全文获取类型
收费全文 | 1210篇 |
免费 | 31篇 |
国内免费 | 9篇 |
专业分类
化学 | 828篇 |
晶体学 | 7篇 |
力学 | 58篇 |
数学 | 104篇 |
物理学 | 253篇 |
出版年
2022年 | 10篇 |
2021年 | 4篇 |
2020年 | 16篇 |
2019年 | 22篇 |
2018年 | 21篇 |
2017年 | 12篇 |
2016年 | 25篇 |
2015年 | 21篇 |
2014年 | 32篇 |
2013年 | 58篇 |
2012年 | 83篇 |
2011年 | 67篇 |
2010年 | 36篇 |
2009年 | 28篇 |
2008年 | 60篇 |
2007年 | 69篇 |
2006年 | 40篇 |
2005年 | 60篇 |
2004年 | 43篇 |
2003年 | 51篇 |
2002年 | 41篇 |
2001年 | 29篇 |
2000年 | 34篇 |
1999年 | 20篇 |
1998年 | 14篇 |
1997年 | 14篇 |
1996年 | 23篇 |
1995年 | 10篇 |
1994年 | 18篇 |
1993年 | 15篇 |
1992年 | 24篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 9篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 21篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 12篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 15篇 |
1974年 | 7篇 |
1973年 | 17篇 |
1970年 | 4篇 |
排序方式: 共有1250条查询结果,搜索用时 0 毫秒
81.
Yao S Hinds MG Murphy JM Norton RS 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,211(2):243-247
Conformational or chemical exchange can cause significant sensitivity loss in NMR spectroscopy through resonance broadening for nuclear spins involved in these processes. While this effect may sometimes be alleviated by manipulating experimental conditions such as temperature, pH, and buffers, conditions optimal for all resonances are not always achievable. As a consequence, any means of recovering or minimizing this exchange-induced sensitivity loss is potentially of significant value in regaining information otherwise lost. We report the experimental observation of significant sensitivity gain for nuclear spins undergoing chemical exchange with solvent (water) at exchange rates ca 1-10 s(-1) in (1)H-(15)N correlation spectra of proteins acquired with band-selective pulses (the SOFAST-HMQC sequence). 相似文献
82.
Murphy K Harris AD Diukova A Evans CJ Lythgoe DJ Zelaya F Wise RG 《Magnetic resonance imaging》2011,29(10):1382-1389
Pulsed arterial spin labeling (PASL) is an increasingly common technique for noninvasively measuring cerebral blood flow (CBF) and has previously been shown to have good repeatability. It is likely to find a place in clinical trials and in particular the investigation of pharmaceutical agents active in the central nervous system. We aimed to estimate the sample sizes necessary to detect regional changes in CBF in common types of clinical trial design including (a) between groups, (b) a two-period crossover and (3) within-session single dosing. Whole brain CBF data were acquired at 3 T in two independent groups of healthy volunteers at rest; one of the groups underwent a repeat scan. Using these data, we were able to estimate between-groups, between-session and within-session variability along with regional mean estimates of CBF. We assessed the number of PASL tag-control image pairs that was needed to provide stable regional estimates of CBF and variability of regional CBF across groups. Forty tag-control image pairs, which take approximately 3 min to acquire using a single inversion label delay time, were adequate for providing stable CBF estimates at the group level. Power calculations based on the variance estimates of regional CBF measurements suggest that comparatively small cohorts are adequate. For example, detecting a 15% change in CBF, depending on the region of interest, requires from 7-15 subjects per group in a crossover design, 6-10 subjects in a within-session design and 20-41 subjects in a between-groups design. Such sample sizes make feasible the use of such CBF measurements in clinical trials of drugs. 相似文献
83.
84.
Calculations with Hartree—Fock electron densities for the rare gas atoms He through Xe show that the gradient expansion for the kinetic energy functional, T[] = T0[] + T2[] + T4[] + … = ∫t() dτ, approximates the kinetic energy by averaging over the shell structure present in the true local kinetic energy density, t(), and that the accuracy of the gradient expansion improves with increasing atomic number. Components of t(), t0(), t2() and t4(), are exhibited and discussed. The defined function t() is everywhere positive. 相似文献
85.
Tsoi WC James DT Kim JS Nicholson PG Murphy CE Bradley DD Nelson J Kim JS 《Journal of the American Chemical Society》2011,133(25):9834-9843
The nature of main in-plane skeleton Raman modes (C=C and C-C stretch) of poly(3-hexylthiophene) (P3HT) in pristine and its blend thin films with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) is studied by resonant and nonresonant Raman spectroscopy and Raman simulations. Under resonant conditions, the ordered phase of P3HT with respect to its disordered phase is identified by (a) a large shift in the C=C mode peak position to lower wavenumber (~21 cm(-1) shift), (b) a narrower fwhm of the C=C mode (~9 cm(-1) narrower), (c) a larger intensity of the C-C mode relative to the C=C mode (~56% larger), and (d) a very small Raman dispersion (~5 cm(-1)) of the C=C mode. The behavior of the C=C and C-C modes of the ordered and disordered phases of P3HT can be explained in terms of different molecular conformations. The C=C mode of P3HT in P3HT:PCBM blend films can be reproduced by simple superposition of the two peaks observed in different phases of P3HT (ordered and disordered). We quantify the molecular order of P3HT after blending with PCBM and the subsequent thermal annealing to be 42 ± 5% and 94 ± 5% in terms of the fraction of ordered P3HT phase, respectively. The increased molecular order of P3HT in blends upon annealing correlates well with enhanced device performance (J(SC), -4.79 to -8.72 mA/cm(2) and PCE, 1.07% to 3.39%). We demonstrate that Raman spectroscopy (particularly under resonant conditions) is a simple and powerful technique to study molecular order of conjugated polymers and their blend films. 相似文献
86.
The interactions of a weak organic acid (acetic acid, HOAc) with a toluene solution of the Co(II)-Schiff base type complex, (R,R')-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II) (labeled [Co(1)]), was investigated using EPR, HYSCORE, and DFT computations. This activated [Co(II)(1)] system is extremely important within the context of asymmetric catalysts (notably the hydrolytic kinetic resolution of epoxides) despite the lack of detailed structural information about the nature of the paramagnetic species present. Under anaerobic conditions, the LS [Co(II)(1)] complex with a |yz, (2)A(2)? ground state is converted into a low-spin (LS) and a high-spin (HS) complex in the presence of the acid. The newly formed LS state is assigned to the coordinated [Co(II)(1)]-(HOAc) complex, possessing a |z(2), (2)A(1)? ground state (species A; g(x) = 2.42, g(y) = 2.28, g(z) = 2.02, A(x) = 100, A(y) = 120, A(z) = 310 MHz). The newly formed HS state is assigned to an acetate coordinated [Co(II)(1)]-(OAc(-)) complex, possessing an S = (3)/(2) spin ground state (species B, responsible for a broad EPR signal with g ≈ 4.6). These spin ground states were confirmed with DFT calculations using the hybrid BP86 and B3LYP functionals. Under aerobic conditions, the LS and HS complexes (species A and B) are not observed; instead, a new HS complex (species C) is formed. This complex is tentatively assigned to a paramagnetic superoxo bridged dimer (AcO(-))[Co(II)(1)···O(2)(-)Co(III)(1)](HOAc), as distinct from the more common diamagnetic peroxo bridged dimers. Species C is characterized by a very broad HS EPR signal (g(x) = 5.1, g(y) = 3.9, g(z) = 2.1) and is reversibly formed by oxygenation of the LS [Co(II)(1)]-(HOAc) complex to the superoxo complex [Co(III)(1)O(2)(-)](HOAc), which subsequently forms the association complex C by interaction with the HS [Co(II)(1)](OAc(-)) species. The LS and HS complexes were also identified using other organic acids (benzoic and propanoic acid). Thermal annealing-quenching experiments revealed the additional presence of [Co(III)(1)O(2)(-)](HOAc) adducts, corroborating the presence of species C and the presence of diamagnetic dimer complexes in the solution, such as the EPR silent (HOAc)[Co(III)(1)(O(2)(2-))Co(III)(1)](HOAc). Overall, it appears that a facile interconversion of the [Co(1)] complex, possessing a LS ground state, occurs in the presence of acetic acid, producing both HS and LS Co(II) states, prior to formation of the oxidized active form of the catalyst, [Co(III)(1)](OAc(-)). 相似文献
87.
Thomas Merakis Annette Murphy Leone Spiccia Alan Beguin Werner Marty 《Helvetica chimica acta》1989,72(5):993-995
Crystalline salts of the hydrolytic dimer of Cr(III), [Cr2(μ-OH)2(H2O)8]X4·n H2O (X = p-toluenesulfonate (tos) or mesitylene-2-sulfonate (dmtos)) have been prepared in good yields via a simple two-step procedure: H+ oxidation of Cr metal to give Cr2+ (T ≈? 70°) followed by O2 oxidation, of Cr2+ to give the dimer (T ≈? 25°). The mechanism of conversion of Cr2+ into the dimer is discussed. 相似文献
88.
The underlying metal was observed to corrode when a ruthenium dioxide-coated titanium electrode was anodized in an aqueous methanol solution. With a similarly coated platinum electrode peaks were observed on the voltammogram below 1.0 V which were attributed to methanol oxidation on the underlying metal. This effect was more pronounced when the electrode was subjected during cycling to potentials close to 0 V. Rapid oxidation of methanol on RuO2 was observed at potentials above 1.0 V, the rate at a given potential increasing in an approximately linear manner with increasing alcohol concentration. The rate of reaction also increased with increasing temperature and increasing surface roughness. Tafel slope values were rather high (>100 mV decade?1) and a mechanism involving anodically generated species such as OHads was proposed to account for these results. The variation of activity with pH was similar to that reported earlier for oxygen evolution at these anodes and this was again explained in terms of partial deactivation of the surface due to a combination of proton loss and phosphate ion adsorption at intermediate pH values. The release of carbon dioxide from aqueous solutions of higher alcohols at 25°C confirmed the high oxidizing power of RuO2 anodes. 相似文献
89.
90.
High-throughput approaches for the discovery and optimization of new olefin polymerization catalysts
Murphy V Bei X Boussie TR Brümmer O Diamond GM Goh C Hall KA Lapointe AM Leclerc M Longmire JM Shoemaker JA Turner H Weinberg WH 《Chemical record (New York, N.Y.)》2002,2(4):278-289
The discovery of new olefin polymerization catalysts is currently a time-intensive trial-and-error process with no guarantee of success. A fully integrated high-throughput screening workflow for the discovery of new catalysts for polyolefin production has been implemented at Symyx Technologies. The workflow includes the design of the metal-ligand libraries using custom-made computer software, automated delivery of metal precursors and ligands into the reactors using a liquid-handling robot, and a rapid primary screen that serves to assess the potential of each metalligand-activator combination as an olefin polymerization catalyst. "Hits" from the primary screen are subjected to secondary screens using a 48-cell parallel polymerization reactor. Individual polymerization reactions are monitored in real time under conditions that provide meaningful information about the performance capabilities of each catalyst. Rapid polymer characterization techniques support the primary and secondary screens. We have discovered many new and interesting catalyst classes using this technology. 相似文献