全文获取类型
收费全文 | 685篇 |
免费 | 56篇 |
国内免费 | 4篇 |
专业分类
化学 | 558篇 |
晶体学 | 1篇 |
力学 | 24篇 |
数学 | 62篇 |
物理学 | 100篇 |
出版年
2024年 | 1篇 |
2023年 | 12篇 |
2022年 | 5篇 |
2021年 | 14篇 |
2020年 | 31篇 |
2019年 | 16篇 |
2018年 | 9篇 |
2017年 | 5篇 |
2016年 | 30篇 |
2015年 | 35篇 |
2014年 | 33篇 |
2013年 | 38篇 |
2012年 | 81篇 |
2011年 | 85篇 |
2010年 | 42篇 |
2009年 | 35篇 |
2008年 | 47篇 |
2007年 | 46篇 |
2006年 | 34篇 |
2005年 | 36篇 |
2004年 | 31篇 |
2003年 | 16篇 |
2002年 | 13篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 4篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1976年 | 1篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1890年 | 2篇 |
排序方式: 共有745条查询结果,搜索用时 15 毫秒
101.
Molecular Dynamics simulations are used to examine the title issue for the I-/HOD/D2O solution system in connection with recent ultrafast infrared spectroscopic experiments. It is argued that the long "modulation time" associated with the spectral diffusion of the OH frequency, extracted in these experiments, should be interpreted as reflecting the escape time of an HOD from the first hydration shell of the I- ion, i.e., the residence time of an HOD in this solvation shell. Shorter time features related to the oscillation of the OH ...I- hydrogen bond and the breaking and making of this bond are also discussed. 相似文献
102.
Evi Vinck Damien M. Murphy Ian A. Fallis Sabine Van Doorslaer 《Applied magnetic resonance》2010,37(1-4):289-303
We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino CoII, [Co(1)], leads to the formation of an unusual coordinated CoIII-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino CoII complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine CoII salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)]. 相似文献
103.
Peng-Wang Zhai Yongxiang Hu Jacek Chowdhary Charles R. Trepte Patricia L. Lucker Damien B. Josset 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(7-8):1025-1040
We report on an exact vector (polarized) radiative transfer (VRT) model for coupled atmosphere and ocean systems. This VRT model is based on the successive order of scattering (SOS) method, which virtually takes all the multiple scattering processes into account, including atmospheric scattering, oceanic scattering, reflection and transmission through the rough ocean surface. The isotropic Cox–Munk wave model is used to derive the ref and transmission matrices for the rough ocean surface. Shadowing effects are included by the shadowing function. We validated the SOS results by comparing them with those calculated by two independent codes based on the doubling/adding and Monte Carlo methods. Two error analyses related to the ocean color remote sensing are performed in the coupled atmosphere and ocean systems. One is the scalar error caused by ignoring the polarization in the whole system. The other is the error introduced by ignoring the polarization of the light transmitted through the ocean interface. Both errors are significant for the cases studied. This code fits for the next generation of ocean color study because it converges fast for absorbing medium as, for instance, ocean. 相似文献
104.
A careful look at rough path topology applied to Brownian motion reveals new possible properties of the well-known Lévy area, in particular the presence of an intrinsic drift of this area. Using renormalization limit of Markov chains on periodic graphs, we present a construction of such a non-trivial drift and give an explicit formula for it. Several examples with explicit computations are included. 相似文献
105.
Damien Weidmann Chad B. Roller Clive Oppenheimer Alan Fried Frank K. Tittel 《Isotopes in environmental and health studies》2013,49(4):293-302
Recent developments of two mid-infrared tunable laser spectrometers dedicated to carbon isotope ratio determination are presented. First, a field deployable quantum cascade laser-based sensor is described, along with line selection strategy for 13/12CO2 ratio measurements. Secondly, an instrument architecture based on difference frequency generation is presented. The analyses of fundamental limitations, specifically temperature and pressure stability, and water vapor collision broadening, are detailed. 相似文献
106.
Nathan J. Downs Damien P. Igoe Alfio V. Parisi Olivia Taylor Shari L. Lazzaroni Alex Rawlings Daniel R. Garzn‐Chavez Simone L. Harrison 《Photochemistry and photobiology》2019,95(4):1083-1093
The risk of keratinocyte skin cancer, malignant melanoma and ultraviolet radiation (UVR)‐induced eye disease is disproportionately higher in Australia and New Zealand compared to equivalent northern hemisphere latitudes. While many teachers are aware of the importance of reinforcing sun safety messages to students, many may not be aware of the considerable personal exposure risk while performing outdoor duties in locations experiencing high to extreme ambient UVR year‐round. Personal erythemally effective exposure of classroom teachers in tropical Townsville (19.3°S) was measured to establish seasonal extremes in exposure behavior. Mean daily personal exposure was higher in winter (91.2 J m‐2, 0.91 Standard Erythema Dose [SED]) than summer (63.3 J m?2, 0.63 SED). The range of exposures represents personal exposures that approximate current national guidelines for Australian workers at the study latitude of approximately 1.2 SED (30 J m?2 effective to the International Commission on Non‐Ionizing Radiation Protection). Similar proportions of teachers spent more than 1 h outdoors per day in winter (28.6%) and summer (23.6%) as part of their teaching duties with seasonal differences having little effect on the time of exposure. Personal exposures for teachers peaked during both seasons near school meal break times at 11:00 am and 1:00 pm, respectively. 相似文献
107.
Simon Dochain Jean-Boris Nshimyumuremyi Damien F. Dewez Jean-François Body Benjamin Elias Michael L. Singleton István E. Markó 《Tetrahedron》2019,75(15):2280-2283
Okadaic acid, a potent and selective inhibitor of Protein Phosphatases 1 and 2A (PP1 and PP2A), is widely used as a probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core. 相似文献
108.
Kirill F. Sheberstov Eduard Sistaré Guardiola Damien Jeannerat 《Magnetic resonance in chemistry : MRC》2020,58(5):376-389
The fundamental concept of phase discussed in this tutorial aimed at providing students with an explanation of the delays and processing parameters they may find in nuclear magnetic resonance (NMR) pulse programs. We consider the phase of radio-frequency pulses, receiver, and magnetization and how all these parameters are related to phases and offsets of signals in spectra. The impact of the off-resonance effect on the phase of the magnetization is discussed before presenting an overview of how adjustment of the time reference of the free induction decay avoids first-order correction of the phase of spectra. The main objective of this tutorial is to show how the relative phase of a pulse and the receiver can be used to change the reference frequency along direct and indirect dimensions of NMR experiments. Unusual of phase incrementation with non-90° angles will be illustrated on one- and two-dimensional NMR spectra. 相似文献
109.
110.
Romain Plais Guy Gouarin Dr. Anne Gaucher Violette Haldys Arnaud Brosseau Dr. Gilles Clavier Dr. Jean-Yves Salpin Prof. Dr. Damien Prim 《Chemphyschem》2020,21(12):1249-1257
The intrinsic properties of tetrazine as a π-anion receptor and as an on/off recognition probe merged with H-bond ability of an urea motif into a single architecture constitutes a new generation of well-defined anion receptors. Complexation properties directly benefit from the dual and synergistic contribution of tetrazine and urea. In this study, we report on the synthesis and assessment of binding properties to anions of diverse geometries. Association constants have been predicted by theoretical calculations and evaluated by multiple and complementary experimental techniques including electrospray-mass tandem spectroscopy, NMR, UV-visible, steady state fluorescence spectroscopies and time resolved fluorescence. These results provide the basis for a better understanding of both the complexation and the anion-dependent quenching mechanism. 相似文献