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931.
This paper is concerned with the dynamics of water around a small globular protein. Dipolar second-rank relaxation time and diffusion properties of surface water were computed by extensive molecular dynamics simulations of lysozyme in water which lasted a total of 28 ns. Our results indicate that the rotational relaxation of water in the vicinity of lysozyme is 3-7 times slower than that in the bulk depending on how the hydration shell is defined in the calculation. We have also verified that the dynamics of water translational diffusion in the vicinity of lysozyme have retardations similar to rotational relaxation. This is a common assumption in nuclear magnetic relaxation dispersion (NMRD) studies to derive residence times. In contrast to bulk water dynamics, surface water is in a dispersive diffusion regime or subdiffusion. Very good agreement of dipolar second-rank relaxation time with NMRD estimates is obtained by using appropriate dimensions of the hydration shell. Although our computed second-rank dipolar retardations are independent of the water model, SPC/E describes more realistically the time scale of the water dynamics around lysozyme than does TIP3P. 相似文献
932.
Fabio de S. Dias Walter N. L. dos Santos Antônio C. S. Costa Bernhard Welz Maria Goreti R. Vale Sérgio L. C. Ferreira 《Mikrochimica acta》2007,158(3-4):321-326
A direct method is proposed for the determination of lead in naphtha and petroleum condensate by electrothermal atomic absorption
spectrometry (ET AAS) using palladium as a permanent modifier. The procedure includes the dilution of 3 mL of sample (naphtha
or petroleum condensate) to a final volume of 10 mL with xylene, and direct injection of 30 μL of this solution into the graphite
furnace. The optimization of the instrumental conditions was performed using multivariate techniques. Firstly, a 23 full factorial design was performed for preliminary evaluation of the factors: pyrolysis time, pyrolysis temperature and
atomization temperature. This experiment showed that in the studied levels only the factors pyrolysis time and atomization
temperature were significant. Then, a 32 full factorial design was performed for the determination of the critical conditions of these variables. The method allows
the determination of lead using the standard calibration technique with a calibration curve from 2.6 to 30 μg L−1 (correlation coefficient higher than 0.998). A limit of detection (3σ) of 0.8 μg L−1 and a characteristic mass of 35 pg were obtained in the presence of palladium as modifier. The precision expressed as relative
standard deviation (RSD) was 1.5 and 0.8% for lead concentrations of 3.0 and 30 μg L−1 (n = 10). Recovery studies demonstrate that lead can be determined in naphtha and petroleum condensate using calibration with
organic standard solutions. This method was applied for the determination of lead in three petroleum condensate and two naphtha
samples. The concentrations found for the petroleum condensate was between 2.7 and 5.7 μg L−1, while the naphtha samples did not contain any detectable lead. 相似文献
933.
We propose a model to investigate the dynamics of fashion traits purely driven by social interactions. We assume that people adapt their style to maximize social success, and we describe the interaction as a repeated group game in which the payoffs reflect the social norms dictated by fashion. On one hand, the tendency to imitate the trendy stereotypes opposed to the tendency to diverge from them to proclaim identity; on the other hand, the exploitation of sex appeal for dating success opposed to the moral principles of the society. These opposing forces promote diversity in fashion traits, as predicted by the modeling framework of adaptive dynamics. Our results link the so-called horizontal dynamics—the primary driver of fashion evolution, compared with the vertical dynamics accounting for interclass and economic drivers—to style variety. 相似文献
934.
Fabio Comin 《Synchrotron Radiation News》2016,29(6)
In 2004, the aim of the X-Tip European Project was to pursue the integration of scanning probe microscopy techniques into synchrotron radiation beamlines to provide new opportunities to both fields of microscopy and spectroscopy. Given the limited X-ray focusing capabilities at that time and the difficulty of alignment, the first emphasis was given to the possibility of exploring the morphology of the sample surface within the area illuminated by the X-rays, selecting an area of interest and, using the scanning tip, aligning it into the X-ray beam and extract by total electron yield spectroscopic information, with lateral resolutions ideally defined by tip dimensions. 相似文献
935.
936.
Characterization of crude oil biomarkers using comprehensive two‐dimensional gas chromatography coupled to tandem mass spectrometry
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Noroska Gabriela Salazar Mogollón Paloma Santana Prata Jadson Zeni dos Reis Eugênio Vaz dos Santos Neto Fabio Augusto 《Journal of separation science》2016,39(17):3384-3391
Oil samples from Recôncavo basin (NE Brazil), previously analyzed by traditional techniques such as gas chromatography coupled to tandem mass spectrometry, were evaluated using comprehensive two‐dimensional gas chromatography coupled to quadrupole mass spectrometry and comprehensive two‐dimensional gas chromatography coupled to tandem mass spectrometry along with simplified methods of samples preparation to evaluate the differences and advantages of these analytical techniques to better understand the development of the organic matter in this basin without altering the normal distribution of the compounds in the samples. As a result, the geochemical parameters calculated by comprehensive two‐dimensional gas chromatography coupled to tandem mass spectrometry described better the origin, maturity, and biodegradation of both samples probably by increased selectivity, resolution, and sensitivity inherent of the multidimensional technique. Additionally, the detection of the compounds such as, the C(14α‐) homo‐26‐nor‐17α‐hopane series, diamoretanes, nor‐spergulanes, C19–C26 A‐nor‐steranes and 4α‐methylsteranes resolved and detected by comprehensive two‐dimensional gas chromatography coupled to tandem mass spectrometry were key to classify and differentiate these lacustrine samples according to their maturity and deposition conditions. 相似文献
937.
In Fragnelli et al. (TOP 22:892–933, 2014), we considered a bankruptcy problem with the additional constraint that the estate has to be assigned in integer unities, allowing for non-integer claims. We dealt with the question of existence and uniqueness of a solution and proposed the “box method” that is strongly oriented towards the constrained equal losses solution; uniqueness may be guaranteed by introducing a ranking on the claimants. Here, we introduce a solution oriented towards the constrained equal awards solution and give three characterizations and a simple method for determining the solution. 相似文献
938.
Fabio Pasquali 《Logica Universalis》2016,10(4):407-418
939.
Denifl S Zappa F Mähr I Mauracher A Probst M Märk TD Scheier P 《Journal of the American Chemical Society》2008,130(15):5065-5071
The inelastic electron interaction (ionization/attachment) with chloroform embedded in helium droplets has been studied utilizing a two-sector field mass spectrometer. Positive mass spectra have been recorded at the electron energy of 70 eV and are compared with previous results in the gas phase and with other systems embedded in helium droplets. Moreover, the negative ion mass spectrum has been recorded at the electron energy of 1.5 eV. Both negative and positive mass spectra show that chloroform clusters are easily formed by embedding single molecules in the helium droplets. Moreover, for anions appearing in the mass spectrum, the ion yield has been determined as function of the electron energy. While no parent anion of chloroform can be observed in the gas phase, the present cluster environment allows the stabilization of the transient negative ion. The influence of the helium droplet upon the ionization or attachment process of the embedded chloroform is discussed. 相似文献
940.
Rosalba Sortino Marina Cunquero Gustavo Castro-Olvera Ricard Gelabert Miquel Moreno Fabio Riefolo Carlo Matera Noèlia Fernàndez-Castillo Luca Agnetta Michael Decker José M. Lluch Jordi Hernando Pablo Loza-Alvarez Pau Gorostiza 《Angewandte Chemie (International ed. in English)》2023,62(51):e202311181
To interrogate neural circuits and crack their codes, in vivo brain activity imaging must be combined with spatiotemporally precise stimulation in three dimensions using genetic or pharmacological specificity. This challenge requires deep penetration and focusing as provided by infrared light and multiphoton excitation, and has promoted two-photon photopharmacology and optogenetics. However, three-photon brain stimulation in vivo remains to be demonstrated. We report the regulation of neuronal activity in zebrafish larvae by three-photon excitation of a photoswitchable muscarinic agonist at 50 pM, a billion-fold lower concentration than used for uncaging, and with mid-infrared light of 1560 nm, the longest reported photoswitch wavelength. Robust, physiologically relevant photoresponses allow modulating brain activity in wild-type animals with spatiotemporal and pharmacological precision. Computational calculations predict that azobenzene-based ligands have high three-photon absorption cross-section and can be used directly with pulsed infrared light. The expansion of three-photon pharmacology will deeply impact basic neurobiology and neuromodulation phototherapies. 相似文献