全文获取类型
收费全文 | 2545篇 |
免费 | 641篇 |
国内免费 | 241篇 |
专业分类
化学 | 2999篇 |
晶体学 | 6篇 |
力学 | 133篇 |
综合类 | 15篇 |
数学 | 110篇 |
物理学 | 164篇 |
出版年
2024年 | 3篇 |
2023年 | 37篇 |
2022年 | 67篇 |
2021年 | 103篇 |
2020年 | 217篇 |
2019年 | 161篇 |
2018年 | 171篇 |
2017年 | 115篇 |
2016年 | 195篇 |
2015年 | 198篇 |
2014年 | 208篇 |
2013年 | 291篇 |
2012年 | 183篇 |
2011年 | 184篇 |
2010年 | 157篇 |
2009年 | 137篇 |
2008年 | 152篇 |
2007年 | 123篇 |
2006年 | 141篇 |
2005年 | 92篇 |
2004年 | 99篇 |
2003年 | 94篇 |
2002年 | 60篇 |
2001年 | 49篇 |
2000年 | 24篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 32篇 |
1996年 | 15篇 |
1995年 | 11篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 10篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 8篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1971年 | 3篇 |
排序方式: 共有3427条查询结果,搜索用时 16 毫秒
141.
N-Arylation of imidazoles with arylboronic acids was efficiently carried out in the presence of a catalytic amount of SiO2-NHC-CuI in methanol at room temperature under base-free reaction conditions. The reactions of a variety of arylboronic acids with imidazoles generated the corresponding products N-arylimidazoles in good to excellent yields. In addition, SiO2-NHC-CuI could be recovered and recycled for six consecutive trials without significant loss of its reactivity. 相似文献
142.
Biswanath Das Boyapati Veeranjaneyulu Maddeboina Krishnaiah P. Balasubramanyam 《合成通讯》2013,43(11):1929-1935
A simple and efficient method has been developed for benzylation and allylation of naphthols by treatment of the compounds with benzylic and allylic alcohols, respectively, in the presence of amberlyst-15. Several heterogeneous catalysts were screened for the reaction, and amberlyst-15 was found to be most effective. 相似文献
143.
Melamine trisulfonic acid, which is easily prepared by the reaction of melamine with neat chlorosulfonic acid, is able to efficiently catalyze the chemoselective methoxymethylation of alcohols with dimethoxymethane (DMM). All reactions were performed under mild and completely heterogeneous reaction conditions in good to high yields. 相似文献
144.
A combination of molybdatophosphoric acid and NaNO2 in the presence of wet SiO2 was used as an effective oxidizing agent for the oxidation of 1,2‐dihydroquinolines to their corresponding quinoline derivatives in dichlomethane at room temperature with excellent yields. 相似文献
145.
Li‐Wei Zhao Hui‐Min Shi Zhe An Jiu‐Zhao Wang Prof. Jing He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12350-12355
Effectively enhancing the enantioselectivity is a persistent challenge in heterogeneous asymmetric catalysis. Here, the validity of a layered double hydroxides (LDH) nanosheet as an efficient planar substituent to enhance the enantioselectivity has been investigated theoretically; first in vanadium‐catalyzed asymmetric epoxidation of allylic alcohols, and then in zinc‐catalyzed direct asymmetric aldol addition. The computational predication is further confirmed experimentally in zinc‐catalyzed direct asymmetric aldol addition by controlling the location of catalytic sites. 相似文献
146.
Dr. Ming‐Hua Xie Xiu‐Li Yang Dr. Yabing He Prof. Dr. Jian Zhang Prof. Dr. Banglin Chen Prof. Dr. Chuan‐De Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14316-14321
A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed‐metal–organic framework (M′MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M′MOF of [Zn2(MnOH–TCPP)(DPNI)] ? 0.5 DMF ? EtOH ? 5.5 H2O ( CZJ‐1 ; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4‐carboxyphenyl)porphyrin); DPNI=N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α‐Po topology in which the basic Zn2(COO)4 paddle‐wheel clusters are bridged by metalloporphyrin to form two‐dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three‐dimensional porous structure. The porosity of CZJ‐1 has been established by both crystallographic studies and gas‐sorption isotherms. CZJ‐1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so‐called K–A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M′MOF catalyst. 相似文献
147.
Astam K. Patra Arghya Dutta Prof. Dr. Asim Bhaumik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12388-12395
Mesoporous nanoparticles composed of γ‐Al2O3 cores and α‐Fe2O3 shells were synthesized in aqueous medium. The surface charge of γ‐Al2O3 helps to form the core–shell nanocrystals. The core–shell structure and formation mechanism have been investigated by wide‐angle XRD, energy‐dispersive X‐ray spectroscopy, and elemental mapping by ultrahigh‐resolution (UHR) TEM and X‐ray photoelectron spectroscopy. The N2 adsorption–desorption isotherm of this core–shell materials, which is of type IV, is characteristic of a mesoporous material having a BET surface area of 385 m2 g?1 and an average pore size of about 3.2 nm. The SEM images revealed that the mesoporosity in this core–shell material is due to self‐aggregation of tiny spherical nanocrystals with sizes of about 15–20 nm. Diffuse‐reflectance UV/Vis spectra, elemental mapping by UHRTEM, and wide‐angle XRD patterns indicate that the materials are composed of aluminum oxide cores and iron oxide shells. These Al2O3@Fe2O3 core–shell nanoparticles act as a heterogeneous Fenton nanocatalyst in the presence of hydrogen peroxide, and show high catalytic efficiency for the one‐pot conversion of cyclohexanone to adipic acid in water. The heterogeneous nature of the catalyst was confirmed by a hot filtration test and analysis of the reaction mixture by atomic absorption spectroscopy. The kinetics of the reaction was monitored by gas chromatography and 1H NMR spectroscopy. The new core–shell catalyst remained in a separate solid phase, which could easily be removed from the reaction mixture by simple filtration and the catalyst reused efficiently. 相似文献
148.
Dr. Baoshun Liu Dr. Xuelei Wang Dr. Liping Wen Prof. Dr. Xiujian Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10751-10759
The in situ open‐circuit voltages (Voc) and the in situ photoconductivities have been measured to study electron behavior in photocatalysis and its effect on the photocatalytic oxidation of methanol. It was observed that electron injection to the conduction band (CB) of TiO2 under light illumination during photocatalysis includes two sources: from the valence band (VB) of TiO2 and from the methanol molecule. The electron injection from methanol to TiO2 is slower than that directly from the VB, which indicates that the adsorption mode of methanol on the TiO2 surface can change between dark and illuminated states. The electron injection from methanol to the CB of TiO2 leads to the upshift of the Fermi level of electrons in TiO2, which is the thermodynamic driving force of photocatalytic oxidation. It was also found that the charge state of nano‐TiO2 is continuously changing during photocatalysis as electrons are injected from methanol to TiO2. Combined with the apparent Langmuir–Hinshelwood kinetic model, the relation between photocatalytic kinetics and electrons in the TiO2 CB was developed and verified experimentally. The photocatalytic rate constant is the variation of the Fermi level with time, based on which a new method was developed to calculate the photocatalytic kinetic rate constant by monitoring the change of Voc with time during photocatalysis. 相似文献
149.
150.
Olga Bortolini Dr. Alberto Cavazzini Pier Paolo Giovannini Roberto Greco Nicola Marchetti Dr. Alessandro Massi Luisa Pasti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7802-7808
The heterogeneous proline‐catalyzed aldol reaction was investigated under continuous‐flow conditions by means of a packed‐bed microreactor. Reaction‐progress kinetic analysis (RPKA) was used in combination with nonlinear chromatography for the interpretation, under synthetically relevant conditions, of important mechanistic aspects of the heterogeneous catalytic process at a molecular level. The information gathered by RPKA and nonlinear chromatography proved to be highly complementary and allowed for the assessment of optimal operating variables. In particular, the determination of the rate‐determining step was pivotal for optimizing the feed composition. On the other hand, the competitive product inhibition was responsible for the unexpected decrease in the reaction yield following an apparently obvious variation in the feed composition. The study was facilitated by a suitable 2D instrumental arrangement for simultaneous flow reaction and online flow‐injection analysis. 相似文献