全文获取类型
收费全文 | 2018篇 |
免费 | 56篇 |
国内免费 | 1篇 |
专业分类
化学 | 1344篇 |
晶体学 | 40篇 |
力学 | 22篇 |
数学 | 125篇 |
物理学 | 544篇 |
出版年
2023年 | 13篇 |
2022年 | 19篇 |
2021年 | 17篇 |
2020年 | 21篇 |
2019年 | 19篇 |
2016年 | 34篇 |
2015年 | 54篇 |
2014年 | 43篇 |
2013年 | 86篇 |
2012年 | 83篇 |
2011年 | 91篇 |
2010年 | 60篇 |
2009年 | 43篇 |
2008年 | 84篇 |
2007年 | 82篇 |
2006年 | 56篇 |
2005年 | 71篇 |
2004年 | 58篇 |
2003年 | 53篇 |
2002年 | 43篇 |
2001年 | 41篇 |
2000年 | 54篇 |
1999年 | 30篇 |
1998年 | 45篇 |
1997年 | 28篇 |
1996年 | 39篇 |
1995年 | 32篇 |
1994年 | 38篇 |
1993年 | 40篇 |
1992年 | 30篇 |
1991年 | 22篇 |
1990年 | 27篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 24篇 |
1986年 | 23篇 |
1985年 | 30篇 |
1984年 | 38篇 |
1983年 | 22篇 |
1982年 | 29篇 |
1981年 | 20篇 |
1980年 | 32篇 |
1979年 | 22篇 |
1978年 | 23篇 |
1977年 | 36篇 |
1976年 | 17篇 |
1975年 | 11篇 |
1974年 | 28篇 |
1973年 | 12篇 |
1968年 | 13篇 |
排序方式: 共有2075条查询结果,搜索用时 15 毫秒
41.
Michael J. Beam Jeannette Schulz Anvita Sinha Pamela Collins Susan Hallenbeck Michael Kustin 《Journal of heterocyclic chemistry》1989,26(2):521-524
Notwithstanding its tendency toward air oxidation in solution, 2-hydrazinobenzothiazole I reacted with aromatic aldehydes in ethanol to give the corresponding hydrazones III-XV in high yields and analytical purity. In related examples, acylation took place under similar conditions to produce hydrazides XVI-XX . The near-infrared bands of the absorption spectra of the araldehyde hydrazones have been associated with charge transfer and appeared to correlate with structural elements of the compounds in a way suggesting that the charge transfer was intermolecular. 相似文献
42.
43.
Hu C Noll BC Schulz CE Scheidt WR 《Journal of the American Chemical Society》2005,127(43):15018-15019
The synthesis, molecular structure, and electronic structure characterization of two five-coordinate high-spin imidazolate-ligated iron(II) porphyrinates are reported. Their electronic structure, as deduced from M?ssbauer spectra obtained in strong magnetic fields, is distinctly different from that of the analogous imidazole-ligated species. The resulting electronic structure models are consistent with all observed differing features in the two classes. 相似文献
44.
Alexander Goerke Gregor Leipelt Hartmut Palm C. P. Schulz I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,32(4):311-320
The first reactive differential scattering study for atomic clusters is reported. Oxidation of Na
x
(x8) with O2 is investigated in a crossed beam apparatus. Sodium oxide (Na
n
O,n4) and sodium dioxide (Na
n
O2,n6) are produced with a total reactive cross section from 50 to 80 Å2, depending on the cluster size. The excess energies for these reactions are estimated by an SCF type ab initio calculation and range from 0.5 to 5 eV. The large cross section may then be understood quantitatively in terms of a harpooning mechanism as a first step in the reaction path. Angular distributions have been determined for the most abundant products, showing strong forward scattering. Two different schemes are discussed for the reaction: while the dioxides Na
n
O2 may be formed by an evaporative cooling process from a highly excited collision complex, formation of Na
n
O appears to originate from a direct process. In both cases the experimental data suggest that most of the exothermicity remains in the reaction products. 相似文献
45.
Dimitris Pantazis Donald N. Schulz Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1476-1483
The synthesis of a model cyclic triblock terpolymer [cyclic(S‐b‐I‐b‐MMA] of styrene (S), isoprene (I), and methyl methacrylate (MMA) was achieved by the end‐to‐end intramolecular amidation reaction of the corresponding linear α,ω‐amino acid precursor [S‐b‐I‐b‐MMA] under high‐dilution conditions. The linear precursor was synthesized by the sequential anionic polymerization of S, I, and MMA with 2,2,5,5‐tetramethyl‐1‐(3‐lithiopropyl)‐1‐aza‐2,5‐disilacyclopentane as an initiator and amine generator and 4‐bromo‐1,1,1‐trimethoxybutane as a terminator and carboxylic acid generator. The separation of the unreacted linear polymer from the cyclic terpolymer was facilitated by the transformation of the unreacted species into high molecular weight polymers by the evaporation of the reaction solvent and the continuation of the reaction under high‐concentration conditions. The intermediate materials and the final cyclic terpolymer, characterized by size exclusion chromatography, vapor pressure osmometry, thin‐layer chromatography, IR and NMR spectroscopy, exhibited high molecular weight and compositional homogeneity. Dilute‐solution viscosity measurements were used as an additional proof of the cyclic structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1476–1483, 2002 相似文献
46.
47.
R. Schaub G. Pensl M. Schulz C. Holm 《Applied Physics A: Materials Science & Processing》1984,34(4):215-222
Hall effect and conductivity measurements are performed on Te-doped silicon in the temperature range 30KT800K. A Hall equipment suited for high temperatures up to 800 K has been constructed. The temperature dependence of the free electron concentration is analyzed for Te-doped silicon including one double-donor and several monovalent donor species. A deep level with an electrical activation energy of 200 meV is determined from the saturation of the free electron concentration at temperatures above 400 K. This level represents the first ionization stage of the Te double-donor. The second ionization stage is estimated to have an activation energy of 440 meV. The maximum electrically active Te concentration obtained is 5×1016cm–3. Three different shallow donor states are resolved in the low-temperature range. The concentrations of these shallow donors are partially sensitive to a subsequent heat-treatment. 相似文献
48.
Tellurium-related defects inn-type silicon have been analysed by deep level transient spectroscopy (DLTS). The tellurium doping of the samples was performed by ion implantation or during epitaxy. In all the samples, a level having a thermal activation energy around 0.37 eV is observed. This activation energy is found to be dependent on the electric field. Taking into account the Poole-Frenkel (FP) effect and a temperature dependence proportional toT ?2 in the capture cross-section, a value ofE A=0.41eV is obtained. A second Te-related level having an activation energy ofE A=0.14eV without correction of the FP effect could only be measured in the implanted samples. The same concentration is observed for the two levels in the implanted samples thus indicating that both peaks in the DLTS spectra are caused by the identical Te-related defect. 相似文献
49.
Katja Schulz R. Klaus Mueller Werner Engewald Adelgunde Graefe Jan Dreßler 《Chromatographia》2007,66(11-12):879-886
Some aroma compounds found in alcoholic beverages are characteristic of a certain beverage (i.e. 2,4-decadienoic acid ethyl ester is characteristic of pear spirit and 5-butyltetrahydro-4-methylfuran-2-on “whiskey lactone” is characteristic of aged spirits like whiskey). These substances were detectable in beverages but not in blood samples. The aim of this investigation was to find a sensitive sampling technique for aroma compounds in whole blood samples. This technique may be used in forensic toxicology for examination of drinking claims. The method comprises dynamic headspace sampling using a purge and trap concentrator, followed by quantitative gas chromatography–mass spectrometry (dynamic HS–GC–MS). The influence of sample preparation, trap adsorbents and sample temperature as well as desorption time and purge time on the quality of the analytical results were investigated. The following optimal parameters were determined: stirred and diluted whole blood sample without salt addition, use of Carbotrap C as trap material, sample temperature at 80 °C, desorption time 20 min and purge time 30 min. These optimal parameters were used for the determination of detection limits (LOD). The LOD of aroma compounds by means of dynamic headspace sampling were compared with the results of conventional sampling: the static headspace technique. Limits of detection for the aroma compounds with conventional static headspace GC are in the range 400–10,000 μg L?1. Dynamic headspace–GC was found to be a more sensitive sampling technique for most of the aroma compounds investigated (e.g. C4–C8 ethyl esters, benzoic acid ethyl ester, linalool oxide and 4-ethylguaiacol) with detection limits between 1 and 50 μg L?1, but there were also limits to the sampling of substances with lower volatility like decanoic acid ethyl ester, 2,4-decadienoic acid ethyl ester, eugenol and whiskey lactone with detection limits of about 1,000 μg L?1. 相似文献
50.
Nuclear Overhauser Effect (NOE) methods in NMR are an important tool for 3D structural analysis of small molecules. Quantitative NOE methods conventionally rely on reference distances, known distances that have to be spectrally separated and are not always available. Here we present a new method for evaluation and 3D structure selection that does not require a reference distance, instead utilizing structures optimized by molecular mechanics, enabling NOE evaluation even on molecules without suitable reference groups.A quantitative Nuclear Overhauser Effect (NOE) analysis approach that avoids the use of and internal reference distance to perform molecular configuration selection. 相似文献