全文获取类型
收费全文 | 186篇 |
免费 | 10篇 |
专业分类
化学 | 134篇 |
晶体学 | 1篇 |
力学 | 13篇 |
数学 | 26篇 |
物理学 | 22篇 |
出版年
2024年 | 2篇 |
2022年 | 8篇 |
2021年 | 17篇 |
2020年 | 7篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 12篇 |
2015年 | 6篇 |
2014年 | 6篇 |
2013年 | 7篇 |
2012年 | 8篇 |
2011年 | 7篇 |
2010年 | 8篇 |
2009年 | 6篇 |
2008年 | 8篇 |
2007年 | 17篇 |
2006年 | 10篇 |
2005年 | 8篇 |
2004年 | 12篇 |
2003年 | 7篇 |
2002年 | 6篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1991年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1982年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有196条查询结果,搜索用时 0 毫秒
101.
Dr. Prokopis C. Andrikopoulos Dr. Zdenek Sobalik Dr. Jana Novakova Dr. Petr Sazama Dr. Stepan Sklenak 《Chemphyschem》2013,14(3):520-531
The role of framework oxygen atoms in N2O decomposition [N2O(g)→N2(g) and 1/2O2(g)] over Fe‐ferrierite is investigated employing a combined experimental (N218O decomposition in batch experiments followed by mass spectroscopy measurements) and theoretical (density functional theory calculations) approach. The occurrence of the isotope exchange indicates that framework oxygen atoms are involved in the N2O decomposition catalyzed by Fe‐ferrierite. Our study, using an Fe‐ferrierite sample with iron exclusively present as FeII cations accommodated in the cationic sites, shows that the mobility of framework oxygen atoms in the temperature range: 553 to 593 K is limited to the four framework oxygen atoms of the two AlO4? tetrahedra forming cationic sites that accomodate FeII. They exchange with the Fe extra‐framework 18O atom originating from the decomposed N218O. We found, using DFT calculations, that O2 molecules facilitate the oxygen exchange. However, the corresponding calculated energy barrier of 87 kcal mol?1 is still very high and it is higher than the assumed experimental value based on the occurrence of the sluggish oxygen exchange at 553 K. 相似文献
102.
Ivan Hevus Dean C. Webster John McNamara Nicole G. Ricapito Stepan Tymoshenko 《Journal of polymer science. Part A, Polymer chemistry》2021,59(8):665-674
The applicability of polyesters across a wide range of fields creates a demand for novel polyester structures that can offer advanced product performance. Two critical factors to the development of unique polymer architectures are the speed at which new polymeric systems can be synthesized and the available selection of monomers from which polymers are designed. Herein, we successfully demonstrate the applicability of a high-throughput (HT) approach to polyesterification reaction between dicarboxylic acids and diols in reaction conditions similar to those used in industry. Furthermore, we apply our HT design to a series of bio-based monomers whose unique structures offer potential for enhanced properties in polyester-based systems. Using a custom-built array of small-scale film reactors, we conducted a parallel screening of 13 bio-based dicarboxylic acids as potential monomers in the synthesis of polyester polyols through copolymerization with 1,6-hexanediol. The polyester polyols were characterized for their molecular weight and thermal properties. Carrying out polyesterification reactions in small-scale film reactors is seen as a quick and powerful tool for screening the effectiveness of a series of potential monomers, as this method offers highly controllable and reproducible reaction conditions in every reactor coupled with the ability to use a minimum amount of reagents. 相似文献
103.
104.
By means of critical point theory, existence theorems for nontrivial solutions to the Hammerstein equation x = KFx are given, where K is a compact linear integral operator and F is a nonlinear superposition operator. To this end, appropriate conditions on the spectrum of the linear parte are combined with growth and representation conditions on the nonlinear part to ensure the applicability of the mountain — pass lemma. The abstract existence theorems are applied to nonlinear elliptic equations and systems subject to Dirichlet boundary conditions. 相似文献
105.
Pinijsuwan S Shipovskov S Surareungchai W Ferapontova EE Gothelf KV 《Organic & biomolecular chemistry》2011,9(18):6352-6356
A lipase-based assay for detection of specific DNA sequences has been developed. Lipase from Candida antarctica was conjugated to DNA and captured on magnetic beads in a sandwich assay, in which the binding was dependent on the presence of a specific target DNA. For amplification and to generate a detectable readout the captured lipase was applied to an optical assay that takes advantage of the enzymatic activity of lipase. The assay applies p-nitrophenol octanoate (NPO) as the substrate and in the presence of lipase the ester is hydrolyzed to p-nitrophenolate which has a strong absorbance at 405 nm. The method provides detection a detection limit of 200 fmol target DNA and it was able to distinguish single base mismatches from the fully complementary target. 相似文献
106.
Dai HX Stepan AF Plummer MS Zhang YH Yu JQ 《Journal of the American Chemical Society》2011,133(18):7222-7228
Modern drug discovery is contingent on identifying lead compounds and rapidly synthesizing analogues. The use of a common pharmacophore to direct multiple and divergent C-H functionalizations of lead compounds is a particularly attractive approach. Herein, we demonstrate the viability of late-stage diversification through the divergent C-H functionalization of sulfonamides, an important class of pharmacophores found in nearly 200 drugs currently on the market, including the non-steroidal anti-inflammatory blockbuster drug celecoxib. We developed a set of six categorically different sulfonamide C-H functionalization reactions (olefination, arylation, alkylation, halogenation, carboxylation, and carbonylation), each representing a distinct handle for further diversification to reach a large number of analogues. We then performed late-stage, site-selective diversification of a sulfonamide drug candidate containing multiple potentially reactive C-H bonds to synthesize directly novel celecoxib analogues as potential cyclooxygenase-II (COX-2)-specific inhibitors. Together with other recently developed practical directing groups, such as CONHOMe and CONHC(6)F(5), sulfonamide directing groups demonstrate that the auxiliary approach established in asymmetric catalysis can be equally effective in developing broadly useful C-H activation reactions. 相似文献
107.
This paper analyzes the double Neimark–Sacker bifurcation occurring in a two-DoF system, subject to PD digital position control. In the model the control force is considered piecewise constant. Introducing a nonlinearity related to the saturation of the control force, the bifurcations occurring in the system are analyzed. The system is generally losing stability through Neimark–Sacker bifurcations, with relatively simple dynamics. However, the interaction of two different Neimark–Sacker bifurcations steers the system to much more complicated behavior. Our analysis is carried out using the method proposed by Kuznetsov and Meijer. It consists of reducing the dynamics of the nonlinear map to its local center manifold, eliminating the non-internally resonant nonlinear terms and transforming the nonlinear map to an amplitude map, that describes the local dynamics of the system. The analysis of this amplitude map allows us to define regions, in the space of the control gains, with a close interaction of the two bifurcations, which generates unstable quasiperiodic motion on a 3-torus, coexisting with two stable 2-torus quasiperiodic motions. Other regions in the space of the control gains show the coexistence of 2-torus quasiperiodic solutions, one stable and the other unstable. All the results described in this work are analytical and obtained in closed form, numerical simulations illustrate and confirm the analytical results. 相似文献
108.
We investigate approximations of the vertex coupling on a star-shaped graph by families of operators with singularly scaled rank-one interactions. We find a family of vertex couplings, generalizing the δ′-interaction on the line, and show that with a suitable choice of the parameters they can be approximated in this way in the norm-resolvent sense. We also analyze spectral properties of the involved operators and demonstrate the convergence of the corresponding on-shell scattering matrices. 相似文献
109.
Kinematic oscillation of railway wheelsets is investigated in the case of a straight track, focusing on the nonlinear effects of the geometry of wheel and rail profiles. Euler angles are used to describe the motion of the wheelset, the contacting bodies are modelled by two-parametric rigid surfaces. The surface parameters of the current contact points are followed during the calculations. The curvatures and their variations are also included in the analysis. From the implicit form of the geometric constraints, the dynamics is determined by means of Taylor expansion. Equations of the local nonlinear motion are derived and the qualitative behaviour of the system is given. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
110.
We investigate the convergence of a two-step modification of the Gauss-Newton method applying the generalized Lipschitz condition for the first and second order derivatives. The convergence order as well as the convergence radius of the method are studied and the uniqueness ball of solution of the nonlinear least squares problem is examined. Finally, we carry out numerical experiments on a set of well-known test problems. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献