全文获取类型
收费全文 | 1450篇 |
免费 | 51篇 |
国内免费 | 3篇 |
专业分类
化学 | 1095篇 |
晶体学 | 16篇 |
力学 | 20篇 |
数学 | 55篇 |
物理学 | 318篇 |
出版年
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 20篇 |
2020年 | 23篇 |
2019年 | 27篇 |
2018年 | 17篇 |
2017年 | 16篇 |
2016年 | 18篇 |
2015年 | 30篇 |
2014年 | 29篇 |
2013年 | 79篇 |
2012年 | 74篇 |
2011年 | 95篇 |
2010年 | 46篇 |
2009年 | 38篇 |
2008年 | 81篇 |
2007年 | 88篇 |
2006年 | 72篇 |
2005年 | 90篇 |
2004年 | 83篇 |
2003年 | 58篇 |
2002年 | 40篇 |
2001年 | 44篇 |
2000年 | 28篇 |
1999年 | 18篇 |
1998年 | 16篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 16篇 |
1994年 | 15篇 |
1993年 | 21篇 |
1992年 | 24篇 |
1991年 | 22篇 |
1990年 | 15篇 |
1989年 | 25篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 18篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 9篇 |
1979年 | 14篇 |
1978年 | 10篇 |
1977年 | 11篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 12篇 |
1973年 | 8篇 |
排序方式: 共有1504条查询结果,搜索用时 218 毫秒
1.
2.
Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species 下载免费PDF全文
Dr. Atsuko Tomita Dr. Takeshi Miki Takeru Tango Tatsuro Murakami Hideyuki Nakagawa Dr. Yutaka Tai 《Chemphyschem》2015,16(9):2015-2020
The structure of FeOx species supported on γ‐Al2O3 was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al2O3 and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe2O3 particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al2O3 surface. 相似文献
3.
Coating properties of a novel water stationary phase in capillary supercritical fluid chromatography 下载免费PDF全文
The coating properties of a novel water stationary phase used in capillary supercritical fluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless‐steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless‐steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm2 regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless‐steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless‐steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless‐steel columns were more resistant to etching than 304 stainless‐steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless‐steel columns used with this supercritical fluid chromatography technique. 相似文献
4.
Dr. Tatsuhiro Murakami Kanon Ogino Yu Hashimoto Prof. Toshiyuki Takayanagi 《Chemphyschem》2023,24(10):e202200939
In the interstellar medium, the H2 adsorption and desorption on the solid water ice are crucial for chemical and physical processes. We have recently investigated the probabilities of H2 sticking on the (H2O)8 ice, which has quadrilateral surfaces. We have extended the previous work using classical MD and ring-polymer molecular dynamics (RPMD) simulations to the larger ice clusters, (H2O)10 and (H2O)12, which have pentagonal and hexagonal surfaces, respectively. The H2 sticking probabilities decreased as the temperature increased for both cluster cases, whereas the cluster-size-independent profiles were observed. It is thought that the size independence of the probabilities is qualitatively understood from the similar binding energies for all the three cluster systems. Furthermore, the RPMD sticking probabilities are smaller than the classical ones because of the reduction in the binding energies owing to nuclear quantum effects, such as vibrational quantization. 相似文献
5.
Herein reported is a photo-induced production of vicinal diols from alkenes under mild reaction conditions. The present dihydroxylation method using diacetyl (= butane-2,3-dione), oxygen, and water dispenses with toxic reagents and intractable waste generation. 相似文献
6.
This study investigates the recovery of electric resistivity in pure iron, Fe–0.6Ni and Fe–1.5Mn as related to isochronal annealing following 1 MeV proton irradiation at lower temperature than 70 K, focusing on the relationship between solute atoms and irradiation defects. Both nickel and manganese prevent stage ID recovery, which corresponds to correlated recombination. Stage II recovery is also changed by the addition of a solute, which corresponds to the migration of small interstitial clusters. In both pure iron and Fe–0.6Ni, no evident difference was observed in the stage III region, which corresponds to the migration of vacancies. In contrast, two substages appeared in the Fe–1.5Mn at a higher temperature than stage IIIB appeared in pure iron. These substages are considered to represent the release of irradiation-induced defects, which was trapped by manganese. 相似文献
7.
The title problem was discussed to facilitate the formulation of constitutive models of cyclic plasticity under general states of loading. A series of plastic strain controlled cyclic tests was performed by applying combined axial force and torque to thin-walled tubular specimens of Type 316 stainless steel at room temperature. These tests consist of cyclic loading along uniaxial, torsional, cruciform, stellate in eight directions, square and circular plastic strain paths with a constant amplitude of equivalent plastic strain.The results of these tests showed that the strain-hardening depends markedly on the shape of the plastic strain path, and that the strain-hardening (measured by equivalent stress amplitudes) in the saturated state is significant in the order of circular, square, stellate, cruciform and proportional paths. It was also observed that these saturated values were independent of the less significant plastic strain cycles experienced in the past. Finally, the characteristic features of strain-hardening mechanisms under non-proportional loadings were discussed in some detail on the basis of the present results. 相似文献
8.
A method for the resolution of all stress components from the first invariant J1 measured by thermoelastic stress analyzer is described. This method may be used to determine, not only surface stress, but also internal stress and stress on the underside.The method is based on the following procedure:
- 1. (1) Pick an arbitrary domain Ω, within the structure, for which the stresses are required.
- 2. (2) Measure J1 on the surface of Ω.
- 3. (3) Determine the optimum traction along the boundary Γ, which is a part of Ω, by the least squares method such that the difference between the measured J1 and the calculated J1 is at a minimum. Either FEM or BEM may be used for this calculation.
9.
Tairin Kawasaki Naoki Ishida Masahiro Murakami 《Angewandte Chemie (International ed. in English)》2020,59(41):18267-18271
A convenient method is reported to specifically acylate phenolic hydroxyl groups through a radical pathway. When a mixture of an aldehyde and a phenol in ethyl acetate is irradiated with blue light in the presence of iridium and nickel bromide catalysts at ambient temperature, phenoxyl and acyl radicals are transiently generated in situ and cross‐couple to furnish an ester. Aliphatic hydroxy groups remain untouched under the reaction conditions. 相似文献
10.
Prof. Tomoaki Tanase Miho Tanaka Mami Hamada Yuka Morita Dr. Kanako Nakamae Prof. Yasuyuki Ura Prof. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8219-8224
A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4−nPtn(μ-rac-dpmppan)2(XylNC)2](PF6)2 (XylNC=xylyl isocyanide; n=0: Pd4 ( 1 ), 1: PtPd3 ( 2 ), 2: PtPd2Pt ( 3 ), 2: Pt2Pd2 ( 4 ), 3: Pt2PdPt ( 5 )), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31P{1H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1 – 5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain. 相似文献