全文获取类型
收费全文 | 2680篇 |
免费 | 88篇 |
国内免费 | 290篇 |
专业分类
化学 | 2484篇 |
晶体学 | 7篇 |
力学 | 7篇 |
综合类 | 3篇 |
数学 | 11篇 |
物理学 | 546篇 |
出版年
2024年 | 5篇 |
2023年 | 54篇 |
2022年 | 51篇 |
2021年 | 33篇 |
2020年 | 40篇 |
2019年 | 31篇 |
2018年 | 33篇 |
2017年 | 45篇 |
2016年 | 74篇 |
2015年 | 68篇 |
2014年 | 95篇 |
2013年 | 171篇 |
2012年 | 179篇 |
2011年 | 182篇 |
2010年 | 147篇 |
2009年 | 176篇 |
2008年 | 138篇 |
2007年 | 190篇 |
2006年 | 158篇 |
2005年 | 151篇 |
2004年 | 141篇 |
2003年 | 80篇 |
2002年 | 77篇 |
2001年 | 69篇 |
2000年 | 57篇 |
1999年 | 44篇 |
1998年 | 55篇 |
1997年 | 45篇 |
1996年 | 36篇 |
1995年 | 40篇 |
1994年 | 39篇 |
1993年 | 33篇 |
1992年 | 39篇 |
1991年 | 45篇 |
1990年 | 41篇 |
1989年 | 36篇 |
1988年 | 36篇 |
1987年 | 16篇 |
1986年 | 11篇 |
1985年 | 12篇 |
1984年 | 23篇 |
1983年 | 8篇 |
1982年 | 15篇 |
1981年 | 5篇 |
1980年 | 10篇 |
1979年 | 5篇 |
1978年 | 11篇 |
1976年 | 2篇 |
1973年 | 3篇 |
1967年 | 1篇 |
排序方式: 共有3058条查询结果,搜索用时 93 毫秒
121.
N. Seshu Babu 《Tetrahedron letters》2007,48(43):7642-7645
The intermolecular hydroamination of vinyl arene derivatives has been efficiently carried out using a tungstophosphoric acid (TPA) catalyst under solvent free and mild reaction conditions. The present protocol provides an environmentally benign, easy to handle and highly active solid acid catalyst for hydroamination of vinyl arenes. The catalyst yields both hydroamination and hydroarylation products and the selectivity mostly depends on the reaction conditions. 相似文献
122.
Shinichi Yamabe Shigeki Kato Hiroshi Fujimoto Kenichi Fukui 《Theoretical chemistry accounts》1973,30(4):327-337
An ab initia molecular orbital calculation was done as to a reacting system, NH3+HF=NH4F, with the inclusion of the solvent effect as the origin of dipolar field. The reactants were assumed to stay in dimers, (NH3)2 and (HF)2, in advance to the reaction, and the respective partners of two reactants were regarded as point dipoles. The system was stabilized to some extent by two dipoles adopted. A study of configuration analysis on this system was made with and without the dipoles. Their effect was found to be favorable for proceeding of the reaction. 相似文献
123.
On the basis of a better analytical exploitation of acid-induced cloud point approach, a systematic study on the phase behaviour of acid aqueous solutions of anionic surfactants and factors affecting anionic surfactant-mediated extractions was performed. The anionic surfactants investigated were alkylsulphonates (ASS) with alkylchain lengths comprised between 8 and 16 carbon atoms. The critical hydrochloric acid concentration (minimal acid concentration required to separation in two liquid phases) was found to increase as alkylchain length of the anionic surfactant increased from 10 to 14. Non-acid-induced liquid-liquid phase separation was observed for sodium octanesulphonate (SOS) or sodium hexadecyl sulphonate (SHS) in the hydrochloric concentration range 0-10 M. Acid aqueous solutions of sodium decylsulphonate (SDeS) and sodium dodecylsulphonate (SDoS) separated into two liquid phases at temperatures ranging between 10 and 80 °C, while temperatures >35 °C were required for sodium tetradecylsulphonate. The influence on extraction efficiency and concentrating ability of experimental variables such as hydrophobicity and concentration of surfactant, nature and concentration of analyte, hydrochloric acid concentration, time and temperature of extraction and time of equilibration and centrifugation was examined. Advantages provided by anionic surfactant-mediated extractions over the use of non-ionic surfactants (cloud point extractions) are discussed. 相似文献
124.
Kathrin Wichmann Bianca Antonioli Tilo Shnel Marco Wenzel Kerstin Gloe Karsten Gloe Jason R. Price Leonard F. Lindoy Alexander J. Blake Martin Schrder 《Coordination chemistry reviews》2006,250(23-24):2987
In the discussion that follows some of the more recent progress in the area of anion binding by synthetic polyamine receptors is presented, with emphasis given to work undertaken by the authors’ groups. A continuing theme in these studies has been the relationship between receptor structure and its anion extraction properties.Systematic solvent extraction and structural studies for halide and perrhenate complexes with polyamines of tripodal, macrocyclic and macrobicyclic architecture that contain both aromatic moieties and four to eight amine functions have been performed in order to derive relevant structure-binding/extractability relationships. The results demonstrate that the binding and extraction behaviour of the polyamines towards halides and perrhenate is a complex function of their structural features, degree of protonation and lipophilic properties. The extraction is characterized by the preferred formation of mono- and diprotonated amine species in the organic phase. X-ray structure studies of iodide and perrhenate complexes with open-chain tetraamino derivatives and octaamino cryptands in different protonation states lead to the conclusion that in the first case only limited chelation of the anion occurs and in the second only highly protonated species are able to encapsulate the anion. The structural patterns observed are strongly influenced by the presence of water molecules in the crystals. 相似文献
125.
G. Wytze Meindersma Lara M. Galán Sánchez Antje R. Hansmeier André B. de Haan 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1125-1136
Summary. Ionic liquids offer tremendous opportunities to intensify reactions and separations in process technologies by tuning their
physical and chemical properties. Several ionic liquids are suitable for the separation of aromatic and aliphatic hydrocarbons.
CO2 absorption behavior was influenced by the functionalized chains appended to the room temperature ionic liquid (RTIL) cation.
Ionic liquids seem able to combine the chemical features of amine solutions with the characteristic advantages of the physical
solvents used for CO2 absorption. 相似文献
126.
Quinazolin-4(3H)-one derivatives were synthesized successfully via a one-pot, three component reaction of isatoic anhydride and an orthoester with ammonium acetate or a primary amine catalyzed by silica sulfuric acid under solvent-free conditions. This is the first report on the synthesis of 2-substituted quinazolin-4(3H)-ones by this procedure. 相似文献
127.
锂离子筛的制备及其交换性能研究 总被引:3,自引:0,他引:3
用浓度为0.5mol/L的盐酸对高温固相合成的前体LiMn2O4进行酸洗脱锂,制得锂离子筛HMn2O4,并在不同pH值和温度下进行了Li 交换性能的研究,同时运用XRD和TEM进行了相应表征。结果表明,锂离子筛吸附交换前后晶体结构只发生了细微变化,但都仍为尖晶石型结构;交换反应在前10min速率最快,约20min就趋于平衡;Li 交换总量随pH值增大而升高,其中pH=7时交换容量为18.5526mg/g;Li 交换量和交换选择性随温度的升高而显著增强。 相似文献
128.
A rapid, robust, sensitive and selective time-based flow injection (FI) on-line solvent extraction system interfaced with electrothermal atomic absorption spectrometry (ETAAS) is described for analyzing ultra-trace amounts of Cr(VI). The sample is initially mixed on-line with isobutyl methyl ketone (IBMK). The Cr(VI) is complexed by reaction with ammonium pyrrolidine dithiocarbamate (APDC), and the non-charged Cr(VI)–PDC chelate formed is extracted into IBMK in a knotted reactor made from PTFE tubing. The organic extractant is separated from the aqueous phase by a gravity phase separator with a small conical cavity and delivered into a collector tube, from which 55 μl organic concentrate is subsequently introduced via an air flow into the graphite tube of the ETAAS instrument. The operations of the FI-system and the ETAAS detector are synchronously coupled. A significant advantage of the approach is that matrix constituents, such as high salt contents, effectively are eliminated. The extraction procedure was optimized by a simplex approach. A central composite design was subsequently employed to verify the estimated operational optimum. An 18-fold enhancement in sensitivity of Cr(VI) was achieved after preconcentration for 99 s at a sample flow rate of 5.5 ml min−1, as compared to direct introduction of 55 μl of sample, yielding a detection limit (3σ) of 3.3 ng l−1. The sampling frequency was 24.2 samples h−1. The proposed method was successfully evaluated by analyzing a NIST Cr(VI)-reference material, synthetic seawater and waste waters, and waste water samples from an incineration plant and a desulphurization plant, respectively. 相似文献
129.
Asymmetric polysulfone membranes were prepared by wet phase inversion method with different demixing rate of casting solutions. The influent factor of demixing rate was focused on the polarity of additive in the polysulfone/N-methyl-2-pyrrolidone/water ternary system. With increasing the polarity of alcohols in the casting solution, the decrease in skin layer thickness was observed and then a poor separation performance of membranes can be obtained. It was found that the polar additive caused the rapidly demixing of casting solution in coagulation bath and formed porous asymmetric membranes with defective skin layer. In the other case, chloroform was used as the non-polar additive in casting solution. With increasing the mount of chloroform in the casting solution, the increase in skin layer thickness was observed and then lead to a good separation performance of these membranes. It was found that of the non-polar additive delays the demixing rate of casting solution in this ternary system. The separation performance of these asymmetric membranes were characterized by the measurement of dehydration of ethanol/water mixture by pervaporation and observed the morphology by scanning electron microscopy. It was found that the separation performance of asymmetric polysulfone membrane strongly depends on the polarity of adding solvent in polysulfone/N-methyl-2-pyrrolidone/water ternary system. 相似文献
130.
在B3LYP/6-31G(d, p)(Rh和P采用LANL2DZ + Polar)水平下,利用自洽反应场(SCRF)的Onsager模型,系统研究了C6H12、C6H6、THF、CH2Cl2、CH3OH和H2O(相对介电常数ε分别为2.02、2.25、7.58、8.93、32.63和78.39)六种溶剂对乙烯氢甲酰化反应中各驻点的结构和反应机理的影响.分别在上述溶剂中优化了反应物、产物、中间体和过渡态的结构,并计算了自由能和活化自由能.计算结果表明,不同溶剂对反应势能面上各驻点的结构和能量均有一定的影响,而且随着相对介电常数ε的增加,反应的活化自由能下降.水是以上六种溶剂中最佳的溶剂,这与大量的实验研究结果一致. 相似文献