全文获取类型
收费全文 | 500篇 |
免费 | 11篇 |
国内免费 | 7篇 |
专业分类
化学 | 277篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 142篇 |
物理学 | 83篇 |
出版年
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 7篇 |
2015年 | 13篇 |
2014年 | 20篇 |
2013年 | 22篇 |
2012年 | 21篇 |
2011年 | 25篇 |
2010年 | 22篇 |
2009年 | 15篇 |
2008年 | 34篇 |
2007年 | 34篇 |
2006年 | 28篇 |
2005年 | 21篇 |
2004年 | 25篇 |
2003年 | 26篇 |
2002年 | 19篇 |
2001年 | 14篇 |
2000年 | 9篇 |
1999年 | 7篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有518条查询结果,搜索用时 15 毫秒
11.
Stable radical 2-(6-uradinyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl shows antiferromagnetic spin pairing with 2J/k= -14 K, attributable to a close contact between unpaired spin density on the imidazole-type nitrogen atoms; hydrogen bonds aid dimer formation, but do not appear to play an eletronic role in the magnetic behaviour. 相似文献
12.
13.
We have used molecular dynamics simulations to study the physical properties of modified TIP3P water model included in the CHARMM program, using four different methods-the Ewald summation technique, and three different spherical truncation methods-for the treatment of the long-range interactions. Both the structure and dynamics of the liquid water model were affected by the methods used to truncate the long-range interactions. For some of the methods artificial structuring of the model liquid was observed around the cutoff radius. The model liquid properties were also affected by the commonly applied temperature control methods. Four different methods for controlling the temperature of the system were studied, and the effects of these methods on the bulk properties for liquid water were analyzed. The system size was also found to change the dynamics of the model liquid water. Two control simulations with the SPC/E water model were carried out. The self-diffusion coefficient (D), the radial distribution function (g(OO)), the distance dependent Kirkwood G-factor [G(k)(r)] and the intermolecular potential energy (E(pot)) were determined from the different trajectories and compared with the experimental data. 相似文献
14.
Pekka Juusola Pentti Minkkinen Lasse Leino Jarmo K. Laihia 《Monatshefte für Chemie / Chemical Monthly》2007,138(10):951-965
Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation
constants (pK
a1 and pK
a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation
(pK
a1 = 3.43 ± 0.12 and pK
a2 = 5.80 ± 0.04) and (pK
a1 = 2.7 ± 0.3 and pK
a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride
solutions up to the isotonic salt concentration (0.154 mol dm−3), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at
temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK
a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric
dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived.
The obtained pK
a1 and pK
a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature.
An erratum to this article is available at . 相似文献
15.
Pekka J. Korhonen Kari Silvennoinen Jyrki WalleniusAnssi Öörni 《European Journal of Operational Research》2012
We investigate in a simple bi-criteria experimental study, whether subjects are consistent with a linear value function while making binary choices. Many inconsistencies appeared in our experiment. However, the impact of inconsistencies on the linearity vs. non-linearity of the value function was minor. Moreover, a linear value function seems to predict choices for bi-criteria problems quite well. This ability to predict is independent of whether the value function is diagnosed linear or not. Inconsistencies in responses did not necessarily change the original diagnosis of the form of the value function. Our findings have implications for the design and development of decision support tools for Multiple Criteria Decision Making problems. 相似文献
16.
Terhi Oja Petri Tähtinen Nadine Dreiack Pekka Mäntsälä Jarmo Niemi Mikko Metsä-Ketelä Karel D. Klika 《Tetrahedron: Asymmetry》2012,23(9):670-682
Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of 1H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties. 相似文献
17.
18.
We have had the chance to live through a fascinating revolution in measuring the fundamental empirical cosmological Hubble law. The key progress is analysed: (1) improvement of observational means (ground-based radio and optical observations, space missions); (2) understanding of the biases that affect both distant and local determinations of the Hubble constant; (3) new theoretical and observational results. These circumstances encourage us to take a critical look at some facts and ideas related to the cosmological red-shift. This is important because we are probably on the eve of a new understanding of our Universe, heralded by the need to interpret some cosmological key observations in terms of unknown processes and substances. 相似文献
19.
We prove an essentially sharp estimate in terms of generalized Hausdorff measures for the images of boundaries of Hölder domains under continuous Sobolev mappings, satisfying suitable Orlicz–Sobolev conditions. This estimate marks a dimension gap, which was first observed in [2] for conformal mappings. 相似文献
20.
Tuomas?N?reojaEmail author Andreas?Ebner Hermann?J.?Gruber Barbara?Taskinen Ferry?Kienberger Pekka?E.?H?nninen Vesa?P.?Hyt?nen Peter?Hinterdorfer Harri?H?rm? 《Analytical and bioanalytical chemistry》2014,406(2):493-503
Nanoparticle labels have enhanced the performance of diagnostic, screening, and other measurement applications and hold further promise for more sensitive, precise, and cost-effective assay technologies. Nevertheless, a clear view of the biomolecular interactions on the molecular level is missing. Controlling the ratio of molecular recognition over undesired nonspecific adhesion is the key to improve biosensing with nanoparticles. To improve this ratio with an aim to disallow nonspecific binding, a more detailed perspective into the kinetic differences between the cases is needed. We present the application of two novel methods to determine complex binding kinetics of bioconjugate nanoparticles, interferometry, and force spectroscopy. Force spectroscopy is an atomic force microscopy technique and optical interferometry is a direct method to monitor reaction kinetics in second-hour timescale, both having steadily increasing importance in nanomedicine. The combination is perfectly suited for this purpose, due to the high sensitivity to detect binding events and the ability to investigate biological samples under physiological conditions. We have attached a single biofunctionalized nanoparticle to the outer tip apex and studied the binding behavior of the nanoparticle in a sandwich-type immunoassay using dynamic force spectroscopy in millisecond timescale. Utilization of the two novel methods allowed characterization of binding kinetics in a time range spanning from 50 ms to 4 h. These experiments allowed detection and demonstration of differences between specific and nonspecific binding. Most importantly, nonspecific binding of a nanoparticle was reduced at contact times below 100 ms with the solid-phase surface. 相似文献