全文获取类型
收费全文 | 2069篇 |
免费 | 80篇 |
国内免费 | 20篇 |
专业分类
化学 | 1285篇 |
晶体学 | 6篇 |
力学 | 40篇 |
数学 | 266篇 |
物理学 | 572篇 |
出版年
2022年 | 14篇 |
2021年 | 19篇 |
2020年 | 27篇 |
2019年 | 30篇 |
2018年 | 19篇 |
2017年 | 16篇 |
2016年 | 47篇 |
2015年 | 48篇 |
2014年 | 57篇 |
2013年 | 98篇 |
2012年 | 126篇 |
2011年 | 125篇 |
2010年 | 71篇 |
2009年 | 55篇 |
2008年 | 94篇 |
2007年 | 119篇 |
2006年 | 103篇 |
2005年 | 91篇 |
2004年 | 75篇 |
2003年 | 47篇 |
2002年 | 40篇 |
2001年 | 31篇 |
2000年 | 34篇 |
1999年 | 23篇 |
1998年 | 18篇 |
1997年 | 17篇 |
1996年 | 31篇 |
1995年 | 36篇 |
1994年 | 39篇 |
1993年 | 30篇 |
1992年 | 28篇 |
1991年 | 25篇 |
1990年 | 17篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 14篇 |
1986年 | 26篇 |
1985年 | 31篇 |
1984年 | 36篇 |
1983年 | 18篇 |
1982年 | 28篇 |
1981年 | 37篇 |
1980年 | 23篇 |
1979年 | 26篇 |
1978年 | 27篇 |
1977年 | 24篇 |
1976年 | 32篇 |
1975年 | 27篇 |
1974年 | 16篇 |
1973年 | 23篇 |
排序方式: 共有2169条查询结果,搜索用时 0 毫秒
991.
Chekmenev EY Hövener J Norton VA Harris K Batchelder LS Bhattacharya P Ross BD Weitekamp DP 《Journal of the American Chemical Society》2008,130(13):4212-4213
We use the PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) method to achieve 13C polarization of approximately 20% in seconds in 1-13C-succinic-d2 acid. The high-field 13C multiplets are observed as a function of pH, and the line broadening of C1 is pronounced in the region of the pK values. The 2JCH, 3JCH, and 3JHH couplings needed for spin order transfer vary with pH and are best resolved at low pH leading to our use of pH approximately 3 for both the molecular addition of parahydrogen to 1-13C-fumaric acid-d2 and the subsequent transfer of spin order from the nascent protons to C1 of the succinic acid product. The methods described here may generalize to hyperpolarization of other carboxylic acids. The C1 spin-lattice relaxation time at neutral pH and 4.7 T is measured as 27 s in H2O and 56 s in D2O. Together with known rates of succinate uptake in kidneys, this allows an estimate of the prospects for the molecular spectroscopy of metabolism. 相似文献
992.
Liu H Ma D Blackley RA Zhou W Bao X 《Chemical communications (Cambridge, England)》2008,(23):2677-2679
A facile one-pot approach gave isolated silver nanoparticles anchored on a mesostructured silica matrix in a self-assembled way; these gave 100% CO conversion in CO oxidation at room temperature, which is higher than or comparable to the conversion obtained using noble metal catalysts. 相似文献
993.
Temperature gradient focusing (TGF) is a new and promising equilibrium gradient focusing method which can provide high concentration factors for improved detection limits in combination with high-resolution separation. In this technique, temperature-dependent buffer chemistry is employed to generate a gradient in the analyte electrophoretic velocity. By the application of a convective counter-flow, a zero-velocity point is created within a microchannel, at which location the ionic analytes accumulate or focus. In general, the analyte concentration is small when compared with buffer ion concentrations, such that the focusing mechanism works in the ideal, linearized regime. However, this presumption may at times be violated due to significant sample concentration growth or the use of a low-concentration buffer. Under these situations the sample concentration becomes non-negligible and can induce strong nonlinear interactions with buffer ions, which eventually lead to peak shifting and distortion, and the loss of detectability and resolution. In this work we combine theory, simulation, and experimental data to present a detailed study on nonlinear sample-buffer interactions in TGF. One of the key results is the derivation of a generalized Kohlrausch regulating function (KRF) that is valid for systems in which the electrophoretic mobilities are not constant but vary spatially. This generalized KRF greatly facilitates analysis, allowing reduction of the problem to a single equation describing sample concentration evolution, and is applicable to other problems with heterogeneous electrophoretic mobilities. Using this sample evolution equation we have derived an understanding of the nonlinear peak deformation phenomenon observed experimentally in TGF. We have used numerical simulations to validate our theory and to quantitatively predict TGF. Our simulation results demonstrate excellent agreement with experimental data, and also indicate that the proper inclusion of Taylor dispersion is important for the accurate modeling of TGF. This work is an important first step towards the understanding and prediction of the more complex, nonlinear, and multi-species interactions which often occur in on-chip electrophoretic assays such as TGF. 相似文献
994.
Izod K Stewart JC Clegg W Harrington RW 《Dalton transactions (Cambridge, England : 2003)》2008,(3):363-370
The reaction between {(Me3Si)2CH}PCl2 and one equivalent of [C10H6-8-NMe2]Li, followed by in situ reduction with LiAlH4, gives the secondary phosphane {(Me3Si)2CH}(C10H6-8-NMe2)PH(1) in good yield as a colourless crystalline solid. Metalation of 1 with Bu(n)Li in diethyl ether gives the lithium phosphanide [{[{(Me3Si)2CH}(C10H6-8-NMe2)P]Li}2(OEt2)](2), which undergoes metathesis with either NaOBu(t) or KOBu(t) to give the heavier alkali metal derivatives [[{(Me3Si)2CH}(C10H6-8-NMe2)P]-Na(tmeda)](3) and [[{(Me3Si)2CH}(C10H6-8-NMe2)P]K(pmdeta)](4), after recrystallisation in the presence of the corresponding amine co-ligand [tmeda = N,N,N',N'-tetramethylethylenediamine, pmdeta = N,N,N',N",N"-pentamethyldiethylenetriamine]. Compounds 2-4 have been characterised by 1H, 13C{1H} and 31P{1H} NMR spectroscopy, elemental analyses and X-ray crystallography. Dinuclear 2 crystallises with the phosphanide ligands arranged in a head-to-head fashion and is subject to dynamic exchange in toluene solution; in contrast, compounds 3 and 4 crystallise as discrete monomers which exhibit no dynamic behaviour in solution. DFT calculations on the model compound [{[(Me)(C10H6-8-NMe2)P]Li},(OMe2)] (2a) indicate that the most stable head-to-head form is favoured by 15.0 kcal mol(-1) over the corresponding head-to-tail form. 相似文献
995.
Macdonald JR 《The journal of physical chemistry. B》2008,112(44):13684-13694
Dynamics of the nonassociated supercooled liquids N-methyl-epsilon-caprolactam (NMEC) and glycerol in the frequency domain are investigated using full complex-nonlinear-least-squares fitting of immittance spectroscopy data for appreciable temperature ranges above the glass transition. Such fitting, not previously used for these materials, helps to identify physical processes responsible for the data and elements of their common behavior. Several different fitting models were applied to find a physically plausible best-fitting one to distinguish quantitatively between the dielectric effects of dipoles and the conductive effects of mobile ions. The utility of many composite fitting models was investigated, and although a pure conductive-system dispersive (CSD) fitting model led to good but physically unrealistic fits of all data sets, the dielectric-system dispersive (DSD) Davidson-Cole model best fitted the alpha-dispersion part of the responses. Nevertheless, the series combination of such a DSD model and a separate CSD model (one not associated with electrode effects) was found to yield much better fitting of the data for both materials. Although the CSD model plays somewhat the role of the conventional parallel DSD Johari-Goldstein beta-response, it is here in series and arises from mobile impurity-ion effects rather than from dipolar ones. Previous analyses of data of the present and other molecular materials have often involved two DSD models in parallel, but fitting with such a composite model led here to less physically plausible parameter values and ones with appreciably more uncertainties. Surprisingly, the series DSD and CSD composite-model fits led to comparable estimated values of the NMEC and glycerol dielectric strength parameters, as well as to the nearly equal small thermal activation energies of these parameters. 相似文献
996.
Steven Ross 《Acta Analytica》2008,23(2):91-114
The author takes up three metaphysical conceptions of morality — realism, projectivism, constructivism — and the account of
justification or reason that makes these pictures possible. It is argued that the right meta-ethical conception should be
the one that entails the most plausible conception of reason-giving, rather than by any other consideration. Realism and projectivism,
when understood in ways consistent with their fundamental commitments, generate unsatisfactory models of justification; constructivism
alone does not. The author also argues for a particular interpretation of how “objective moral obligation” is to be understood
within constructivism.
相似文献
Steven RossEmail: |
997.
Ross Stokke 《Proceedings of the American Mathematical Society》2008,136(4):1477-1487
We study the amenability of a locally compact group in relation to the amenability properties of a variety of -algebras and (quantized/dual) Banach algebras naturally associated to a unitary representation of .
998.
Zhao H Bhattacharjee S Chow R Wallace D Masliyah JH Xu Z 《Langmuir : the ACS journal of surfaces and colloids》2008,24(22):12899-12910
The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8. 相似文献
999.