全文获取类型
收费全文 | 526篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 347篇 |
晶体学 | 1篇 |
力学 | 52篇 |
数学 | 55篇 |
物理学 | 96篇 |
出版年
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 3篇 |
2018年 | 4篇 |
2016年 | 16篇 |
2015年 | 16篇 |
2014年 | 12篇 |
2013年 | 27篇 |
2012年 | 32篇 |
2011年 | 28篇 |
2010年 | 19篇 |
2009年 | 8篇 |
2008年 | 29篇 |
2007年 | 25篇 |
2006年 | 23篇 |
2005年 | 22篇 |
2004年 | 27篇 |
2003年 | 12篇 |
2002年 | 13篇 |
2001年 | 10篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 9篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 3篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 3篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1960年 | 3篇 |
排序方式: 共有551条查询结果,搜索用时 15 毫秒
91.
Caffeine (CAF) in aqueous solutions was extracted into acetonitrile (MeCN) using solid phase extraction (SPE). The voltammetric detection of CAF in MeCN was performed in a microcentrifuge tube after SPE in order to minimise the required amount of MeCN and reagents used during the analysis. The voltammetric determination of CAF from a range of beverages extracted into MeCN was in good agreement with the results obtained from HPLC measurements on the same samples. The SPE‐coupled voltammetric method gave more accurate results than those obtained via the direct voltammetric detection of CAF in real beverage samples. 相似文献
92.
The diphosphane o-C6H4(PMe2)2 reacts with GaX3 (X = Cl, Br, or I) in a 1:1 molar ratio in dry toluene to give trans-[GaX2{o-C6H4(PMe2)2}2][GaX4], the cations of which contain the first examples of six-coordinate gallium in a phosphane complex. The use of a 1:2 ligand/GaCl3 ratio produced [GaCl2{o-C6H4(PMe2)2}][GaCl4], containing a pseudotetrahedral cation, and similar pseudotetrahedral [GaX2{o-C6H4(PPh2)2}][GaX4] complexes are the only products isolated with the bulkier o-C6H4(PPh2)2. On the other hand, Et2P(CH2)2PEt2, which has a flexible aliphatic backbone, formed [(X3Ga)2{mu-Et2P(CH2)2PEt2}], in which the ligand bridges two pseudotetrahedral gallium centers. The diarsane, o-C6H4(AsMe2)2, formed [GaX2{o-C6H4(AsMe2)2}][GaX4], also containing pseudotetrahedral cations, and in marked contrast to the diphosphane analogue, no six-coordinate complexes form; a very rare example where these two much studied ligands behave differently towards a common metal acceptor. The complexes [(I3Ga)2{mu-Ph2As(CH2)2AsPh2}] and [GaX3(AsMe3)] are also described. The X-ray structures of trans-[GaX2{o-C6H4(PMe2)2}2][GaX4] (X = Cl, Br or I), [GaCl2{o-C6H4(PPh2)2}][GaCl4], [GaX2{o-C6H4(AsMe2)2}][GaX4] (X = Cl or I), [(I3Ga)2{mu-Ph2As(CH2)2AsPh2}], and [GaX3(AsMe3)] (X = Cl, Br or I) are reported, and the structural trends are discussed. The solution behavior of the complexes has been explored using a combination of 31P{1H} and 71Ga NMR spectroscopy. 相似文献
93.
Pirrung MC Li Z Hensley E Liu Y Tanksale A Lin B Pai A Webster NJ 《Journal of combinatorial chemistry》2007,9(5):844-854
A synthetic route to bis-indolyldihydroxybenzoquinones was adapted for parallel organic synthesis. The route involves selective conjugate addition of an indole to dichlorobenzoquinone promoted by Br?nsted acid, followed by a Lewis acid-promoted conjugate addition of a second indole and a final hydrolysis. Methods for high-throughput purification of the products of this synthesis were also developed. Using these methods, we prepared a library whose structures are based on asterriquinone natural products, which have a wide range of biological activities. In this report, the activities of the library members in activation of the insulin receptor on mammalian cells were examined. Novel compounds were discovered that fall outside earlier developed structure-activity relationships for insulin mimics, supporting the value of systematic investigation (inspired by Nature) for the discovery of novel biologically active molecules. 相似文献
94.
A newly developed interface coupling a CHN combustion device (elemental analyser 'EA') to an isotope ratio mass spectrometer is described and evaluated. The purpose of the device is to extend the dynamic range of delta(13)C and delta(15)N analysis from less than 2 orders of magnitude to more than 3 orders of magnitude. Carbon isotope ratio measurements of atropine as a model compound have been performed analysing between 1 μg to 5 mg C with acceptable to excellent precision (0.6 to 0.06 per thousand, delta-notation). The correction due to the blank signal is critical for sample amounts smaller than 4 μg C. The maximum sample weight is determined by the combustion capacity of the EA. Larger sample amounts are measured using dilution of a small part of the EA effluent with helium. The dilution mechanism works virtually free of isotope fractionation. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
95.
X‐ray crystal structures are reported for Na6[RuO2{TeO4(OH)2}2]·16H2O and Na5[Ag{TeO4(OH)2}2]·16H2O which contain respectively RuVI and AgIII coordinated to chelating bidentate tellurate ([TeO4(OH)2]4−) groups. Na6[RuO2{TeO4(OH)2}2]·16H2O: Space group P1¯, Z = 2, lattice dimensions at 120 K; a = 6.9865(1), b = 8.7196(2), c = 11.7395(2)Å, α = 74.008(1), β = 79.954(1), γ = 88.514(1)°; R1 = 0.025. Na5[Ag{TeO4(OH)2}2]·16H2O: Space group P1¯, Z = 2, lattice dimensions at 120 K; a = 5.888(1), b = 8.932(1), c = 12.561(2)Å, α = 98.219(6), β = 97.964(9), γ = 93.238(14)°; R1 = 0.047. 相似文献
96.
Qingran Zhang Richard F. Webster Soshan Cheong Richard D. Tilley Xunyu Lu Rose Amal 《Particle & Particle Systems Characterization》2019,36(1)
The development of highly active and cost‐effective catalyst materials toward electrochemical water splitting is of great importance for converting and storing the intermittent solar energy in the form of hydrogen. Herein, for the first time, an ultrathin Fe and N‐co‐doped carbon nanosheet encapsulated Fe‐doped CoNi alloy nanoparticle (FeCoNi@FeNC) composite is obtained and applied as a bifunctional catalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This catalyst exhibits prominent catalytic performances for both HER and OER, which only requires overpotentials of 102 and 330 mV, respectively, to reach a current density of 10 mA cm?2 in alkaline media. The high catalytic activity is intrinsically associated with the presence of Fe in both nanosheets and nanoparticles, which has triggered the occurrence of coordinative effects between Fe‐N‐C and FeCoNi that are beneficial for HER and OER, as revealed by electrochemical techniques. In an overall water splitting electrolyzer, FeCoNi@FeNC is employed as both the cathode and anode catalysts, achieving 12 mA cm?2 at 1.63 V for a duration of more than 12 h. 相似文献
97.
Yu A Bekyarova E Itkis ME Fakhrutdinov D Webster R Haddon RC 《Journal of the American Chemical Society》2006,128(30):9902-9908
We report a further advance in the bulk purification of nitric acid-treated single-walled carbon nanotubes (SWNTs) by use of high-speed centrifugation. We have already shown that low-speed centrifugation is effective in removing amorphous carbon (AC). In these earlier experiments, the AC preferentially suspends in aqueous dispersions on low-speed centrifugation (2000g), leaving the SWNTs in the sediment. In a surprising reversal, we now show that high-speed centrifugation (20000g) of well-dispersed preparations is effective in sedimenting carbon nanoparticles (CNP), while leaving the SWNTs suspended in aqueous media. Taken together, these two techniques allow the bulk scale (10 g) purification of SWNTs by efficiently separating the two main contaminants, in an industrially viable process. We show that the mechanism of these separations is based on the differential charging (zeta-potential) of the AC, CNPs, and SWNTs that comes about during the chemical processing. Due to their more robust structure, nitric acid oxidation leaves the CNPs with a surface charge density lower than that of the SWNTs, and thus the CNPs do not form stable dispersions in aqueous media during high-speed centrifugation. The efficiency of the process was confirmed by the high purification recovery factor (PRF = 90%), which is a measure of the fractional quantity of the product recovered after the purification. We demonstrate that the purity of SWNTs significantly affects their mechanical and electrical properties. 相似文献
98.
Lorena Bociu Giovanna Guidoboni Riccardo Sacco Justin T. Webster 《Archive for Rational Mechanics and Analysis》2016,222(3):1445-1519
We consider the initial and boundary value problem for a system of partial differential equations describing the motion of a fluid–solid mixture under the assumption of full saturation. The ability of the fluid phase to flow within the solid skeleton is described by the permeability tensor, which is assumed here to be a multiple of the identity and to depend nonlinearly on the volumetric solid strain. In particular, we study the problem of the existence of weak solutions in bounded domains, accounting for non-zero volumetric and boundary forcing terms. We investigate the influence of viscoelasticity on the solution functional setting and on the regularity requirements for the forcing terms. The theoretical analysis shows that different time regularity requirements are needed for the volumetric source of linear momentum and the boundary source of traction depending on whether or not viscoelasticity is present. The theoretical results are further investigated via numerical simulations based on a novel dual mixed hybridized finite element discretization. When the data are sufficiently regular, the simulations show that the solutions satisfy the energy estimates predicted by the theoretical analysis. Interestingly, the simulations also show that, in the purely elastic case, the Darcy velocity and the related fluid energy might become unbounded if indeed the data do not enjoy the time regularity required by the theory. 相似文献
99.
Wu X Xing G Tan SL Webster RD Sum TC Yeow EK 《Physical chemistry chemical physics : PCCP》2012,14(26):9511-9519
Hole transfer dynamics of Atto647N sensitized p-type NiO nanoparticle (NP) thin films is investigated using both ensemble-averaged and single-molecule spectroscopy techniques. The rate of hole transfer is dependent on the processing conditions and is enhanced when the NiO is pre-annealed in air as compared to vacuum. This is possibly due to an upward shift of the valence band of the semiconductor and an increase in the free energy for hole transfer as more Ni(2)O(3) are formed in the presence of air. The stretched exponential fluorescence decay profile of Atto647N on NiO NP suggests the presence of a distribution of hole transfer rates. This is in agreement with the observed emission lifetime and intensity fluctuations and non-monoexponential fluorescence decays for individual Atto647N molecules on NiO NP films. A plausible explanation for the heterogeneous hole transfer rates is an inhomogeneous distribution of (defect) sites on the metal oxide due to the processing conditions and a fluctuation in the intermolecular interaction. 相似文献
100.
A simple and robust solid phase synthetic method for the ligation of diamondoids on the phosphate backbone of DNA with "click" chemistry using [Cu(CH(3)CN)(4)]PF(6) without a stabilizing ligand is reported. It was found that as the size of dimondoid increased, a corresponding increase in melting temperature was observed. 相似文献