全文获取类型
收费全文 | 4900篇 |
免费 | 1367篇 |
国内免费 | 453篇 |
专业分类
化学 | 1373篇 |
晶体学 | 21篇 |
力学 | 883篇 |
综合类 | 74篇 |
数学 | 415篇 |
物理学 | 3954篇 |
出版年
2024年 | 10篇 |
2023年 | 44篇 |
2022年 | 138篇 |
2021年 | 166篇 |
2020年 | 168篇 |
2019年 | 155篇 |
2018年 | 159篇 |
2017年 | 212篇 |
2016年 | 272篇 |
2015年 | 220篇 |
2014年 | 360篇 |
2013年 | 371篇 |
2012年 | 345篇 |
2011年 | 364篇 |
2010年 | 260篇 |
2009年 | 302篇 |
2008年 | 337篇 |
2007年 | 320篇 |
2006年 | 304篇 |
2005年 | 269篇 |
2004年 | 211篇 |
2003年 | 211篇 |
2002年 | 197篇 |
2001年 | 174篇 |
2000年 | 156篇 |
1999年 | 145篇 |
1998年 | 112篇 |
1997年 | 95篇 |
1996年 | 105篇 |
1995年 | 78篇 |
1994年 | 73篇 |
1993年 | 51篇 |
1992年 | 51篇 |
1991年 | 38篇 |
1990年 | 25篇 |
1989年 | 32篇 |
1988年 | 19篇 |
1987年 | 30篇 |
1986年 | 20篇 |
1985年 | 21篇 |
1984年 | 20篇 |
1983年 | 12篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 10篇 |
1979年 | 13篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1969年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有6720条查询结果,搜索用时 15 毫秒
141.
With the combination of the the stoichiometric displacement model for retention (SDM-R) in reversed phase liquid chromatography (RPLC) and the stoichiometric displacement model for adsorption (SDM-A) in physical chemistry,the total number of moles of the re-solvated methanol of stationary phase side.nr,and that of solute side in the mobile phase,q,corresponding the one mole of the desorbing solute,were separately determined and referred as the characterization parameters of the contributions of the adsorption mechanism and partition mechanism to the solute retention,respectively.A chromatographic system of insulin,using mobile phase consisting of the pseudo-homologue of alcohols(methanol,ethanol and 2-propanol)-water and trifluoroacetic acid was employed.The maximum number of the methanol layers on the stationary phase surface was found to be 10.6,only 3 of which being valid in usual RPLC,traditionally referred as a volume process in partition mechanism.However,it still follows the SDM-R.Both of q and nr of insulin were found not to be zero,indicating that the retention mechanism of insulin is a mixed mode of partition mechanism and adsorption mechanism.When methanol is used as the organic modifier,the ratio of q/nr was 1.13,indicating the contribution to insulin retention due to partition mechanism being a bit greater than that due to adsorption mechanism.A linear relationship between q,or nr and the carbon number of the pseudo-homologue in the mobile phase was also found.As a methodology for investigating the retention mechanism retention and behavior of biopolymers.a homologue of organic solvents as the organic modifier in mobile phase has also been explored. 相似文献
142.
喜树碱类抗肿瘤药物作用模式的柔性分子对接研究 总被引:3,自引:0,他引:3
研究采用柔性分子对接技术,将15个喜树碱类化合物对接到拓扑异构酶I (Topo I)-DNA切割复合物中,从原子水平和分子力场角度阐明了喜树碱类抗肿瘤药 物与DNA,Topo I的相互作用机制。研究发现,喜树碱分子插入Topp I-DNA复合物 的切割位点,并与Asn722,Asp533,Lys532和Lys720形成氢键作用网络。定量构效 关系研究进一步表明喜树碱分子可以与Topo I-DNA切割复合物形成电荷迁移作用。 该对接模型系统解释了喜树碱类化合物的构效关系、定点突变等诸多实验事实,为 下一步设计、合成新型高效的喜树碱类衍生物打下了坚实基础。 相似文献
143.
The voltammetric behavior of the LMF-Mg(II) complex with DNA at a mercury electrode is reported for the first time. In NH3–NH4Cl buffer (pH=9.10), the adsorption phenomena of the LMF–Mg(II) complex were observed by linear sweep voltammetry. The mechanism of the electrode reaction was found to be a reduction of LMF in the complex, and the composition of the LMF–Mg(II) complex is 2:1. In the presence of calf thymus DNA (ctDNA), the peak current of LMF–Mg(II) complex decreased considerably, and a new well-defined adsorptive reduction peak appeared at −1.63 V (vs. SCE). The electrochemical kinetic parameters and the binding number of LMF–Mg(II) with ctDNA were also obtained. Moreover, the new peak currents of LMF–Mg(II)–DNA system increased linearly correlated to the concentration of DNA in the 4.00×10−7–2.60×10−6 g ml−1 range when the concentrations of LMF–Mg(II) complex was fixed at 5.00×10−6 mol l−1, with the detection limits of 2.33×10−7 g ml−1. An electrostatic interaction was suggested by electrochemical method. 相似文献
144.
Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions. 相似文献
145.
Both the spectra and infrared transition strengths of C6H6 and C6D6 for the C? H stretching overtones up to as high as v = 10 are described in high precision with few parameters (six for the spectra and four for the transition strengths) by the Iachello–Oss algebraic model. The Hamiltonian model is solved in the symmetry adapted bases, which are constructed by the symmetrized boson representation (SBR) technique. The results show that the combination of the algebraic method and SBR technique is a powerful method for describing vibrations of large molecules and high overtones. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
146.
147.
介绍了一个综合型有机化学实验,作为一个整体项目大约安排12周时间来完成。以不含香兰素的丁香花为原料,提取其中的丁香酚来多步合成香兰素,并进行物理和化学性质检验,整个实验技术路线包含了蒸馏、合成、重结晶等多种操作,同时在纯化和结构鉴定过程中还用到红外、紫外-可见和高效液相色谱等多种大型仪器分析技术。 相似文献
148.
IMPACT MODEL RESOLUTION ON PAINLEVE’S PARADOX 总被引:1,自引:0,他引:1
Painlevé‘s paradox is one of the basic difficulties for solving LCP of dynamic systems subjected to unilateral constraints. A bi-nonlinear parameterized impact model, consistent with dynamic principles and experimental results, is established on the localized and quasi-static impact model theory. Numerical simulations are carried out on the dynamic motion of Painlevé‘s example. The results confirm ““““impact without collision““““ in the inconsistent states of the system. A ““““critical normal force““““ which brings an important effect on the future movement of the system in the indeterminate states is found. After the motion pattern for the impact process is obtained from numerical results, a rule of the velocity‘s jump that incorporates the tangential impact process is deduced by using an approximate impulse theory and the coefficient of restitution defined by Stronge. The results of the jump rule are quite precise if the system rigidity is big enough. 相似文献
149.
Asia Al-jabiry Dr. Martin Palmer Dr. James Langridge Dr. Jeddidiah Bellamy-Carter Dr. David Robinson Prof. Neil J. Oldham 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13783-13792
Native mass spectrometry is now an important tool in structural biology. Thus, the nature of higher protein structure in the vacuum of the mass spectrometer is an area of significant interest. One of the major goals in the study of gas-phase protein structure is to elucidate the stabilising role of interactions at the level of individual amino acid residues. A strategy combining protein chemical modification together with collision induced unfolding (CIU) was developed and employed to probe the structure of compact protein ions produced by native electrospray ionisation. Tractable chemical modification was used to alter the properties of amino acid residues, and ion mobility-mass spectrometry (IM-MS) utilised to monitor the extent of unfolding as a function of modification. From these data the importance of specific intramolecular interactions for the stability of compact gas-phase protein structure can be inferred. Using this approach, and aided by molecular dynamics simulations, an important stabilising interaction between K6 and H68 in the protein ubiquitin was identified, as was a contact between the N-terminus and E22 in a ubiquitin binding protein UBA2. 相似文献
150.
This article discussed "teaching-practice-test" teaching mode with teaching practical experience and content matching.Results showed that this mode highlighted the proportion of practice and problem-solving in the process of learning; improved students' ability to solve problems using professional and disciplinary knowledge; changed learning styles from cramming way to autonomous learning step by step and trained students' creativity. 相似文献