全文获取类型
收费全文 | 366篇 |
免费 | 17篇 |
专业分类
化学 | 273篇 |
力学 | 7篇 |
数学 | 36篇 |
物理学 | 67篇 |
出版年
2024年 | 2篇 |
2023年 | 8篇 |
2022年 | 1篇 |
2021年 | 12篇 |
2020年 | 4篇 |
2019年 | 8篇 |
2018年 | 9篇 |
2017年 | 9篇 |
2016年 | 12篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 18篇 |
2012年 | 17篇 |
2011年 | 45篇 |
2010年 | 16篇 |
2009年 | 9篇 |
2008年 | 31篇 |
2007年 | 35篇 |
2006年 | 22篇 |
2005年 | 25篇 |
2004年 | 9篇 |
2003年 | 18篇 |
2002年 | 10篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1977年 | 1篇 |
1972年 | 1篇 |
1858年 | 1篇 |
排序方式: 共有383条查询结果,搜索用时 547 毫秒
1.
2.
The Zakai equation for the unnormalized conditional density is derived as a mild stochastic bilinear differential equation on a suitableL
2 space. It is assumed that the Markov semigroup corresponding to the state process isC
0 on such space. This allows the establishment of the existence and uniqueness of the solution by means of general theorems on stochastic differential equations in Hilbert space. Moreover, an easy treatment of convergence conditions can be given for a general class of finite-dimensional approximations, including Galerkin schemes. This is done by using a general continuity result for the solution of a mild stochastic bilinear differential equation on a Hilbert space with respect to the semigroup, the forcing operator, and the initial state, within a suitable topology. 相似文献
3.
The preliminary results described here show the complete transfer of Hg(II) ions, in the absence of a chelating agent in 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids; the lag time required to gain the quantitative metal ion partition turned out to be strongly dependent both on alkyl chain length on the imidazolium ring and on the working temperature. 相似文献
4.
5.
Sottini S Abbruzzetti S Spyrakis F Bettati S Ronda L Mozzarelli A Viappiani C 《Journal of the American Chemical Society》2005,127(49):17427-17432
Biphasic geminate rebinding of CO to myoglobin upon flash photolysis has been associated to ligand distribution in hydrophobic cavities, structurally detected by time-resolved crystallography, xenon occupancy, and molecular simulations. We show that the time course of CO rebinding to human hemoglobin also exhibits a biphasic geminate rebinding when the protein is entrapped in wet nanoporous silica gel. A simple branched kinetic scheme, involving the bound state A, the primary docking site C, and a secondary binding site B was used to calculate the microscopic rates and the time-dependent population of the intermediate species. The activation enthalpies of the associated transitions were determined in the absence and presence of 80% glycerol. Potential hydrophobic docking cavities within the alpha and beta chains of hemoglobin were identified by computational modeling using xenon as a probe. A hydrophobic pocket on the distal side of the heme, corresponding to Xe4 in Mb, and a nearby site that does not have a correspondence in Mb were detected. Neither potential xenon sites on the proximal side nor a migration channel from the distal to proximal site was located. The small enthalpic barriers between states B and C are in very good agreement with the location of the xenon sites on the distal side. Furthermore, the connection between the two xenon sites is relatively open, explaining why the decreased mobility of the protein with viscosity only slightly perturbs the energetics of ligand migration between the two sites. 相似文献
6.
Daniela P. Mesquita Cristiano Leal Jorge R. Cunha Adrian Oehmen A. Luís Amaral Maria A.M. Reis Eugénio C. Ferreira 《Analytica chimica acta》2013
The present study focuses on predicting the concentration of intracellular storage polymers in enhanced biological phosphorus removal (EBPR) systems. For that purpose, quantitative image analysis techniques were developed for determining the intracellular concentrations of PHA (PHB and PHV) with Nile blue and glycogen with aniline blue staining. Partial least squares (PLS) were used to predict the standard analytical values of these polymers by the proposed methodology. Identification of the aerobic and anaerobic stages proved to be crucial for improving the assessment of PHA, PHB and PHV intracellular concentrations. Current Nile blue based methodology can be seen as a feasible starting point for further enhancement. Glycogen detection based on the developed aniline blue staining methodology combined with the image analysis data proved to be a promising technique, toward the elimination of the need for analytical off-line measurements. 相似文献
7.
Dr. Gabriel Menendez Rodriguez Dr. Francesco Zaccaria Leonardo Tensi Prof. Cristiano Zuccaccia Prof. Paola Belanzoni Prof. Alceo Macchioni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2050-2064
The degradation pathways of highly active [Cp*Ir(κ2-N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO3), 2 undergoes partial protonation of the amide moiety, inducing rapid κ2-N,N to κ2-N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ2-N,N key intermediate of FA dehydrogenation ( INH ), bearing a N-protonated pica, can easily transform into the κ2-N,O analogue ( INH2 ; ΔG≠≈11 kcal mol−1, ΔG ≈−5 kcal mol−1). Intramolecular hydrogen liberation from INH2 is predicted to be rather prohibitive (ΔG≠≈26 kcal mol−1, ΔG≈23 kcal mol−1), indicating that FA dehydrogenation should involve mostly κ2-N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c . DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible. 相似文献
8.
Alisson J. Santana Denis A. Turchetti Cristiano Zanlorenzi Jos C. R. Santos Edson Laureto Adilson J. A. De Oliveira Leni Akcelrud 《Journal of Polymer Science.Polymer Physics》2019,57(6):304-311
Poly[9,9′‐dihexylfluorene‐2,7‐diyl)‐6,6″‐(2,2′:6′,2″‐terpyridine)] (LaPPS75) and its complexes with neodymium were synthesized and characterized. Magnetic measurements showed that the noncomplexed polymer presented a ferromagnetic contribution due to the formation of π stacking, and that in absence of those, the ferromagnetic behavior is suppressed. The pristine polymer, the complexed one and a low‐molecular‐weight model compound with the same structure of the complexed site in the parent polymer were studied. The observed behavior found is presented and discussed, the most important finding was that when a conjugated chain is used as a host for the metallic ion, an amplification of four times for the magnetization is achieved, using the same metallic content for complexed polymer and model compound for comparison. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 304–311 相似文献
9.
10.