全文获取类型
收费全文 | 838篇 |
免费 | 46篇 |
国内免费 | 26篇 |
专业分类
化学 | 480篇 |
晶体学 | 21篇 |
力学 | 42篇 |
综合类 | 1篇 |
数学 | 161篇 |
物理学 | 205篇 |
出版年
2023年 | 11篇 |
2022年 | 8篇 |
2021年 | 7篇 |
2020年 | 16篇 |
2019年 | 19篇 |
2018年 | 24篇 |
2017年 | 33篇 |
2016年 | 36篇 |
2015年 | 26篇 |
2014年 | 45篇 |
2013年 | 80篇 |
2012年 | 77篇 |
2011年 | 58篇 |
2010年 | 49篇 |
2009年 | 34篇 |
2008年 | 40篇 |
2007年 | 43篇 |
2006年 | 42篇 |
2005年 | 32篇 |
2004年 | 35篇 |
2003年 | 22篇 |
2002年 | 19篇 |
2001年 | 5篇 |
2000年 | 16篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 17篇 |
1995年 | 15篇 |
1994年 | 10篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1968年 | 1篇 |
1937年 | 2篇 |
排序方式: 共有910条查询结果,搜索用时 31 毫秒
21.
Alvarez CM Alvarez MA García-Vivó D García ME Ruiz MA Saáez D Falvello LR Soler T Herson P 《Dalton transactions (Cambridge, England : 2003)》2004,(24):4168-4179
The new hydride complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4] having bulky substituents (R = 2,4,6-C(6)H2tBu3= Mes*, R = 2,4,6-C6H2Me3= Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(mu-PHR)(CO)4]-. Protonation of the Mes* compound with either [H(OEt2)2][B{3,5-C6H3(CF3)2}4] or HBF4.OEt2 gives the cationic phosphinidene complex [Mo2Cp2(mu-H)(mu-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp2(mu-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(mu-PHR)(mu-CO)(CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(mu-H)(mu-PFR)(CO)4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo2ClCp2(mu-PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(mu-H)(mu-PHMes)(CO)4](cis isomer), [Mo2Cp2(mu-H)(mu-PFMes)(CO)4](trans isomer), [Mo2Cp2(mu-PHCy)(mu-CO)(CO)4](BF4) and [Mo2ClCp2(mu-PHPh)(CO)4]. 相似文献
22.
A simple and rapid densitometric method has been developed for the simultaneous determination of amoxycillin trihydrate and clavulanate potassium in pharmaceutical preparations. After extraction of the analytes with distilled water, the extracts were spotted on precoated silica gel plates, which were then eluted with butyl acetate-methanol-glacial acetic acid-water (15 + 7.5 + 7.5 + 3, v/v). Quantitative evaluation was performed by measuring the absorbance reflectance of the analyte spots at lambda = 240 nm. The densitometric method is rapid, selective, precise, and accurate and, thus, can be used for routine analysis of pharmaceutical preparations in quality control laboratories of the pharmaceutical industry. 相似文献
23.
24.
25.
Gordan Horvat Josip Požar Zvonimir Dojnović Dragutin Grgec Saša Blažeka 《Journal of Thermal Analysis and Calorimetry》2014,117(2):901-907
A quasi-adiabatic calorimeter for determining the molar solution enthalpies (Δsol H) of non-volatile solids was constructed. The design of the instrument was adjusted to allow the determination of solution enthalpies of small amounts of solids. For that purpose, the novel apparatus for sample dosage with virtually negligible “blank heat” was built. The rather low heat capacity of the calorimeter was achieved by reducing the volume of the reaction cell (20 mL), the dosing unit, and electric elements (the thermistor and the heater). Good thermal isolation of the reaction cell from the surroundings was accomplished by placing the cell into an evacuated polypropylene vessel. A computer program for processing the calorimetric data according to modified Regnault–Pfaundler method was written. The performance of the calorimeter was tested by determining the heats of the reactions serving as thermochemical standards at 25 °C (the dissolution of KCl and NaCl in water and the dissolution of tris(hydroxymethyl)-aminomethane in 0.1 mol dm?3 HCl(aq)). The obtained data were in very good agreement with the literature values. 相似文献
26.
Electroinitiated polymerization of N-vinylcarbazole has been accomplished by constant potential electrolysis. It was found that direct electron transfer from the monomer to the anode initiates the polymerization even at a potential as low as +0.95 V versus Ag?/ Ag+. Dichloromethane was used as the solvent, and the electrolyte was tetrabutylammonium fluoroborate. Conversions as high as 86% were reached even when a microelectrode was used. Effects of electrode area, temperature, and electrode potential on polymerization were studied. Percent conversion was followed by cyclic voltammetry. 相似文献
27.
Dr. Damián Padín Prof. Jesús A. Varela Prof. Carlos Saá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(33):7470-7478
Ruthenium vinyl carbenes derived from Cp/Cp*RuCl-based complexes (Cp=cyclopentadiene, Cp*=1,2,3,4,5-pentamethylcyclopentadiene) have been routinely invoked as key intermediates in tandem reactions involving a carbene/alkyne metathesis (CAM). A priori, these intermediates resemble the Grubbs-type family of catalysts, but they exhibit a completely different reactivity pattern that few, if any, other catalytic system can reproduce so far. The reactivity of these species with α-unsubstituted and α-substituted alkynals showcases the peculiarities of these intermediates. Although Z-vinyl dihydrooxazines are preferentially obtained with the former, Z-vinyl epoxypyrrolidines are obtained with the latter. A combination of spectroscopic and computational data now prove that a η3-coordination mode of the ruthenium vinyl carbene and the presence of a Lewis basic chloride ligand give rise to two markedly different stereoelectronic faces, which are responsible for the unconventional reactivity of these species. 相似文献
28.
Young Jin Sa Chiyoung Park Hu Young Jeong Seok‐Hee Park Zonghoon Lee Kyoung Taek Kim Gu‐Gon Park Sang Hoon Joo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(16):4186-4190
A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom‐doped carbon (CNT/HDC) core–sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom‐containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom‐containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom‐doped nanocarbon catalysts in terms of half‐wave potential and kinetic current density. The four‐electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long‐term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites. 相似文献
29.
Kunchala Dhanunjayarao Shreenibasa Sa Basava Punna Rao Aradhyula Krishnan Venkatasubbaiah 《Tetrahedron》2018,74(40):5819-5825
The synthesis of N,C-coordinated organoboron compounds (B1-B4) based on phenanthroimidazole described. All the compounds were characterized by various spectroscopic techniques. Single crystal X-ray diffraction analysis of the compounds B1 and B3 revealed that the vicinity around the boron atom adopts tetrahedral geometry. Except compound B4, other organoboron compounds (B1-B3) does not show solvatochromism. All our newly synthesized organoboron compounds exhibited moderate to good solution state quantum yields (0.07–0.88) and moderate solid state quantum yields. 相似文献
30.
Suparna Chakraborty Manoj Kumar Mitra Mahua Ghosh Chaudhuri Biswanath Sa Satadal Das Rajib Dey 《Applied biochemistry and biotechnology》2012,168(7):2043-2056
Sol/gel-derived silica gel was prepared at room temperature from tetraethyl orthosilicate precursor. The extracts of Terminalia chebula (Haritoki) were entrapped into the porous silica gel. Fourier transform infrared analysis revealed the proper adsorption of herbal values in the nanopores of the silica gel. Porosity was estimated by transmission electron microscope studies. The release kinetics of the extract in both 0.1 N HCl, pH 1.2, and Phosphate-buffer saline (PBS), pH 7.2, were determined using UV–Vis spectroscopy. Different dissolution models were applied to release data in order to evaluate the release mechanisms and kinetics. Biphasic release patterns were found in every formulation for both the buffer systems. The kinetics followed a zero-order equation for first 4 h and a Higuchi expression in a subsequent timeline in the case of 0.1 N HCl. In the case of PBS, the formulations showed best linearity with a first-order equation followed by Higuchi’s model. The sustained release of the extract predominantly followed diffusion and super case II transport mechanism. The release value was always above the minimum inhibitory concentration. 相似文献