全文获取类型
收费全文 | 4116篇 |
免费 | 618篇 |
国内免费 | 460篇 |
专业分类
化学 | 2978篇 |
晶体学 | 40篇 |
力学 | 234篇 |
综合类 | 36篇 |
数学 | 475篇 |
物理学 | 1431篇 |
出版年
2024年 | 15篇 |
2023年 | 101篇 |
2022年 | 125篇 |
2021年 | 155篇 |
2020年 | 192篇 |
2019年 | 174篇 |
2018年 | 146篇 |
2017年 | 112篇 |
2016年 | 185篇 |
2015年 | 188篇 |
2014年 | 175篇 |
2013年 | 289篇 |
2012年 | 293篇 |
2011年 | 301篇 |
2010年 | 215篇 |
2009年 | 215篇 |
2008年 | 244篇 |
2007年 | 196篇 |
2006年 | 197篇 |
2005年 | 198篇 |
2004年 | 181篇 |
2003年 | 120篇 |
2002年 | 116篇 |
2001年 | 111篇 |
2000年 | 113篇 |
1999年 | 102篇 |
1998年 | 86篇 |
1997年 | 81篇 |
1996年 | 85篇 |
1995年 | 62篇 |
1994年 | 72篇 |
1993年 | 51篇 |
1992年 | 44篇 |
1991年 | 34篇 |
1990年 | 41篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 25篇 |
1986年 | 20篇 |
1985年 | 22篇 |
1984年 | 13篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有5194条查询结果,搜索用时 15 毫秒
91.
Zong ChunYan Gao QingYu Wang YuMei Feng JiaMin Mao ShanCheng Zhang Lu 《中国科学B辑(英文版)》2007,50(2):205-211
The ferroin-catalyzed Belousov-Zhabotinsky(BZ) reaction,the oxidation of malonic acid by acidic bromate,is the most commonly investigated chemical system for understanding spatial pattern forma-tion. Various oscillatory behaviors were found from such as mixed-mode and simple period-doubling oscillations and chaos on both Pt electrode and Br-ISE at high flow rates to mixed-mode oscillations on Br-ISE only at low flow rates. The complex dynamic behaviors were qualitatively reproduced with a two-cycle coupling model proposed initially by Gy?rgyi and Field. This investigation offered a proper medium for studying pattern formation under complex temporal dynamics. In addition,it also shows that complex oscillations and chaos in the BZ reaction can be extended to other bromate-driven nonlinear reaction systems with different metal catalysts. 相似文献
92.
93.
本文报导了四种不同N/Pd摩尔比的聚γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成及其催化加氢活性,这类催化剂与聚γ-((L-酷氨酸)丙基硅氧烷钯催化剂相比较,虽然均具有类似的N→Pd配位的活性中心组成,但它们对底物的加氢活性则明显不同,前者对丙烯腈、丙烯酸、环己烯和1-癸烯的催化活性比后者高,对苯乙烯则相反。N/Pd摩尔比、反应温度、溶剂以及体系的pH值对催化活性的影响,两者的情况大致相同,标题催化剂对衣康酸的催化加氢,产物的光学纯度为30%。 相似文献
94.
Juan Jia Dierk Raabe Wei-min Mao 《高分子科学》2006,(4):403-411
The orientation and crystallinity evolution of isotactic polypropylene (iPP) induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of (010)[001], (130)[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction: high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction. 相似文献
95.
This study reports magnitudes and the orientation of the (13)C(alpha) chemical shift anisotropy (CSA) tensors of peptides obtained using quantum chemical calculations. The dependency of the CSA tensor parameters on the energy optimization of hydrogen atom positions and hydrogen bonding effects and the use of zwitterionic peptides in the calculations are examined. Our results indicate that the energy optimization of the hydrogen atom positions in crystal structures is necessary to obtain accurate CSA tensors. The inclusion of intermolecular effects such as hydrogen bonding in the calculations provided better agreement between the calculated and experimental values; however, the use of zwitterionic peptides in calculations, with or without the inclusion of hydrogen bonding, did not improve the results. In addition, our calculated values are in good agreement with tensor values obtained from solid-state NMR experiments on glycine-containing tripeptides. In the case of peptides containing an aromatic residue, calculations on an isolated peptide yielded more accurate isotropic shift values than the calculations on extended structures of the peptide. The calculations also suggested that the presence of an aromatic ring in the extended crystal peptide structure influences the magnitude of the delta(22) which the present level of ab initio calculations are unable to reproduce. 相似文献
96.
Weike Zhong Diandou Xu Zhifang Chai Xueying Mao 《Journal of Radioanalytical and Nuclear Chemistry》2004,259(3):485-488
Instrumental neutron activation analysis (INAA) has been used for the determination of extractable organohalogens (EOX) in
milk. The detection limits are 50 ng, 8 ng and 3.5 ng for Cl, Br and I, respectively. The EOX concentrations in milk samples
from various regions of China were determined. Meanwhile, organochlorine pesticides residues were detected by gas chromatography.
The concentrations of the EOX in the milk samples are decreasing in the order of EOCl >> EOBr > EOI, and EOCl accounts for
95% of the total EOX. The average concentration of EOCl in milk is 4.44 ·g/g expressed as fat weight basis, with the highest
value of 17.6 ·g/g from South China. The mean concentrations of total HCH and DDT are 0.038 ·g/g and 0.046 ·g/g, respectively.
Organochlorine pesticides account only for 1.6% of the EOCl, indicating the very high proportion of the unknown EOCl in the
milk sample.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
97.
The addition of gem-difluorinated alkyl iodides to alkynes initiated by AIBN neatly gave the corresponding difluoromethylene vinyl iodides among which the stereoselectivity of aromatic acetylenes was high. The further coupling reaction of E-phenyl difluoromethylene vinyl iodides with terminal alkynes in the presence of catalytic palladium afforded the substituted difluorinated enynes. 相似文献
98.
Mechanical properties and stability measurement of cholesterol-containing liposome on mica by atomic force microscopy 总被引:1,自引:0,他引:1
The micromechanical properties of pure and cholesterol modified egg yolk phosphatidylcholine (EggPC) vesicles prepared by sonication were studied by atomic force microscopy (AFM) on mica surface. The force curves between an AFM tip and an unruptured vesicle were obtained by contact mode. During approach, two repulsion regions with two breaks were observed. The slopes of the two repulsive force regimes for the pure EggPC vesicles are determined to be several times lower than that of EggPC/cholesterol vesicles. The elastic properties from force plot analysis based on the Hertzian model showed that Young's modulus (E) and the bending modulus (kc) of cholesterol-modified vesicles increased several-fold compared with pure EggPC vesicles. The significant difference is attributed to the enhanced rigidity of the EggPC vesicles as a result of the incorporation of cholesterol molecules. The behavior of cholesterol-modified vesicles upon adsorption is different from that in solution as revealed by mechanical properties. The results indicate that AFM can provide a direct method to measure the mechanical properties of adsorbed small liposomes and to detect the stability change of liposomes. 相似文献
99.
Yu Mao Wenxuan Zhao Shuo Lu Lei Yu Yi Wang Yong Liang Shengyang Ni Yi Pan 《Chemical science》2020,11(19):4939
Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation. 相似文献
100.
Jemal M Huang M Mao Y Whigan D Powell ML 《Rapid communications in mass spectrometry : RCM》2001,15(12):994-999
The feasibility of quantitative bioanalysis by parallel-column liquid chromatography in conjunction with a conventional single-source electrospray mass spectrometer has been investigated using plasma samples containing a drug and its three metabolites. Within a single chromatographic run time, sample injections were made alternately onto each of two analytical columns in parallel at specified intervals, with a mass spectrometer data file opened at every injection. Thus, the mass spectrometer collected data from two sample injections into separate data files within a single chromatographic run time. Therefore, without sacrificing the chromatographic separation or the selected reaction monitoring (SRM) dwell time, the sample throughput was increased by a factor of two. Comparing the method validation results obtained using the two-column system with those obtained using the corresponding conventional single-column approach, the methods on the two systems were found to be equivalent in terms of accuracy and precision. The parallel-column system is simple and can be implemented using existing laboratory equipment with no additional capital outlays. A parallel-column system configured in this manner can be used not only for the within-a-run analysis of two samples containing two different sets of chemical entities, but also for the within-a-run analysis of two samples containing the same set of chemical entities. 相似文献