全文获取类型
收费全文 | 545篇 |
免费 | 27篇 |
专业分类
化学 | 414篇 |
力学 | 7篇 |
数学 | 61篇 |
物理学 | 90篇 |
出版年
2024年 | 2篇 |
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 16篇 |
2019年 | 11篇 |
2018年 | 7篇 |
2017年 | 10篇 |
2016年 | 14篇 |
2015年 | 22篇 |
2014年 | 21篇 |
2013年 | 39篇 |
2012年 | 47篇 |
2011年 | 56篇 |
2010年 | 34篇 |
2009年 | 31篇 |
2008年 | 40篇 |
2007年 | 32篇 |
2006年 | 35篇 |
2005年 | 20篇 |
2004年 | 12篇 |
2003年 | 13篇 |
2002年 | 14篇 |
2001年 | 4篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1969年 | 1篇 |
1967年 | 6篇 |
1966年 | 7篇 |
1956年 | 1篇 |
排序方式: 共有572条查询结果,搜索用时 15 毫秒
31.
A new method has been developed for the determination of the isotope abundance ratios of deuterium, D, and oxygen-18, 18O, in water vapor (and water) using selected ion flow tube mass spectrometry (SIFT-MS). H3O+ ions are injected into the helium carrier gas where they associate with the H2O and HDO molecules in a sample of water introduced into the carrier gas. The D and 18O contents of the product cluster ions H8DO4+ and H9(18)OO3+ at m/e = 74 and 75, respectively, are determined by reference to the majority cluster ion H9O4+ at m/e = 73. Allowance is made for the contribution of the H8(17)OO3+ ions to the m/z = 74 ions. Absolute isotopic ratios are measured within seconds without the need for precalibration of the SIFT-MS instrument, currently to an accuracy of better than 2%. 相似文献
32.
Ryding MJ Ruusuvuori K Andersson PU Zatula AS McGrath MJ Kurtén T Ortega IK Vehkamäki H Uggerud E 《The journal of physical chemistry. A》2012,116(20):4902-4908
Molecular cluster ions H(+)(H(2)O)(n), H(+)(pyridine)(H(2)O)(n), H(+)(pyridine)(2)(H(2)O)(n), and H(+)(NH(3))(pyridine)(H(2)O)(n) (n = 16-27) and their reactions with ammonia have been studied experimentally using a quadrupole-time-of-flight mass spectrometer. Abundance spectra, evaporation spectra, and reaction branching ratios display magic numbers for H(+)(NH(3))(pyridine)(H(2)O)(n) and H(+)(NH(3))(pyridine)(2)(H(2)O)(n) at n = 18, 20, and 27. The reactions between H(+)(pyridine)(m)(H(2)O)(n) and ammonia all seem to involve intracluster proton transfer to ammonia, thus giving clusters of high stability as evident from the loss of several water molecules from the reacting cluster. The pattern of the observed magic numbers suggest that H(+)(NH(3))(pyridine)(H(2)O)(n) have structures consisting of a NH(4)(+)(H(2)O)(n) core with the pyridine molecule hydrogen-bonded to the surface of the core. This is consistent with the results of high-level ab initio calculations of small protonated pyridine/ammonia/water clusters. 相似文献
33.
Errata to: “Vector-valued Modulation Spaces and Localization Operators with Operator-valued Symbols”
Patrik Wahlberg 《Integral Equations and Operator Theory》2008,62(4):575-577
In our article “Vector-valued Modulation Spaces and Localization Operators with Operator-valued Symbols”, Integr. equ. oper.
theory 59 (1) (2007), 99–128, Example 4.4 is false. We present a corrected example.
相似文献
34.
Felix Schmidt-Stein Robert Hahn Jan-Frederik Gnichwitz Yan Yan Song Nabeen K. Shrestha Andreas Hirsch Patrik Schmuki 《Electrochemistry communications》2009,11(11):2077-2080
The photocatalytic activity of titanium dioxide under X-ray radiation is of great interest for biomedical applications. In the present work we explore the use of compact TiO2 layers and TiO2 nanotubes for X-ray induced photocatalysis, in particular the degradation of organics and monolayer chain scission for drug release. The radiation was done with a conventional X-ray source and doses up to 50 × 10?3 J/kg. The results show the feasibility of X-ray catalysis on TiO2 and X-ray induced monolayer chain scission by the release of surface attached Zn–porphyrin molecules. Furthermore, a higher efficiency for anatase films and nanotubes is obtained than for amorphous morphologies. 相似文献
35.
36.
37.
Andriy Pysanenko Tianshu Wang Patrik Španěl David Smith 《Rapid communications in mass spectrometry : RCM》2009,23(8):1097-1104
Urine is commonly analysed in clinical practice by a variety of liquid‐phase techniques to check for excessive ketone bodies, proteins and salts to name just a few compounds. However, little work has been carried out to measure the volatile compounds emitted by urine since these do not yet have an established role in clinical diagnosis. There is, however, a growing body of evidence that these volatile compounds can be indicators of adverse physiological conditions and disease and with the advent of sensitive gas‐phase analytical methods they can be quickly quantified in urine headspace and potentially provide valuable support for clinical diagnosis. Thus, we are developing selected ion flow tube mass spectrometry, SIFT‐MS, for the real‐time analysis of urine headspace, ultimately to support rapid diagnosis in the clinical environment. In this paper we focus on volatile ketones in the headspace of aqueous solutions and urine donated by three healthy volunteers. Using SIFT‐MS, we have unambiguously quantified in urine headspace acetone, by far the most abundant ketone, butanone, pentanone, hexanone and heptanone using NO+ precursor ions. Further to this, we have determined the Henry's Law coefficients, HLC, for these ketones in aqueous solution to allow the liquid‐phase concentrations in urine to be estimated from headspace levels of their vapours. In addition, the influence of the addition of physiological amounts of dissolved urea, sodium chloride and hydrochloric acid on the partitioning of these ketones between the aqueous phase and gas phase has been investigated and found to be small, which gives greater credence to the use of the HLC obtained using aqueous solutions for the estimation of ketone concentrations in urine. Finally, parallel measurements of the levels of acetone in exhaled breath and urine headspace have been obtained and shown to be very similar, which gives support to the previous deduction from breath analysis that acetone is a truly systemic compound. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
38.
We consider the totally asymmetric simple exclusion process, a model in the KPZ universality class. We focus on the fluctuations of particle positions, starting with certain deterministic initial conditions. For large time t, one has regions with constant and linearly decreasing density. The fluctuations on these two regions are given by the Airy1 and Airy2 processes, whose one‐point distributions are the GOE and GUE Tracy‐Widom distributions of random matrix theory. In this paper we analyze the transition region between these two regimes and obtain the transition process. Its one‐point distribution is a new interpolation between GOE and GUE edge distributions. © 2007 Wiley Periodicals, Inc. 相似文献
39.
40.
Andersson M Hedin J Johansson P Nordström J Nydén M 《The journal of physical chemistry. A》2010,114(50):13146-13153
Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position. 相似文献