全文获取类型
收费全文 | 207篇 |
免费 | 25篇 |
国内免费 | 15篇 |
专业分类
化学 | 145篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 16篇 |
物理学 | 80篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 7篇 |
2016年 | 9篇 |
2015年 | 3篇 |
2014年 | 8篇 |
2013年 | 8篇 |
2012年 | 11篇 |
2011年 | 9篇 |
2010年 | 10篇 |
2009年 | 11篇 |
2008年 | 14篇 |
2007年 | 16篇 |
2006年 | 9篇 |
2005年 | 7篇 |
2004年 | 11篇 |
2003年 | 3篇 |
2002年 | 10篇 |
2001年 | 10篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有247条查询结果,搜索用时 187 毫秒
31.
Polysaccharide-based chiral stationary phases (CSPs) are efficient for enantioseparation of many chiral compounds. Immobilized
polysaccharide CSP, as used in the Chiralpak IA column, is a new configuration that was recently introduced for application
in chiral separation. As shown in several previous studies, the characteristics of Chiralpak IA columns cannot be simply extrapolated
from the coated version. In this study, hold-up volume of a Chiralpak IA column was evaluated by static and dynamic methods.
The static pyconometry method gave similar hold-up volumes either as an average value from a range of solvents or a direct
measurement from the carbon tetrachloride-isopropanol (IPA) solvent pair. The dynamic method with 1,3,5-tri-tert-butylbenzene (TTBB) was influenced by the ratio of n-hexane and 2-propanol in the mobile phase but not by the dissolving solvent of TTBB. The two methods resulted in the same
hold-up volume of ∼3.0 mL. TTBB showed weaker retention on the IA column after correction of isobaric thermal expansion of
the mobile phase. During temperature variations in the range of 15–50 °C, the hold-up volume of TTBB was highly reproducible.
Results of this study improve our understanding of the chromatographic features of the immobilized polysaccharide IA column. 相似文献
32.
Anushree Das Emily A. Lao Anna D. Gudmundsdottir 《Photochemistry and photobiology》2016,92(3):388-398
Photolysis of ester 1 in argon‐saturated methanol and acetonitrile does not produce any product, whereas irradiation of 1 in oxygen‐saturated methanol yields peroxide 2 . Laser flash photolysis studies demonstrate that 1 undergoes intramolecular H atom abstraction to form biradical 3 (λ max ~ 340 nm), which intersystem crosses to form photoenols Z ‐ 4 and E ‐ 4 (λ max ~ 380 nm). Photoenols 4 decay by regenerating ester 1 . With the aid of density functional theory calculations, it was concluded the photoenol E ‐ 4 does not undergo spontaneous lactonization or electrocyclic ring closure because the transition state barriers for these reactions are too large to compete with reketonization of E ‐ 4 to form 1 . 相似文献
33.
This paper presents different experimental results of the influence of an immersion angle (θ, the angle between the surface of a quartz crystal resonator and the horizon) on the resonant frequency of a quartz crystal microbalance (QCM) sensor exposed one side of its sensing surfaces to liquid. The experimental results show that the immersion angle is an added factor that may influence the frequency of the QCM sensor. This type of influence is caused by variation of the reflection conditions of the longitudinal wave between the QCM sensor and the walls of the detection cell. The frequency shifts, measured by varying θ, are related to the QCM sensor used. When a QCM sensor with a weak longitudinal wave is used, its resonant frequency is nearly independent of θ. But, if a QCM sensor with a strong longitudinal wave is employed, the immersion angle is a potential error source for the measurements performed on the QCM sensor. When the reflection conditions of the longitudinal wave are reduced, the influence of θ on the resonant frequency of the QCM sensor is negligible. The slope of the plot of frequency shifts (ΔF) versus (ρη)1/2, the square root of the product of solution density (ρ) and viscosity (η), may be influenced by θ in a single experiment for the QCM sensor with a strong longitudinal wave in low viscous liquids, which can however, be effectively weakened by using the averaged values of reduplicated experiments. In solutions with a large (ρη)1/2 region (0-55 wt% sucrose solution as an example, with ρ value from 1.00 to 1.26 g cm−3 and η value from 0.01 to 0.22 g cm−1 s−1, respectively), the slope of the plot of ΔF versus (ρη)1/2 is independent of θ even for the QCM sensor with a strong longitudinal wave in a single experiment. The influence of θ on the resonant frequency of the QCM sensor should be taken into consideration in its applications in liquid phase. 相似文献
34.
Jenikova G Lao UL Gao D Mulchandani A Chen W 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2277-2279
In this work, we report a new method to reversibly immobilize proteins to a surface in a functionally active orientation directly from cell lysate by employing a fusion protein consisting of a thermal-responsive elastin (ELP) domain as the surface anchor and a calcium-responsive calmodulin (CalM) domain for protein capturing. Incorporation of an M13 tag into recombinant proteins enables not only easy surface immobilization but also direct purification from cell lysates. The feasibility of concept was demonstrated using the M13-tagged yellow fluorescent protein (M13-YFP). The ELP-CalM functionalized surfaces were shown to capture M13-YFP directly from cell lysate through the specific calmodulin-M13 association in a calcium-dependent manner. We also demonstrated that immobilization is reversible; the bound proteins were released from the surface in the presence of EDTA. 相似文献
35.
在多晶A l2O3衬底上,以B2H6作为硼源,化学气相沉积先驱B薄膜,采用Mg扩散方法,在不同退火时间条件下制备了MgB2超导薄膜。通过电阻-温度曲线测量、X射线衍射分析和扫描电子显微镜形貌观测方法,研究了退火时间对MgB2薄膜的超导特性、晶体结构、表面形貌的影响。 相似文献
36.
Many chiral pesticides exhibit enantioselectivity in biotransformation and ecotoxicity in the environment. A significant class of chiral pesticides is imidazolinone herbicides, of which enantioselectivity has not been well studied. Development of efficient chiral separation methods is the first step for allowing characterization of enantioselectivity in environmental processes. In this study, we attempted to resolve enantiomers of imidazolinone herbicides using reversed-phase and normal-phase high-performance liquid chromatography with polysaccharide-type chiral columns. Enantiomers of imazethapyr, imazaquin, and imazamox were separated on a Chiralcel OD-R column using 50mM phosphate buffer-acetonitrile as mobile phase. Enantiomers of imazapyr, imazapic, imazethapyr, imazamox and imazaquin were resolved on a Chiralcel OJ column using n-hexane (0.1% trifluoroacetic acid)-alcohol as mobile phase. The enantiomers of five methyl derivatives of imidazolinone herbicides were also resolved on the Chiralcel OJ column. The Deltak' values revealed a structure-enantioselectivity relationship for the separation behaviors of the enantiomers on the OJ column. The described method was successfully applied for chiral analysis of two imidazolinone herbicides (imazapyr and imazaquin) in spiked soil samples. 相似文献
37.
在经典单路段元胞自动机交通流模型的基础上,将多个路段视为一个道路系统,提出并研究了多路段条件下的交通流问题.针对多路段道路的特点,通过引入车辆流入规则、路口随机慢化规则和路口车辆流入规则,控制车辆从上一路段流入下一路段.首先提出了"汽车池"的概念,来控制每一路口车辆的流入;然后通过路口随机慢化,来模拟路口对交通的影响;最后,当车辆离开时,依直行率进入下一路段,实现车流的继续流动.同时,通过数值模拟,仿真了不同条件下的交通情况,对重要参数进行了研究.结果表明,出现了混合流这一新的现象,拥堵地段与非拥堵地段间存在明显的界限.拥堵往往最先从路口开始,然后蔓延到整个路段.多路段道路还存在临界突变的特性.随着车辆流入概率的增大,路口对平均速度和车流密度的影响愈加明显.当流入概率超过一定阈值时,车辆缓慢地增加也会引起整体道路通行能力的迅速下降. 相似文献
38.
评价网络中节点的信息传播影响力对于理解网络结构与网络功能具有重要意义.目前,许多基于最短路径的指标,如接近中心性、介数中心性以及半局部(SP)指标等相继用于评价节点传播影响力.最短路径表示节点间信息传播途径始终选择最优方式,然而实际上网络间的信息传播过程更类似于随机游走,信息的传播途径可以是节点间的任一可达路径,在集聚系数高的网络中,节点的局部高聚簇性有利于信息的有效扩散,若只考虑信息按最优传播方式即最短路径传播,则会低估节点信息传播的能力,从而降低节点影响力的排序精度.综合考虑节点与三步内邻居间的有效可达路径以及信息传播率,提出了一种SP指标的改进算法,即ASP算法.在多个经典的实际网络和人工网络上利用SIR模型对传播过程进行仿真,结果表明ASP指标与度指标、核数指标、接近中心性指标、介数中心性指标以及SP指标相比,可以更精确地对节点传播影响力进行排序. 相似文献
39.
Herbert JM Jacobson LD Lao KU Rohrdanz MA 《Physical chemistry chemical physics : PCCP》2012,14(21):7679-7699
A method that we have recently introduced for rapid computation of intermolecular interaction energies is reformulated and subjected to further tests. The method employs monomer-based self-consistent field calculations with an electrostatic embedding designed to capture many-body polarization (the "XPol" procedure), augmented by pairwise symmetry-adapted perturbation theory (SAPT) to capture dispersion and exchange interactions along with any remaining induction effects. A rigorous derivation of the XPol+SAPT methodology is presented here, which demonstrates that the method is systematically improvable, and moreover introduces some additional intermolecular interactions as compared to the more heuristic derivation that was presented previously. Applications to various non-covalent complexes and clusters are presented, including geometry optimizations and one-dimensional potential energy scans. The performance of the XPol+SAPT methodology in its present form (based on second-order intermolecular perturbation theory and neglecting intramolecular electron correlation) is qualitatively acceptable across a wide variety of systems-and quantitatively quite good in certain cases-but the quality of the results is rather sensitive to the choice of one-particle basis set. Basis sets that work well for dispersion-bound systems offer less-than-optimal performance for clusters dominated by induction and electrostatic interactions, and vice versa. A compromise basis set is identified that affords good results for both induction and dispersion interactions, although this favorable performance ultimately relies on error cancellation, as in traditional low-order SAPT. Suggestions for future improvements to the methodology are discussed. 相似文献
40.