全文获取类型
收费全文 | 321篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 207篇 |
晶体学 | 4篇 |
力学 | 23篇 |
数学 | 88篇 |
物理学 | 24篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 4篇 |
2019年 | 9篇 |
2018年 | 4篇 |
2017年 | 5篇 |
2016年 | 5篇 |
2015年 | 24篇 |
2014年 | 21篇 |
2013年 | 23篇 |
2012年 | 20篇 |
2011年 | 26篇 |
2010年 | 17篇 |
2009年 | 14篇 |
2008年 | 19篇 |
2007年 | 30篇 |
2006年 | 23篇 |
2005年 | 10篇 |
2004年 | 17篇 |
2003年 | 18篇 |
2002年 | 11篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有346条查询结果,搜索用时 15 毫秒
61.
Jardar Andersen Teodor Gabriel Crainic Marielle Christiansen 《European Journal of Operational Research》2009
We present a new optimization model for the tactical design of scheduled service networks for transportation systems where several entities provide service and internal exchanges and coordination with neighboring systems is critical. Internal exchanges represent border crossings necessitating changes of vehicles, while the coordination with neighboring systems represents intermodal operations. For a given demand, the model determines departure times of the services such that throughput time of the demand in the system is minimized. The model is an extension of the design-balanced capacitated multicommodity network design model that we denote service network design with asset management and multiple fleet coordination to emphasize the explicit modeling of different vehicle fleets. Data from a real-world problem addressing the planning of new rail freight services across borders serves to illustrate the capabilities of the formulation. We analyze how synchronization with collaborating services and removal of border-crossing operations impact the throughput time for the freight. We identify a significant potential for system performance enhancement from synchronization among collaborating services for the problem studied. 相似文献
62.
Linke-Schaetzel M Anson CE Powell AK Buth G Palomares E Durrant JD Balaban TS Lehn JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1931-1940
A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W conformation an energy-transfer process is seen from the free base to the Zn-metallated porphyrin. In the U conformation in Zn2Au the donor luminescence resulting from the singlet excited state of the Zn wing is strongly, quenched not only due to the heavy atom effect but also due to a fast electron-transfer process to the ground state of the Au wing. Furthermore, the binding of (alpha,omega)-diamine substrates to the Zn(II)-porphyrin sites can also influence the conformation of the system. For the Zn2Zn construct, single-crystal diffraction experiments with synchrotron radiation allowed the structure to be solved by direct methods and fully refined; it shows the expected U conformation. The central Zn atom is six-coordinate, whereby the zinc atom is coordinated by the eta3-terpy ligand as well by monodentate and semi-chelating acetate anions. The structure is made rigid by hydrogen bonds involving the aqua ligands on the outer Zn centres and acetate oxygen atoms. The present system thus represents a double-trigger-modulated optomechanical switching device with selective substrate binding for either metal atoms or tailored ligands. Both energy- and electron-transfer processes can be controlled opening a means of improving the on/off ratio in future constructs. 相似文献
63.
Masllorens E Rodríguez M Romero I Roglans A Parella T Benet-Buchholz J Poyatos M Llobet A 《Journal of the American Chemical Society》2006,128(16):5306-5307
Three new Ru-aqua complexes containing a mixed carbene and pyridylic ligands with general formulas [Ru(CNC)(bpy)(H2O)](PF6)2 (1) (CNC is 2,6-bis(butylimidazol-2-ylidene)pyridine; bpy is 2,2'-bipyridine) and cis-/trans-[Ru(CNC)(nBu-CN)(H2O)](PF6)2 (cis-2 and trans-2) (nBu-CN is 2-(butylimidazol-2-ylidene)pyridine) have been prepared and structurally characterized both in the solid state (monocrystal X-ray diffraction analysis for 1 and for the related complex trans-[Ru(Br)(CNC)(nBu-CN)](PF6)) and in solution (for all of them) through NMR. The electrochemical properties of these three Ru-aqua complexes have been investigated by cyclic voltammetry, differential pulse voltammetry and Coulombimetric techniques. It is found that, for complex 1 at pH 7, the difference between the IV/III and the III/II redox couples (DeltaE1/2) is 50 mV, which is the smallest ever reported for this type of complex. On the other hand, for complexes cis-2 and trans-2, the oxidation state III is unstable with respect to disproportionation to II and IV. The reactivity of their Ru=O species has been tested toward cis-beta-methylstyrene oxidation, and it has been compared to [Ru(O)(trpy)(bpy)]2+. An inverse correlation between the degree of cis/trans-epoxide isomerization and DeltaE1/2 is found. In particular, for complexes cis-2 and trans-2, which have a DeltaE1/2 < 0, the epoxidation is highly stereoselective, yielding only cis-epoxide. 相似文献
64.
Nolis P Espinosa JF Parella T 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,180(1):39-50
Most conventional heteronuclear spin-state-selective (S(3)) NMR experiments only work for a specific multiplicity, typically IS spin systems. Here, we introduce a general and efficient IPAP strategy to achieve S(3) editing simultaneously for all multiplicities in the acquisition dimension of the HSQC experiment. Complementary in-phase (HSQC-IP) and anti-phase (HSQC-AP) data are separately recorded with a simple phase exchange of two 90 degrees proton pulses involved in the mixing process of the F2-coupled sensitivity-improved HSQC pulse sequence. Additive and subtractive linear combination of these IP/AP data generates simplified F2-alpha/beta-spin-edited HSQC subspectra for all IS, I(2)S, and I(3)S spin systems and combines enhanced and optimized sensitivity with excellent tolerance to unwanted cross-talk contributions over a considerable range of coupling constants. Practical aspects such as pulse phase settings, transfer efficiency dependence, inter-pulse delay optimization, and percentage of cross-talk are theoretically analyzed and discussed as a function of each I(n)S multiplicity. Particular emphasis on the features associated to spin-editing in diastereotopic I(2)S spin systems and application to the measurement of long-range proton-carbon coupling constants are also provided. 相似文献
65.
Antoine Souliès Jeremy Pruvost Jack Legrand Cathy Castelain Teodor I. Burghelea 《Rheologica Acta》2013,52(6):589-605
A systematic study of the rheological properties of solutions of non-motile microalgae (Chlorella vulgaris CCAP 211-19) in a wide range of volume fractions is presented. As the volume fraction is gradually increased, several rheological regimes are observed. At low volume fractions (but yet beyond the Einstein diluted limit), the suspensions display a Newtonian rheological behaviour and the volume fraction dependence of the viscosity can be well described by the Quemada model (Quemada, Eur Phys J Appl Phys 1:119–127, 1997). For intermediate values of the volume fraction, a shear thinning behaviour is observed and the volume fraction dependence of the viscosity can be described by the Simha model (Simha, J Appl Phys 23:1020–1024, 1952). For the largest values of the volume fraction investigated, an apparent yield stress behaviour is observed. Increasing and decreasing stress ramps within this range of volume fractions indicate a thixotropic behaviour as well. The rheological behaviour observed within the high concentration regime bears similarities with the measurements performed by Heymann and Aksel (Phys Rev E 75:021505, 2007) on polymethyl methacrylate suspensions: irreversible flow behaviour (upon increasing/decreasing stresses) and dependence of the flow curve on the characteristic time of forcing (the averaging time per stress values). All these findings indicate a behaviour of the microalgae suspensions similar to that of suspensions of rigid particles. A deeper insight into the physical mechanisms underlying the shear thinning and the apparent yield stress regime is obtained by an in situ analysis of the microscopic flow of the suspension under shear. The shear thinning regime is associated to the formation of cell aggregates (flocs). Based on the Voronoi analysis of the correlation between the cell distribution and cell sizes, we suggest that the repulsive electrostatic interactions are responsible for this microscale organisation. The apparent yield stress regime originates in the formation of large-scale cell aggregates which behave as rigid plugs leading to a maximally random jammed state. 相似文献
66.
67.
68.
Gómez L Garrabou X Joglar J Bujons J Parella T Vilaplana C Cardona PJ Clapés P 《Organic & biomolecular chemistry》2012,10(31):6309-6321
The synthesis, conformational study and inhibitory properties of diverse indolizidine and quinolizidine iminocyclitols are described. The compounds were chemo-enzymatically synthesized by two-step aldol addition and reductive amination reactions. The aldol addition of dihydroxyacetone phosphate (DHAP) to N-Cbz-piperidine carbaldehyde derivatives catalyzed by L-rhamnulose 1-phosphate aldolase from Escherichia coli provides the key intermediates. The stereochemical outcome of both aldol addition and reductive amination depended upon the structure of the starting material and intermediates. The combination of both reactions furnished five indolizidine and six quinolizidine type iminocyclitols. A structural analysis by NMR and in silico density functional theory (DFT) calculations allowed us to determine the population of stereoisomers with the trans or cis ring fusion, as a consequence of the inversion of configuration of the bridgehead nitrogen. The trans fusion was by far the most stable, but for certain stereochemical configurations of the 3-hydroxymethyl and hydroxyl substituents both trans and cis fusion stereoisomers coexisted in different proportions. Some of the polyhydroxylated indolizidines and quinolizidines were shown to be moderate to good inhibitors against α-L-rhamnosidase from Penicillium decumbens. Indolizidines were found to be moderate inhibitors of the rat intestinal sucrase and of the exoglucosidase amyloglucosidase from Aspergillus niger. In spite of their activity against α-L-rhamnosidase, all the compounds were ineffective to inhibit the growth of the Mycobacterium tuberculosis, the causative agent of tuberculosis. 相似文献
69.
This paper presents a parallel tabu search algorithm that utilizes several different neighborhood structures for solving the capacitated vehicle routing problem. Single neighborhood or neighborhood combinations are encapsulated in tabu search threads and they cooperate through a solution pool for the purpose of exploiting their joint power. The computational experiments on 32 large scale benchmark instances show that the proposed method is highly effective and competitive, providing new best solutions to four instances while the average deviation of all best solutions found from the collective best results reported in the literature is about 0.22%. We are also able to associate the beneficial use of special neighborhoods with some test instance characteristics and uncover some sources of the collective power of multi-neighborhood cooperation. 相似文献
70.
We present an experimental investigation of the solid–fluid transition in a yield stress shear thinning physical gel (Carbopol® 940) under shear. Upon a gradual increase of the external forcing, we observe three distinct deformation regimes: an elastic solid-like regime (characterized by a linear stress–strain dependence), a solid–fluid phase coexistence regime (characterized by a competition between destruction and reformation of the gel), and a purely viscous regime (characterized by a power law stress-rate of strain dependence). The competition between destruction and reformation of the gel is investigated via both systematic measurements of the dynamic elastic moduli (as a function of stress, the amplitude, and temperature) and unsteady flow ramps. The transition from solid behavior to fluid behavior displays a clear hysteresis upon increasing and decreasing values of the external forcing. We find that the deformation power corresponding to the hysteresis region scales linearly with the rate at which the material is being forced (the degree of flow unsteadiness). In the asymptotic limit of small forcing rates, our results agree well with previous steady state investigations of the yielding transition. Based on these experimental findings, we suggest an analogy between the solid–fluid transition and a first-order phase transition, e.g., the magnetization of a ferro-magnet where irreversibility and hysteresis emerge as a consequence of a phase coexistence regime. In order to get further insight into the solid–fluid transition, our experimental findings are complemented by a simple kinetic model that qualitatively describes the structural hysteresis observed in our rheological experiments. The model is fairly well validated against oscillatory flow data by a partial reconstruction of the Pipkin space of the material’s response and its nonlinear spectral behavior. 相似文献