全文获取类型
收费全文 | 5685篇 |
免费 | 226篇 |
国内免费 | 27篇 |
专业分类
化学 | 3505篇 |
晶体学 | 41篇 |
力学 | 138篇 |
数学 | 873篇 |
物理学 | 1381篇 |
出版年
2023年 | 46篇 |
2022年 | 46篇 |
2021年 | 68篇 |
2020年 | 92篇 |
2019年 | 111篇 |
2018年 | 66篇 |
2017年 | 60篇 |
2016年 | 159篇 |
2015年 | 174篇 |
2014年 | 181篇 |
2013年 | 281篇 |
2012年 | 318篇 |
2011年 | 359篇 |
2010年 | 196篇 |
2009年 | 201篇 |
2008年 | 307篇 |
2007年 | 241篇 |
2006年 | 230篇 |
2005年 | 234篇 |
2004年 | 196篇 |
2003年 | 161篇 |
2002年 | 151篇 |
2001年 | 109篇 |
2000年 | 98篇 |
1999年 | 73篇 |
1998年 | 55篇 |
1997年 | 68篇 |
1996年 | 84篇 |
1995年 | 94篇 |
1994年 | 90篇 |
1993年 | 99篇 |
1992年 | 86篇 |
1991年 | 59篇 |
1990年 | 56篇 |
1989年 | 51篇 |
1988年 | 46篇 |
1987年 | 55篇 |
1986年 | 53篇 |
1985年 | 59篇 |
1984年 | 53篇 |
1983年 | 41篇 |
1982年 | 47篇 |
1981年 | 48篇 |
1980年 | 46篇 |
1979年 | 39篇 |
1978年 | 42篇 |
1977年 | 44篇 |
1976年 | 46篇 |
1974年 | 27篇 |
1973年 | 44篇 |
排序方式: 共有5938条查询结果,搜索用时 0 毫秒
201.
202.
Klaus van Benthem Stephan Krämer Wilfried Sigle Manfred Rühle 《Mikrochimica acta》2002,138(3-4):181-193
An understanding of the correlation between microstructures and properties of materials require the characterization of the
material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations
and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and
of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron
microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which
can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen
and on the scattering power of the atoms (ions) present in the analyzed column.
The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray
spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss
near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms
and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the
electron charge density distribution of the bulk (defect-free) material.
The different techniques are described and applied to different problems in materials science. It will be shown that nearly
atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments
in electron microscopy instrumentation will result in atomic resolution in the foreseeable future. 相似文献
203.
204.
Multidimensional nano-HPLC coupled with tandem mass spectrometry for analyzing biotinylated proteins
Jens Sproß Sebastian Brauch Friedrich Mandel Moritz Wagner Stephan Buckenmaier Bernhard Westermann Andrea Sinz 《Analytical and bioanalytical chemistry》2013,405(7):2163-2173
Multidimensional high-performance liquid chromatography (HPLC) is a key method in shotgun proteomics approaches for analyzing highly complex protein mixtures by complementary chromatographic separation principles. Here, we describe an integrated 3D-nano-HPLC/nano-electrospray ionization quadrupole time-of-flight mass spectrometry system that allows an enzymatic digestion of proteins followed by an enrichment and subsequent separation of the created peptide mixtures. The online 3D-nano-HPLC system is composed of a monolithic trypsin reactor in the first dimension, a monolithic affinity column with immobilized monomeric avidin in the second dimension, and a reversed phase C18 HPLC-Chip in the third dimension that is coupled to a nano-ESI-Q-TOF mass spectrometer. The 3D-LC/MS setup is exemplified for the identification of biotinylated proteins from a simple protein mixture. Additionally, we describe an online 2D-nano-HPLC/nano-ESI-LTQ-Orbitrap-MS/MS setup for the enrichment, separation, and identification of cross-linked, biotinylated species from chemical cross-linking of cytochrome c and a calmodulin/peptide complex using a novel trifunctional cross-linker with two amine-reactive groups and a biotin label. Figure
Schematic representations of the online 3D-nano-HPLC/nano-ESI-Q-TOF-MS/MS setup; LP loading pump, NP nano-pump 相似文献
205.
Composite membranes were prepared by (a) infiltrating NAFION with SiO2-P2O5-ZrO2 sol, and (b) recasting a film using NAFION solution containing SiO2-P2O5-ZrO2 sol. The membranes were characterized by Differential Thermal Analysis and ac-impedance spectroscopy as a function of relative humidity. The influences of the heat treatment (80°C–150°C) and cleaning on the electrical properties were investigated. The incorporation of SiO2-P2O5-ZrO2 gels into NAFION lead to improvements in its thermal stability and proton conductivity. 相似文献
206.
A high-performance liquid chromatography-mass spectrometry method has been developed for the simultaneous determination of native carnitine and eight acylcarnitines in urine. The procedure uses a solid-phase extraction on a cation-exchange column and the separation is performed without derivatization within 17 min on a reversed-phase C8 column in the presence of a volatile ion-pairing reagent. The detector was an ion trap mass spectrometer and quantification was carried out in the MS-MS mode. Validation was done for aqueous standards at ranges between 0.75 and 200 micromol/l, depending on the compound. Carnitine was quantified in urine and comparison with a radioenzymatic assay gave a satisfactory correlation (R2 = 0.981). The assay could be successfully applied to the diagnostic of pathological acylcarnitines profile of metabolic disorders in urines of patients suffering from different organic acidurias. 相似文献
207.
Haddad Paula S. Mauro Antonio E. Nogueira Vânia M. Klein Stanlei I. 《Transition Metal Chemistry》2003,28(8):899-904
[M(CO)4(N—N)] reacts with CuCl to give new heterobimetallic metal carbonyls of the type [M(CO)4(N—N)(CuCl)], M = W, Mo; N—N = 2,2-bipyridine (bipy), 1,10-phenanthroline (phen). Reactions of [M(CO)4(N—N)(CuCl)] with NaSCN produced the series of complexes of general formula [M(CO)4(N—N)(CuSCN)]. The i.r. spectral of all the bimetallic carbonyls exhibited the general four (CO) band patterns of the precursors. The u.v.–vis. spectral data for precursors and products showed bands associated with * (nitrogen ligands), dd (intrametal), as well as MLCT d* (nitrogen ligands) and MLCT d *(CO) transitions. The [M(CO)4(N—N)(CuX)] (X = Cl, SCN) emission spectra showed only one band associated with the MLCT transition. The t.g. curves revealed a stepwise loss of CO groups. The initial decomposition temperatures of the [M(CO)4(N—N)(CuX)] series suggest that the bimetallic compounds are indeed thermally less stable than their precursors, and the X-ray data showed the formation of MO3, CuMO4, Cu2O and CuO as final decomposition products, M = W, Mo. The spectroscopic data suggests that the heterobimetallic compounds are polymeric. 相似文献
208.
209.
Bruijnincx PC Buurmans IL Huang Y Juhász G Viciano-Chumillas M Quesada M Reedijk J Lutz M Spek AL Münck E Bominaar EL Klein Gebbink RJ 《Inorganic chemistry》2011,50(19):9243-9255
The newly synthesized dinuclear complex [Fe(III)(2)(μ-OH)(2)(bik)(4)](NO(3))(4) (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) ?) and Fe-O distances (1.941(2)/1.949(2) ?) compared to other unsupported Fe(III)(2)(μ-OH)(2) complexes. The bridging hydroxide groups of 1 are strongly hydrogen-bonded to a nitrate anion. The (57)Fe isomer shift (δ = 0.45 mm s(-1)) and quadrupole splitting (ΔE(Q) = 0.26 mm s(-1)) obtained from Mo?ssbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable-temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm(-1) and H = JS(1)·S(2)) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 ?, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 ?) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [Fe(II)(bik)(3)](2+) species. Variable-temperature magnetic susceptibility measurements of [Fe(II)(bik)(3)](OTf)(2) (2) revealed spin-crossover behavior. Thermal hysteresis was observed with 2, due to a loss of cocrystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [Fe(II)(bik)(3)](OTf)(2) (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O(2), and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen peroxide yielding epoxides was observed under both limiting oxidant and substrate conditions. 相似文献
210.
A novel type of graph is described, where the graph G has an orientation \({\stackrel{\rightarrow}G}\) and reverse orientation \({\stackrel{\leftarrow}G}\) such that \({G={\stackrel{\rightarrow}G\cup\stackrel{\leftarrow}G}}\) and the adjacency matrices \({A(\stackrel{\rightarrow}G)}\) and \({A(\stackrel{\leftarrow}G)}\) of \({\stackrel{\rightarrow}G}\) and \({\stackrel{\leftarrow}G}\) commute. Some general characterization and examples are given, e.g., for toroidal graphs. 相似文献