全文获取类型
收费全文 | 1568篇 |
免费 | 77篇 |
国内免费 | 169篇 |
专业分类
化学 | 809篇 |
晶体学 | 7篇 |
力学 | 81篇 |
综合类 | 6篇 |
数学 | 338篇 |
物理学 | 573篇 |
出版年
2024年 | 4篇 |
2023年 | 51篇 |
2022年 | 34篇 |
2021年 | 23篇 |
2020年 | 48篇 |
2019年 | 34篇 |
2018年 | 40篇 |
2017年 | 43篇 |
2016年 | 49篇 |
2015年 | 42篇 |
2014年 | 62篇 |
2013年 | 110篇 |
2012年 | 78篇 |
2011年 | 117篇 |
2010年 | 100篇 |
2009年 | 117篇 |
2008年 | 126篇 |
2007年 | 109篇 |
2006年 | 89篇 |
2005年 | 93篇 |
2004年 | 86篇 |
2003年 | 52篇 |
2002年 | 54篇 |
2001年 | 35篇 |
2000年 | 35篇 |
1999年 | 25篇 |
1998年 | 31篇 |
1997年 | 18篇 |
1996年 | 21篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 12篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1814条查询结果,搜索用时 31 毫秒
41.
Halogen bonding has been used to hold two hydrogen bonded aromatic amide foldamers to form supramolecular macrocycles. 相似文献
42.
Double metal cyanide (DMC) complexes based on Zn3[Fe(CN)6]2 were synthesized using different molar ratios of ZnCl2 to K3[Fe(CN)6] and special complexing agents. IR spectroscopy, electron spectroscopy for chemical analysis, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and other analytical techniques were employed to characterize these catalysts. The morphology and structure of these DMC catalysts were attributed to the different complexing agents as well as to the different molar ratios of ZnCl2 to K3[Fe(CN)6]. In addition, the catalytic activity was strongly correlated with the morphology and noncrystalline content of DMC catalysts. High-activity catalysts could be prepared by controlling the structure of DMC catalysts by incorporating complexing agents. The active species of DMC catalysts for ring-opening polymerization are Zn2+, [Fe(CN)6]3–, Cl–, and the compound of their ligands. 相似文献
43.
44.
The electrooxidation of L -dopa at GC electrode was studied by in situ UV-vis spectroelectrochemistry (SEC) and cyclic voltammetry. The mechanism of electrooxidation and some reaction parameters were obtained. The results showed that the whole electrooxidation reaction of L -dopa at glassy carbon (GC) electrode was an irreversible electrochemical process followed by a chemical reaction in neutral solution (EC mechanism). The spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E0=228 mV, the apparent electron-transfer number of the electrooxidation reaction αn=0.376 (R=0.99, SD=0.26), the standard electrochemical rate constant k0=(3.93±0.12)×10−4 cm s−1 (SD=1.02×10−2), and the formation equilibrium constant of the following chemical reaction kc=(5.38±0.34)×10−1 s−1 (SD=1.02×10−2) were also obtained. 相似文献
45.
《Electroanalysis》2005,17(8):668-673
A self‐sampling‐and‐flow biosensor was fabricated by sandwiching a nitrocellulose strip on the working electrode side of the double‐sided microporous gold electrodes and a wicking pad on the counter electrode side. The double‐sided microporous electrodes were formed by plasma sputtering of gold on a porous nylon substrate. Sample was taken up to the enzyme‐immobilized working electrode by the capillary action of the front nitrocellulose strip dipped into the sample solution, analyzed electrochemically at the enzyme‐immobilized electrode, and diffuses out to the backside wicking pad through the micropores of the electrodes, constituting a complete flow cell device with no mechanical liquid‐transporting device. Biosensor was formed by co‐immobilizing the glucose oxidase and electron transfer mediator (ferrocene acetic acid) on the thioctic acid self‐assembled monolayer‐modified working electrode. A typical response time of the biosensor was about 5 min with the sensitivity of 2.98 nA/mM glucose, providing linear response up to 22.5 mM. To demonstrate the use of self‐sampling‐and‐flow biosensor, the consumption rate of glucose in the presence of yeast was monitored for five days. 相似文献
46.
A multidimensional GC-system containing two capillary columns of different polarities, operated within a double oven instrument, was used for the optimized separation of complex isomeric mixtures of various types of chlorinated aromatic compounds such as PCB, PCDD, or PCDF. Electron capture was applied parallel to flame ionization detection to obtain sensitive signals of the PCB or PCDD and the n-alkane standards required for identification by Kovats indices, respectively. Electron capture detection within a valvelessly operated MDGC system forced changes in the usual instrumental set-up, the live-switching coupling piece being located within the second oven of the double oven instrument. This oven is operated isothermally to ensure optimal and interference-free detection, for stable flow conditions within the coupling piece and for the determination of the isothermal retention indices (Kovats), which are much more suitable for identification by retention than the so-called “linear” indices. 相似文献
47.
M. Tseggai R. Mathieu R. Tellgren D.N.H. Nam N.V. Khiem F. Bourée 《Journal of solid state chemistry》2004,177(3):966-971
Magnesium substitution in Nd0.7Sr0.3MnO3 has been studied by neutron powder diffraction. Polycrystalline samples of nominal compositions Nd0.7Sr0.3Mn1−yMgyO3 with y=0.0, 0.1, 0.2 and 0.3 were synthesized by the standard solid-state reaction method. Rietveld refinements of the neutron powder diffraction data showed that all samples had distorted perovskite structure of orthorhombic symmetry. Mg initially preferred to substitute for Nd and only at Mg concentration greater than 0.1, a substantial substitution for Mn occurred. Our study also showed that Mg-substitution did not change the crystal structure of Nd0.7Sr0.3MnO3. 相似文献
48.
K.L. Holman Q. Huang K. Trzebiatowski E. Morosan R.J. Cava 《Journal of solid state chemistry》2007,180(1):75-83
The double perovskites La2CoVO6, La2CoTiO6, and La2NiVO6, are described. Rietveld fitting of neutron and powder X-ray diffraction data show La2NiVO6 and La2CoVO6 to have a disordered arrangement of B-cations whereas La2CoTiO6 shows ordering of the B-cations (with ∼5% Co/Ti inversion). Curie-Weiss fits to the linear region of the 1/χ plots reveal Weiss temperatures of −107, −34.8, and 16.3 K for La2CoVO6, La2CoTiO6, and La2NiVO6, respectively, and magnetic transitions are observed. La2CoTiO6 prepared by our method differs from material prepared by lower-temperature routes. A simple antiferromagnetic spin model is consistent with the data for La2CoTiO6. These compounds are semiconductors with bandgaps of 0.41 (La2CoVO6), 1.02 (La2CoTiO6) and 0.45 eV (La2NiVO6). 相似文献
49.
多色蓝在核酸分子上的Langmuir聚集吸附 总被引:4,自引:0,他引:4
用微相吸附-光谱修正(MPASC)新技术研究核酸与多色蓝(PCB)探针分子间的相互作用,分析核酸分子内双静电膜的形成与Langmuir吸附的关联性.通过pH 7.24的介质核酸-PCB反应的光谱研究,测定了结合产物的物理化学参数:结合比1PCB:2DNA-PCB、1PCB:3RNA-PCB, 平衡常数KDNA-PCB=5.42×104, KRNA-PCB=2.82×104,摩尔吸收系数ε(DNA-PCB, 625 nm)=5.65×103(mo1-1•L )•cm-1, ε(RNA-PCB, 625 nm)=3.85×103 (mol-1•L)•cm-1.结果表明, RNA分子仅形成约60%双螺旋结构链,核酸双螺旋每一周期的负静电沟最大聚集10个PCB分子.该吸附反应用于核酸样品测定,结果良好. 相似文献
50.
The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects
of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well
as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The
contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material
have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and
power characteristics manifested by current–potential and energy–power (Ragone plots) are elucidated. 相似文献