全文获取类型
收费全文 | 629篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 437篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 111篇 |
物理学 | 85篇 |
出版年
2023年 | 7篇 |
2022年 | 3篇 |
2021年 | 9篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 6篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 29篇 |
2012年 | 30篇 |
2011年 | 34篇 |
2010年 | 19篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 32篇 |
2006年 | 33篇 |
2005年 | 29篇 |
2004年 | 28篇 |
2003年 | 21篇 |
2002年 | 21篇 |
2001年 | 12篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 5篇 |
1997年 | 8篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 9篇 |
1980年 | 4篇 |
1978年 | 7篇 |
1977年 | 9篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1974年 | 8篇 |
1868年 | 2篇 |
排序方式: 共有650条查询结果,搜索用时 15 毫秒
1.
A two-dimensional framework (G,p) is
a graph G = (V,E) together with a map p: V → ℝ2. We view (G,p) as a straight line realization of G in ℝ2. Two realizations of G are equivalent if the corresponding edges in the two frameworks have the same length.
A pair of vertices {u,v} is globally linked in G if %and for all equivalent frameworks (G,q), the distance between the points
corresponding to u and v is the same
in all pairs of equivalent generic realizations of G. The graph G is globally rigid
if all of its pairs of vertices are globally linked. We extend the characterization of globally rigid graphs given by the
first two authors [13] by characterizing globally linked pairs in M-connected graphs, an important family of rigid graphs.
As a byproduct we simplify the proof of a result of Connelly [6] which is a key step in the characterization of globally rigid
graphs. We also determine the number of distinct realizations of an M-connected graph, each of which is equivalent to a given
generic realization. Bounds on this number for minimally rigid graphs were obtained by Borcea and Streinu in [3]. 相似文献
2.
3.
Let G = (V,E) be a graph or digraph and r : V → Z+. An r‐detachment of G is a graph H obtained by ‘splitting’ each vertex ν ∈ V into r(ν) vertices. The vertices ν1,…,νr(ν) obtained by splitting ν are called the pieces of ν in H. Every edge uν ∈ E corresponds to an edge of H connecting some piece of u to some piece of ν. Crispin Nash‐Williams 9 gave necessary and sufficient conditions for a graph to have a k‐edge‐connected r‐detachment. He also solved the version where the degrees of all the pieces are specified. In this paper, we solve the same problems for directed graphs. We also give a simple and self‐contained new proof for the undirected result. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 67–77, 2003 相似文献
4.
5.
Spikmans V Lane SJ Leavens B Manz A Smith NW 《Rapid communications in mass spectrometry : RCM》2002,16(14):1377-1388
A system is presented that demonstrates the principle of on-line and on-chip post-column derivatisation reactions in micro-high-performance liquid chromatography (micro-HPLC) hyphenated to electrospray time-of-flight mass spectrometry (ESI-TOFMS). In this micro-HPLC-chip-MS set-up, the analytes are separated using gradient micro-HPLC and subsequently derivatised on-chip and detected. One of the major limitations of MS detection is its dependency on the degree of ionisation, which is widely variable and compound-specific. Optimising and controlling the degree of ionisation in a simple manner would allow MS detection to be truly generic. One way of achieving this is by pre-ionisation of analytes using simple derivatisation procedures that are both rapid and quantitative. Performing this in situ on the system described here overcomes issues of sample handling and efficiency losses when time-consuming "bench chemistry" is necessary prior to analysis. The power of the system is demonstrated by the separation of primary and secondary amines, which are subsequently derivatised with a positively charged phosphonium complex and detected in an enhanced manner. Typically, molecular cations (M(+)) are detected showing that the ionisation process is dominated by the phosphonium species, leading to more constant ionisation for a variety of compounds. In addition, stable isotopically labelled ((12)C/(13)C)-phosphonium reagent is used for the reactions, allowing for inherent signal/noise (S/N) improvement and automated data processing using cluster analysis. A similar reaction scheme is used for the derivatisation of ketones and aldehydes, also demonstrating dramatic increases in sensitivity, especially with increasing temperature. Minimal loss in chromatographic fidelity in terms of retention times is observed by the introduction of the micromixer chip into the system. Optimal flow rates in micro-HPLC and ESI-MS are compatible with flow rates for the chip as well as a multitude of in-line optical detectors including UV and fluorescence. In addition, the micromixer chip can be positioned pre-column if preferred. The system is robust, easily fully automated and applicable to a wide variety of reactions. The system has a major advantage in its simple robust connection to the "normal scale" outside world. 相似文献
6.
7.
57Fe electric and magnetic hyperfine parameters were calculated for a series of 10 iron model complexes, covering a wide range of oxidation and spin states. Employing the B3LYP hybrid method, results from nonrelativistic density functional theory (DFT) and quasi-relativistic DFT within the zero-order regular approximation (ZORA) were compared. Electron densities at the iron nuclei were calculated and correlated with experimental isomer shifts. It was shown that the fit parameters do not depend on a specific training set of iron complexes and are, therefore, more universal than might be expected. The nonrelativistic and quasi-relativistic electron densities gave fit parameters of similar quality; the ZORA densities are only shifted by a factor of 1.32, upward in the direction of the four-component Dirac-Fock value. From a correlation of calculated electric field gradients and experimental quadrupole splittings, the value of the 57Fe nuclear quadrupole moment was redetermined to a value of 0.16 barn, in good agreement with other studies. The ZORA approach gave no additional improvement of the calculated quadrupole splittings in comparison to the nonrelativistic approach. The comparison of the calculated and measured 57Fe isotropic hyperfine coupling constants (hfcc's) revealed that both the ZORA approach and the inclusion of spin-orbit contributions lead to better agreement between theory and experiment in comparison to the nonrelativistic results. For all iron complexes with small spin-orbit contributions (high-spin ferric and ferryl systems), a distinct underestimation of the isotropic hfcc's was found. Scaling factors of 1.81 (nonrelativistic DFT) and 1.69 (ZORA) are suggested. The calculated 57Fe isotropic hfcc's of the remaining model systems (low-spin ferric and high-spin ferrous systems) contain 10-50% second-order contributions and were found to be in reasonable agreement with the experimental results. This is assumed to be the consequence of error cancellation because g-tensor calculations for these systems are of poor quality with the existing DFT approaches. Excellent agreement between theory and experiment was found for the 57Fe anisotropic hfcc's. Finally, all of the obtained fit parameters were used for an application study of the [Fe(H2O)6]3+ ion. The calculated spectroscopic data are in good agreement with the Mossbauer and electron paramagnetic resonance results discussed in detail in a forthcoming paper. 相似文献
8.
Bill Boggess Kelsey D. Cook 《Journal of the American Society for Mass Spectrometry》1994,5(2):100-105
The flux or beam density (equivalent current/area) of xenon atoms striking the sample target from a saddle field fast-atom bombardment (FAB) gun has been compared with that from a cesium ion gun mounted on the same instrument. A shielded Faraday cup mounted on the end of a solids probe was used to measure directly the flux of the Cs+ beam. Samples of methylene blue in glycerol solution were then exposed to the ion beam at different fluxes and the extents of reduction were measured. The extent of reduction varied linearly with flux up to a value of about 1.16 × 1013 particles s?1 cm?2 (1.85 μ cm?2); above this level, the reduction effect appeared to saturate. FAB spectra were obtained from the same dye solution by using varying settings of the FAB gun. By comparing the extents of reduction of the dye from the two guns, the flux from the atom gun could be estimated. Observation of luminescence from a CsI-coated target allowed estimation of the area of the atom beam. The atom beam “equivalent current” could then be calculated by multiplying the flux times the area. It was noted that for given settings, the flux from the atom gun depended on the physical condition of the gun electrodes. With new electrodes, a flux ≥ 1.16 × 1013 particles s?1 cm?2 was obtained with nominal gun emission currents of 0.60–1.0 mA. Electrodes used extensively, but freshly cleaned, provided a flux of ~ 8 × 1012 particles s?1 cm?2 at nominal emission currents of 0.40–1.0 mA. With dirty electrodes this flux could only be achieved at the highest (1.0 mA) emission current. This decline in performance occurs over a matter of months as a result of contamination and erosion of the electrodes during use. Such behavior can adversely affect spectral reproducibility even when nominal FAB gun voltage and emission current are carefully reproduced. 相似文献
9.
Current methods of analysis for ethylene oxide (EO) in medical devices include headspace and simulated-use extractions followed by gas chromatography with either a packed or a capillary column. The quantitation limits are about 0.5-1.0 microg/g for a packed column and about 0.1-0.2 microg/g for a capillary column. The current allowable levels of EO on medical devices sterilized with EO gas as outlined in International Organization for Standardization (ISO) 10993-7 may be significantly reduced from current levels by applying the ISO Draft International Standard 10993-17 method for establishing allowable limits. This may require EO test methods with detection and quantitation limits that are much lower than those of the currently available methods. This paper describes a new method that was developed for the determination of low-level EO by solid-phase microextraction using the direct-immersion method. Factors such as temperature and stirring were found to affect absorption efficiency and absorption time. A low extraction temperature (about 6 degrees C) was found to be more efficient than room-temperature extraction. Stirring was found to reduce absorption time by about 50%. Under these conditions, detection and quantitation limits of 0.002 and 0.009 microg/g, respectively, were obtained by using a capillary column. As a result, this method makes compliance with lower EO limits feasible. 相似文献
10.
M. Müther E. Bill A. X. Trautwein D. Mandon R. Weiss A. Gold K. Jayaraj R. N. Austin 《Hyperfine Interactions》1994,91(1):803-808
In order to study structural influences on the interaction of Fe(IV) (S=1) and porphyrin cation radical (S=1/2) in high-valent iron porphyrin complexes of the type ¦X-(TMP)Fe=O¦+(Cl–), X=I, Br2, Br4 were generated by mCPBA oxidation of corresponding Fe(III) porphyrins. The halogen substitution at the peripheral positions of the porphyrin leads to distortion of the planar porphyrin ring of ¦(TMP)Fe=O¦+. The new species have beeen investigated by temperature-dependent EPR and field-dependent Mössbauer spectroscopy; for the evaluation of spectra, we adopted the spin-Hamiltonian formalism including exchange interaction explicitly. As in ¦(TMP)Fe=O¦+, strong ferromagnetic spin coupling was observed with|J0|D=0.9–1 and a zero-field spltting ofD32 cm–1. For consistent parametrization of EPR and Mössbauer results, anisotropic coupling had to be introduced. Compared to ¦(TMP)Fe=O¦+ [1], analysis of the spectroscopic data shows that zero-field splitting and spin coupling is only slightly affected by the halogen distortion of the porphyrin structure. 相似文献