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421.
Visible and Near Infrared (Vis–NIR) Spectroscopy is a powerful non destructive analytical method used to analyze major compounds in bulk materials and products and requiring no sample preparation. It is widely used in routine analysis and also in-line in industries, in-vivo with biomedical applications or in-field for agricultural and environmental applications. However, highly scattering samples subvert Beer–Lambert law's linear relationship between spectral absorbance and the concentrations. Instead of spectral pre-processing, which is commonly used by Vis–NIR spectroscopists to mitigate the scattering effect, we put forward an optical method, based on Polarized Light Spectroscopy to improve the absorbance signal measurement on highly scattering samples. This method selects part of the signal which is less impacted by scattering. The resulted signal is combined in the Absorption/Remission function defined in Dahm's Representative Layer Theory to compute an absorbance signal fulfilling Beer–Lambert's law, i.e. being linearly related to concentration of the chemicals composing the sample. The underpinning theories have been experimentally evaluated on scattering samples in liquid form and in powdered form. The method produced more accurate spectra and the Pearson's coefficient assessing the linearity between the absorbance spectra and the concentration of the added dye improved from 0.94 to 0.99 for liquid samples and 0.84–0.97 for powdered samples. 相似文献
422.
A new circular dichroism sensor for detecting Ni2+ and Co2+ was proposed for the first time using chiral chelating quantum dots. The detection principle was based on changing of circular dichroism signals of the chiral quantum dots when forming a chiral complex with Ni2+ or Co2+. l-Cysteine capped cadmium sulfide quantum dots (l-Cyst-CdS QDs) were proposed as a chiral probe. The CD spectrum of l-Cyst-CdS QDs was significantly changed in the presence of Ni2+ and Co2+. On the other hand, other studied cations did not alter the original CD spectrum. Moreover, when increasing the concentration of Ni2+ or Co2+, the intensity of the CD spectrum linearly increased as a function of concentration and could be useful for the quantitative analysis. The proposed CD sensor showed linear working concentration ranges of 10–60 μM and 4–80 μM with low detection limits of 7.33 μМ and 1.13 μM for the detection of Ni2+ and Co2+, respectively. Parameters possibly affected the detection sensitivity such as solution pH and incubation time were studied and optimized. The proposed sensor was applied to detect Ni2+ and Co2+ in real water samples, and the results agreed well with the analysis using the standard ICP-OES. 相似文献
423.
Kessarin Ngamdee Theerapong Puangmali Thawatchai Tuntulani Wittaya Ngeontae 《Analytica chimica acta》2015
A new chemical sensor based on the measuring of circular dichroism signal (CD) was fabricated from cysteamine capped cadmium sulfide quantum dots (Cys-CdS QDs). The chiral-thiol molecules, d-penicillamine (DPA) and l-penicillamine (LPA), were used to evaluate potentials of this sensor. Basically, DPA and LPA provide very low CD signals. However, the CD signals of DPA and LPA can be enhanced in the presence of Cys-CdS QDs. The CD spectra of DPA and LPA exhibited a mirror image profile. Parameters affecting the determination of DPA and LPA were thoroughly investigated in details. Under the optimized condition, the CD signals of DPA and LPA displayed a linear relationship with the concentrations of both enantiomers, ranging from 1 to 35 μM. Detection limits of this sensor were 0.49 and 0.74 μM for DPA and LPA, respectively. To demonstrate a potential application of this sensor, the proposed sensor was used to determine DPA and LPA in real urine samples. It was confirmed that the proposed detection technique was reliable and could be utilized in a broad range of applications. 相似文献
424.
425.
Unambiguous Determination of Protein Arginine Ionization States in Solution by NMR Spectroscopy 下载免费PDF全文
《Angewandte Chemie (International ed. in English)》2017,56(1):239-242
Because arginine residues in proteins are expected to be in their protonated form almost without exception, reports demonstrating that a protein arginine residue is charge‐neutral are rare and potentially controversial. Herein, we present a 13C‐detected NMR experiment for probing individual arginine residues in proteins notwithstanding the presence of chemical and conformational exchange effects. In the experiment, the 15Nη and 15Nϵ chemical shifts of an arginine head group are correlated with that of the directly attached 13Cζ. In the resulting spectrum, the number of protons in the arginine head group can be obtained directly from the 15N–1H scalar coupling splitting pattern. We applied this method to unambiguously determine the ionization state of the R52 side chain in the photoactive yellow protein from Halorhodospira halophila . Although only three Hη atoms were previously identified by neutron crystallography, we show that R52 is predominantly protonated in solution. 相似文献
426.
《化学:亚洲杂志》2017,12(9):949-953
Hyperpolarization is an emerging method that dramatically enhances NMR signal intensity. As a result of their increased sensitivity, hyperpolarized (HP) NMR molecular probes can be used to perform time‐resolved spectroscopy and imaging in vitro and in vivo. It is, however, challenging to design such probes de novo. Herein, the [1‐13C]α‐amino acid is reported as a scaffold structure to design HP 13C NMR molecular probes. The [1‐13C]α‐amino acid can be converted to various HP 13C chemical probes that show sufficient chemical shift change by altering the chemical state of the α nitrogen upon interaction with the target. Several previously reported HP probes could be explained by this design principle. To demonstrate the versatility of this approach, two α‐amino‐acid‐based HP 13C chemical probes, sensitive to pH and Ca2+ ion, were developed and used to detect targets. 相似文献
427.
用三维弹性力学方法研究任意边界条件圆板的轴对称稳定问题,利用H变换和Stockes变换,导出位移函数及其偏导数的一种新型双重极数式,并由数学弹性定理论的基本方程和边界条件建立的特征方程,求得最小临界载荷的精确解,文末以简支圆板为例进行数字计算,结果表明:在弹性失稳范围内,三维弹性力学方法求得的临界载荷略低于经典理论的结果,对于薄板的弹性稳定问题,经典板理论有足够的精度。 相似文献
428.
Ala Hasan 《Heat and Mass Transfer》2005,41(8):724-733
The thermal-hydraulic performance of five oval tubes is experimentally investigated and compared with that for a circular tube in a cross-flow of air. The range of Reynolds numbers ReD is approximately between 1,000 and 11,000. The nominal axis ratios R (major axis/minor axis) for three of the investigated oval tubes are 2, 3, and 4. Two other configurations of oval tubes are also tested, an oval tube R=3 with two wires soldered on its upper and lower top positions, and a cut-oval tube. The performance of the tubes is corrected for the effects of area blockage and turbulence intensity. The measurement results show that the mean Nusselt numbers NuD for the oval tubes are close to that for the circular tube for ReD<4,000. For a higher ReD, the NuD for the oval tubes is lower than that for the circular tube and it decreases with the increase in the axis ratio R. The drag coefficients Cd for the tubes are measured and the combined thermal-hydraulic performance is indicated by the ratio NuD/Cd, which shows a better combined performance for the oval tubes. 相似文献
429.
430.
Effects of interfacial dislocations on properties of thin-film ferroelectric materials, such as the self-polarization distribution, Curie temperature, dielectric constant and the switching behaviors, are investigated via the system dynamics based on the Landau-Devonshire functional. Dislocation generation in the film is found to reduce the overall self-polarization and the Curie temperature. The spatial variations are both very strong, particularly in the immediate neighborhood of the dislocation cores. In agreement with previous results based on a stationary model, a dead layer exists near the film/substrate interface, in which the average self-polarization is much reduced. Moreover, it is evident from our results that interface dislocations play an important role in suppressing the remnant polarization and the coercive field of the polarization. 相似文献