全文获取类型
收费全文 | 11397篇 |
免费 | 1527篇 |
国内免费 | 976篇 |
专业分类
化学 | 3254篇 |
晶体学 | 60篇 |
力学 | 792篇 |
综合类 | 242篇 |
数学 | 4890篇 |
物理学 | 4662篇 |
出版年
2023年 | 77篇 |
2022年 | 177篇 |
2021年 | 272篇 |
2020年 | 248篇 |
2019年 | 225篇 |
2018年 | 240篇 |
2017年 | 323篇 |
2016年 | 364篇 |
2015年 | 297篇 |
2014年 | 582篇 |
2013年 | 819篇 |
2012年 | 618篇 |
2011年 | 718篇 |
2010年 | 612篇 |
2009年 | 729篇 |
2008年 | 813篇 |
2007年 | 777篇 |
2006年 | 673篇 |
2005年 | 654篇 |
2004年 | 516篇 |
2003年 | 482篇 |
2002年 | 437篇 |
2001年 | 339篇 |
2000年 | 308篇 |
1999年 | 304篇 |
1998年 | 308篇 |
1997年 | 237篇 |
1996年 | 194篇 |
1995年 | 189篇 |
1994年 | 203篇 |
1993年 | 129篇 |
1992年 | 127篇 |
1991年 | 98篇 |
1990年 | 78篇 |
1989年 | 85篇 |
1988年 | 78篇 |
1987年 | 74篇 |
1986年 | 54篇 |
1985年 | 83篇 |
1984年 | 55篇 |
1983年 | 39篇 |
1982年 | 53篇 |
1981年 | 23篇 |
1980年 | 24篇 |
1979年 | 34篇 |
1978年 | 35篇 |
1977年 | 22篇 |
1976年 | 20篇 |
1975年 | 10篇 |
1973年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
51.
Josef Janča 《International Journal of Polymer Analysis and Characterization》2015,20(8):671-680
Micro-thermal field-flow fractionation was used to characterize the particle size distribution of nanometer-sized diamond nanoparticles. Although the experimental conditions were chosen to perform high-speed separation, and, consequently, the resolution achieved experimentally was not very high, the application of the original correction method for the zone spreading allowed for obtaining of very good calculated particle size distribution or, explicitly, a true polydispersity index of the diamond nanoparticle sample. The future use of several samples of diamond nanoparticles of different average sizes and different surface chemistries should allow deeper insight into the effect of these particulate characteristics on the retention in micro-thermal field-flow fractionation. 相似文献
52.
Mingliang Zhang Abul K. Mallik Makoto Takafuji Hirotaka Ihara Hongdeng Qiu 《Analytica chimica acta》2015
Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. 相似文献
53.
The objective of this study was to develop a model to predict the viscoelastic material functions of a vinyl ester (VE) polymer with variations in its experimentally obtained material properties under combined isothermal and mechanical loading. Short-term tensile creep experiments were conducted at three temperatures below the glass transition temperature of the VE polymer, with 10 replicates for each test configuration. The measured creep strain versus time responses were used to determine the creep compliances using the generalized viscoelastic constitutive equation with a Prony series representation. The variation in the creep compliances of a VE polymer was described by formulating the probability density functions (PDFs) and the corresponding cumulative distribution functions (CDFs) of the creep compliances using a two-parameter Weibull distribution. Both Weibull scale and shape parameters of the creep compliance distributions were shown to be time and temperature dependent. Two-dimensional quadratic Lagrange interpolation functions were used to characterize the Weibull parameters to obtain the PDFs and, subsequently, the CDFs of the creep compliances for the complete design temperature range during steady state creep. At each test temperature, creep compliance curves were obtained for constant CDF values and compared with the experimental data. The predicted creep compliances of the selected VE polymer in the design space are in good agreement with the experimental data for all three test temperatures. 相似文献
54.
Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers 下载免费PDF全文
Ru Zhang Dr. Jinxiang Liu Dr. Hongfang Yang Shoushan Wang Meng Zhang Prof. Dr. Yuxiang Bu 《Chemphyschem》2015,16(2):436-446
Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs. 相似文献
55.
Experimental Charge Density Evidence for Pnicogen Bonding in a Crystal of Ammonium Chloride 下载免费PDF全文
Dr. Yulia V. Nelyubina Prof. Alexander A. Korlyukov Prof. Konstantin A. Lyssenko 《Chemphyschem》2015,16(3):676-681
Chemical binding in crystalline ammonium chloride, a simple inorganic salt with an unexpectedly complex bonding pattern, was studied by using a topological analysis of electron density function derived from high‐resolution X‐ray diffraction. Supported by periodic quantum chemical calculations, it provided experimental evidence for weak σ‐hole bonds (1.5 kcal mol?1) that involve ammonium cations in a crystal. Our results show this type of supramolecular interaction to be more numerous than has been found to date by using gas‐phase calculations or statistical analysis of CSD. 相似文献
56.
Development of a liquid chromatography with mass spectrometry method for the determination of gelsemine in rat plasma and tissue: Application to a pharmacokinetic and tissue distribution study 下载免费PDF全文
Shuangshuang Zhang Shuping Hu Xiangxiang Yang Jiaqi Shen Xiaoyong Zheng Kexin Huang Zheng Xiang 《Journal of separation science》2015,38(6):936-942
Gelsemine from Gelsemium elegans Benth is a potential anesthetic and analgesic agent with no physical dependence and opiate addiction. This study was aimed at developing an ultrafast liquid chromatography coupled to tandem mass spectrometry method to quantify gelsemine in rat plasma and tissues. Plasma and tissues were processed with acetonitrile precipitation, and dendrobine was chosen as the internal standard. Sample separation was performed on an ACQUITY HSS T3 column. The mobile phase consisted of acetonitrile and 0.1% formic acid aqueous solution. Multiple reactions monitoring mode was utilized to detect the compounds of interest. The mass spectrometer was operated in the positive ion mode for detection. The MS/MS ion transitions monitored were m/z 323.2→70.5 for gelsemine and 264.2→108.05 for dendrobine, respectively. The calibration curves were linear over the range of 1–500 ng/mL in all biological matrices. The lower limit of quantification for rats plasma and tissues was 1.0 ng/mL. The values for inter‐ and intraday precision and accuracy were well within the ranges acceptable (< 15%). It was successfully applied to the pharmacokinetic and tissue distribution studies of gelsemine after intravenous doses of 5, 2, and 0.5 mg/kg in rats. These data of gelsemine would be useful for clinical application and further development. 相似文献
57.
Coating properties of a novel water stationary phase in capillary supercritical fluid chromatography 下载免费PDF全文
The coating properties of a novel water stationary phase used in capillary supercritical fluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless‐steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless‐steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm2 regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless‐steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless‐steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless‐steel columns were more resistant to etching than 304 stainless‐steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless‐steel columns used with this supercritical fluid chromatography technique. 相似文献
58.
Xi-Yang Tang Zi-Qin Dai Jia-Xing Zeng Zi-Ting Li Cai-Lian Fan Zhi-Hong Yao Xin-Sheng Yao Yi Dai 《Journal of separation science》2022,45(13):2177-2189
In the present study, a specific and sensitive approach using ultra-high-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry was developed and validated for the quantitative analysis of 14 constituents in rat plasma, liver, and heart. The method was fully validated and successfully applied to pharmacokinetic, hepatic disposition, and heart tissue distribution studies of 14 compounds after the oral administration of Qi-Li-Qiang-Xin capsule. Ginsenoside Rb1, alisol A, astragaloside IV, and periplocymarin were found to be highly exposed in rat plasma, while toxic components such as hypaconitine, mesaconitine, and periplocin had low circulation levels in vivo. Moreover, sinapine thiocyanate, neoline, formononetin, calycosin, and alisol A exhibited significant liver first-pass effects. Notably, high levels of alisol A, periplocymarin, benzoylmesaconine, and benzoylhypaconine were observed in the heart. Based on high exposure and appropriate pharmacokinetic features in the systemic plasma and heart, astragaloside IV, ginsenoside Rb1, periplocymarin, benzoylmesaconine, benzoylhypaconine, and alisol A can be considered as the main potentially effective components. Ultimately, the results provide relevant information for discovery of effective substances, as well as further anti-heart failure action mechanism investigations of Qi-Li-Qiang-Xin capsule. 相似文献
59.
The structure, size, and main physicochemical characteristics of the SARS-CoV-2 virion with the spike transmembrane protein corona were discussed. Using these data, diffusion coefficients of the virion in aqueous media and in air were calculated. The structure and dimensions of the spike protein derived from molecular dynamic modeling and thorough cryo-electron microscopy measurements were also analyzed. The charge distribution over the molecule was calculated and shown to be largely heterogeneous. Although the stalk part is negatively charged, the top part of the spike molecule, especially the receptor binding domain, remains positively charged for a broad range of pH. It is underlined that such a charge distribution promotes the spike corona stability and enhances the virion attachment to receptors and surfaces, mostly negatively charged. The review is completed by the analysis of experimental data pertinent to the spike protein adsorption at abiotic surfaces comprising nanoparticle carrier particles. It is argued that these theoretical and experimental data can be used for developing quantitative models of virus attachment to surfaces, facilitating adequate analysis of future experimental results. 相似文献
60.