全文获取类型
收费全文 | 38551篇 |
免费 | 2407篇 |
国内免费 | 1867篇 |
专业分类
化学 | 21631篇 |
晶体学 | 205篇 |
力学 | 3829篇 |
综合类 | 535篇 |
数学 | 8059篇 |
物理学 | 8566篇 |
出版年
2024年 | 32篇 |
2023年 | 344篇 |
2022年 | 614篇 |
2021年 | 942篇 |
2020年 | 996篇 |
2019年 | 946篇 |
2018年 | 851篇 |
2017年 | 1083篇 |
2016年 | 1476篇 |
2015年 | 1097篇 |
2014年 | 1574篇 |
2013年 | 2767篇 |
2012年 | 2256篇 |
2011年 | 2036篇 |
2010年 | 1746篇 |
2009年 | 2251篇 |
2008年 | 2225篇 |
2007年 | 2511篇 |
2006年 | 2081篇 |
2005年 | 1881篇 |
2004年 | 1810篇 |
2003年 | 1498篇 |
2002年 | 1139篇 |
2001年 | 925篇 |
2000年 | 875篇 |
1999年 | 749篇 |
1998年 | 724篇 |
1997年 | 668篇 |
1996年 | 598篇 |
1995年 | 625篇 |
1994年 | 552篇 |
1993年 | 456篇 |
1992年 | 421篇 |
1991年 | 362篇 |
1990年 | 327篇 |
1989年 | 218篇 |
1988年 | 219篇 |
1987年 | 137篇 |
1986年 | 117篇 |
1985年 | 141篇 |
1984年 | 112篇 |
1983年 | 58篇 |
1982年 | 94篇 |
1981年 | 54篇 |
1980年 | 44篇 |
1979年 | 74篇 |
1978年 | 33篇 |
1977年 | 14篇 |
1976年 | 22篇 |
1957年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 19 毫秒
991.
研究含汞土壤的修复问题,采用热解析和低温等离子体综合技术探究新途径,调整温度、添加剂、时间等因素来判断脱汞效果并探究其不同形态,分析工艺过程废料的内部联系,并对废气处理进行分析实验。结论如下:(1)通过改良技术的BCR连续萃取法,得出研究区汞的形态主要为有机结合态(53%)。之后依次是氧化物结合态(33%)、酸可提取态(8%)、残渣态(6%)。(2)温度对热解析程度影响较大。在500℃以上的热解析条件下,土壤中的汞浓度不足1.5 mg·kg-1。(3)当选用400℃的解析温度时,40 min汞去除总体完成。在低于1 700 mg·kg-1的浓度下,汞去除率随着土壤中的含量的增大而减小。(4)氯化钙对于热解析的促进作用最强,柠檬酸、升华硫也有一定作用,硫化钠对于汞去除形成阻滞。(5)低温等离子体的最佳状态是电源设置电压为22 kV,频率为660 Hz。整个系统的汞去除程度可达近90%。 相似文献
992.
Coordination compounds of Fe(III), Zn(II), Ni(II), Co(II), Cu(II), Cd(II) and Mn(II) ions were synthesized from the ligand [4,4′‐((((ethane‐1,2‐diylbis(oxy))bis(2,1‐phenylene))bis(methanylylidene))bis(azanylylidene))diphenol]ethane (H2L) derived from the condensation of bisaldehyde and 4‐aminophenol. Microanalysis, magnetic susceptibility, infrared, 1H NMR and mass spectroscopies, molar conductance, X ray powder diffraction and thermal analysis were used to confirm the structure of the synthesized chelates. According to the data obtained, the composition of the 1:1 metal ion–bis‐Schiff base ligand was found to be [M(H2L)(H2O)2]Cln (M = Zn(II), Ni(II), Co(II), Cu(II), Cd(II) and Mn(II), n = 2; Fe(III), n = 3). Magnetic susceptibility measurements and reflectance spectra suggested an octahedral geometry for the complexes. Central metals ions and bis‐Schiff base coordinated together via O2 and N2 donor sites which as evident from infrared spectra. The Gaussian09 program was applied to optimize the structural formula for the investigated Schiff base ligand. The energy gaps and other important theoretical parameters were calculated applying the DFT/B3LYP method. Molecular docking using AutoDock tools was utilized to explain the experimental behaviour of the Schiff base ligand towards proteins of Bacillus subtilis (5 h67), Escherichia coli (3 t88), Proteus vulgaris (5i39) and Staphylococcus aureus (3ty7) microorganisms through theoretical calculations. The docked protein receptors were investigated and the energies of hydrogen bonding were calculated. These complexes were then subjected to in vitro antibacterial studies against several organisms, both Gram negative (P. vulgaris and E. coli) and Gram positive (S. pyogones and B. subtilis). The ligand and metal complexes exhibited good microbial activity against the Gram‐positive and Gram‐negative bacteria. 相似文献
993.
Pedro Marcos Frugeri Camila Marchioni Ayla Campos do Lago Célio Wisniewski 《Analytical letters》2018,51(10):1492-1504
This work proposes a flow injection analysis system for sulfaguanidine determination in pharmaceutical and food samples. The method was based on the reaction of sulfaguanidine with nitronium ion to produce a colored complex whose absorbance was measured at 545?nm. The flow injection analysis system’s significant parameters were checked by a fractional factorial design 27–2 and optimization by a Doehlert matrix. The flow injection analysis system shows optimum values at 0.28, 2.00, and 0.11% (w/v) for N-naphtil ethylenediamine, ammonium sulfamate, and sodium nitrite concentrations, respectively. The possible interferents present in pharmaceutical and food samples were assessed by a multivariate technique and depicted on probability charts, indicating no significant interferences at the 95% level of confidence interval. The method showed detection and quantification limits of 0.012 and 0.039?mg?L?1, an analytical frequency of 30 readings h?1 and precision always lower than 5.0% expressed as the relative standard deviation. The obtained results were in accordance with those obtained by high-performance liquid chromatography. 相似文献
994.
It is well known that the apparent concentration of a solute element in metal, detected by atom probe tomography analysis, depends on the measurement condition such as specimen temperature, pulse fraction, and pulse frequency. The dependence was qualitatively interpreted to be caused by preferential evaporation and retention in field evaporation. A quantitative physical model accounting for the preferential evaporation and retention was proposed herein for the first time. The proposed model was applied to a ferritic iron–copper (Fe–Cu) alloy for preferential evaporation and a ferritic iron–silicon (Fe–Si) alloy for preferential retention. The model explained the temperature dependence on the apparent concentration of the solute element and the unwindowed background noise in each alloy well, whereas the dependence of pulse fraction and pulse frequency was not completely explained. The cause of the difference between the experimental and calculated results based on the model was discussed. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
995.
Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells 下载免费PDF全文
Bin Deng Zhi‐Ming Wang Zi‐Hao Zhou Yi‐Meng Liu Xi‐Liang Yang Jian Song Yu‐Xiu Xiao 《Biomedical chromatography : BMC》2014,28(10):1393-1401
Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
996.
The trust region method which originated from the Levenberg–Marquardt (LM) algorithm for mixed effect model estimation are considered in the context of second level functional magnetic resonance imaging (fMRI) data analysis. We first present the mathematical and optimization details of the method for the mixed effect model analysis, then we compare the proposed methods with the conventional expectation-maximization (EM) algorithm based on a series of datasets (synthetic and real human fMRI datasets). From simulation studies, we found a higher damping factor for the LM algorithm is better than lower damping factor for the fMRI data analysis. More importantly, in most cases, the expectation trust region algorithm is superior to the EM algorithm in terms of accuracy if the random effect variance is large. We also compare these algorithms on real human datasets which comprise repeated measures of fMRI in phased-encoded and random block experiment designs. We observed that the proposed method is faster in computation and robust to Gaussian noise for the fMRI analysis. The advantages and limitations of the suggested methods are discussed. 相似文献
997.
998.
Ethanol determination in frozen fruit pulps: an application of quantitative nuclear magnetic resonance 下载免费PDF全文
Wilian da Silva Nunes Caroline Silva de Oliveira Glaucia Braz Alcantara 《Magnetic resonance in chemistry : MRC》2016,54(4):334-340
This study reports the chemical composition of five types of industrial frozen fruit pulps (acerola, cashew, grape, passion fruit and pineapple fruit pulps) and compares them with homemade pulps at two different stages of ripening. The fruit pulps were characterized by analyzing their metabolic profiles and determining their ethanol content using quantitative Nuclear Magnetic Resonance (qNMR). In addition, principal component analysis (PCA) was applied to extract more information from the NMR data. We detected ethanol in all industrial and homemade pulps; and acetic acid in cashew, grape and passion fruit industrial and homemade pulps. The ethanol content in some industrial pulps is above the level recommended by regulatory agencies and is near the levels of some post‐ripened homemade pulps. This study demonstrates that qNMR can be used to rapidly detect ethanol content in frozen fruit pulps and food derivatives. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
999.
Metal Oxide Assisted Preparation of Core–Shell Beads with Dense Metal–Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants 下载免费PDF全文
Mateo del Rio Dr. Carlos Palomino Cabello Veronica Gonzalez Dr. Fernando Maya Dr. Jose B. Parra Dr. Victor Cerdà Dr. Gemma Turnes Palomino 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11770-11777
Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings. 相似文献
1000.
Single crystals of a diphosphate NaLuP2O7 have been synthesized by the flux method and characterized by single-crystal X-Ray diffraction. NaLuP2O7 crystallizes in the monoclinic system with P21/n space group with cell parameters: a = 8.9985(8) Å, b = 5.3473(5) Å, c = 12.756(1) Å, β = 103.174° (1), V = 597.67 (9) Å3, Z = 4. Its structure consists of a three-dimensional framework of P2O7 units that are corner-shared by LuO6 octahedra, forming tunnels running parallel to [010] which are occupied by Na atoms. NaLuP2O7 powder was characterized by XRD, SEM, FTIR and Raman spectroscopy. The activation energy of (1.49 eV) obtained by electrical measurements suggests the charge carriers to be the sodium cations. The activation energies obtained from impedance and loss spectra were analyzed in order to explain the mechanism of conduction. The correlation between ionic conductivity of NaLuP2O7 and its crystallographic structure was investigated and the most probable transport pathway model was determined. 相似文献