract considerable research interest as effective drug carriers with good biocompatibility and high cellular uptake rates. We used these versatile features to tap the considerable biomedical potential of polyoxometalates (POMs) through their encapsulation into a carboxymethyl chitosan (CMC) matrix. The nanocapsules were prepared by ionic gelification with Ca(2+); their size distribution ranges from 60 to 150 nm. Because [Co(4)(H(2)O)(2)(PW(9)O(34))(2)](10-) is well known for its manifold properties, such as antiviral activity, it was selected as a model POM. The resulting composites were characterised with a wide range of analytical methods, which pointed to quantitative encapsulation of intact POMs within the CMC matrix. We studied the biocompatibility of the POM/CMC nanocomposites on HeLa cells through MTT and proliferation assays. Even after prolonged incubation times at high concentrations, the composites did not display cytotoxicity, thereby drastically reducing the side effects of the pristine POMs. This opens up new avenues for designing novel inorganic drug prototypes from bioactive POMs. 相似文献
106.
107.
A novel approach of using a gold disc microelectrode to analyze sweat samples for copper ions by anodic square wave stripping voltammetry (SW stripping voltammetry) is described. Sweat was collected from the lower back of four subjects after physical exercise and the sample volume required for the determinations was 100 μL. Under the optimized conditions, the calibration plot was linear over the range 1-100 μmol L−1 Cu(II) with a limit of detection of 0.25 μmol L−1. The precision was evaluated by carrying out five replicate measurements in a 1 μmol L−1 Cu(II) solution and the standard deviation was found to be 1.5%. Measurements were performed by inserting the microelectrode into sweat drops and Cu(II) concentrations in the analyzed samples ranged from 0.9 to 28 μmol L−1. Values obtained by the proposed voltammetric method agreed well with those found using graphite furnace atomic absorption spectroscopy (GFAAS). 相似文献
108.
The dynamical behavior of a single K or Na alkali metal atom on the surface of a C(60) molecule is investigated via Car-Parrinello molecular dynamics simulations in a temperature range up to 300 K. These provide direct evidence for the heteroatom motion, postulated earlier in pioneering experiments, and show that an alkali metal atom can move both on the surface and radially outward from the surface, resulting in a dynamics ranging from diffusive to free orbital motion, on time-scales of up to a few picoseconds. 相似文献
109.
Gioacchini AM De Santi M Guescini M Brandi G Stocchi V 《Rapid communications in mass spectrometry : RCM》2010,24(23):3405-3412
Fossa cheese is an Italian hard cheese, ripened for up to 3 months in underground pits dug into tuffaceous rock. During this period, the cheese develops a unique flavour and intense and somewhat piquant aroma. Solid-phase microextraction gas chromatography/mass spectrometry (SPME-GC/MS) was utilized to characterize the volatile organic compounds (VOCs) of Fossa cheese. A total of 75 VOCs were separated and identified; in particular, the major class of compounds found in the cheeses ripened in the pits were the esters of fatty acids. Discriminant analysis of volatile profiles allowed us to distinguish between cheeses in different stages of seasoning (60-day-old cheese and cheese ripened an additional 90 days in and out of the pits). 相似文献
110.
Mauro L. Bonardi Flavia Groppi Simone Manenti Elisa Persico Luigi Gini Kamel Abbas Uwe Holzwarth Federica Simonelli Zeev B. Alfassi 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(1):1-7
Very high specific activity (AS) 186gRe could be produced by either proton or deuteron cyclotron irradiation on highly enriched 186W target in no-carrier-added (NCA) form, leading to a AS very close to the theoretical carrier free (CF) value of 6.88 GBq μg−1. Thick Target Yields (TTYs), obtained irradiating both thick metal W targets of natural isotopic composition and highly enriched powdered 186W targets, were measured at different particles energies taking into account high accuracy and precision. The evaluation of radionuclidic purities of 186gRe obtained activating highly enriched 186W by both p and d were also carried out and accurately compared. The thin-target excitation functions for all Re (A = 181, 182, 183, 184, 186 and their metastable levels), and W and Ta coproduced radionuclides will be presented elsewhere in deep details. 相似文献