全文获取类型
收费全文 | 1282篇 |
免费 | 93篇 |
国内免费 | 242篇 |
专业分类
化学 | 1558篇 |
晶体学 | 1篇 |
力学 | 2篇 |
综合类 | 1篇 |
数学 | 4篇 |
物理学 | 51篇 |
出版年
2023年 | 19篇 |
2022年 | 17篇 |
2021年 | 21篇 |
2020年 | 33篇 |
2019年 | 25篇 |
2018年 | 33篇 |
2017年 | 30篇 |
2016年 | 47篇 |
2015年 | 55篇 |
2014年 | 71篇 |
2013年 | 122篇 |
2012年 | 48篇 |
2011年 | 77篇 |
2010年 | 77篇 |
2009年 | 65篇 |
2008年 | 87篇 |
2007年 | 65篇 |
2006年 | 80篇 |
2005年 | 90篇 |
2004年 | 92篇 |
2003年 | 70篇 |
2002年 | 48篇 |
2001年 | 29篇 |
2000年 | 33篇 |
1999年 | 25篇 |
1998年 | 26篇 |
1997年 | 51篇 |
1996年 | 35篇 |
1995年 | 24篇 |
1994年 | 12篇 |
1993年 | 30篇 |
1992年 | 24篇 |
1991年 | 7篇 |
1990年 | 13篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1617条查询结果,搜索用时 15 毫秒
1.
Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis. 相似文献
2.
Optimization of the Heck reaction of 4-bromoacetophenone with styrene by a polymer supported, sulfur-containing palladacycle, varying 6 factors at a total of 28 different levels, corresponding to 5760 different possibilities was undertaken. Conversion improved from 34%, with large observable leaching to 88% with no leaching. This was accomplished using a Design of Experiments approach facilitated by the Statistical Design Package, MODDE 7.0TM. 相似文献
3.
Leonard M Khalilov Ludmila V Parfenova Askhat G Ibragimov Usein M Dzhemilev 《Journal of organometallic chemistry》2004,689(2):444-453
This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt3 and i-Bu2AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp2ZrCl2. 相似文献
4.
Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. 相似文献
5.
The synthesis of enantiopure bis-THF is described, starting from d-mannitol. Bis-THF is used as chiral ligand for organolithium reagents in four different reactions. The enantioselectivity provided by this ligand is moderate, and the asymmetric induction is in line with the expected model. 相似文献
6.
A photoemission study of molybdenum hexacarbonyl adsorption and decomposition on TiO2(1 1 0) surface
The adsorption and decomposition of molybdenum hexacarbonyl on (1 1 0) TiO2 surfaces were studied using both core levels and valence band photoemission spectroscopies. It was found that after an adsorption at 140 K, when going back to room temperature, only a small part of molybdenum compounds, previously present at low temperature, remained on the TiO2 surface. This indicates that the desorption temperature on such a surface is lower than the decomposition one. The use of photon irradiation to decompose the hexacarbonyl molecule was also studied. It was shown that during such a decomposition molecular fragments were chemisorbed on the surface allowing a higher amount of metal to remain on the surface. It was also shown that it was possible to get rid of adsorbed subcarbonyl groups and to organize the metal atoms by thermal treatments at temperatures as low as 400 K, i.e. much lower than the one needed to obtain the same structures using physical vapour deposition (PVD). Moreover, due to lower used temperatures, this chemical way of deposition allows a better control of the interface than during PVD growth. 相似文献
7.
Sølvi Storsæter 《Surface science》2006,600(10):2051-2063
The heats of adsorption of different C1 and C2 molecules assumed to be present during the initial steps of the Fischer-Tropsch synthesis and activation energies for elementary steps envisioned to occur in the synthesis are calculated for Co by using the unity bond index-quadratic exponential potential (UBI-QEP) method. The preexponential factors for the elementary steps are calculated from transition-state theory, and the rate constants are calculated according to the Arrhenius equation. The activation barrier for hydrogenation of CO is found to be lower compared to hydrogen assisted dissociation of CO, which has a smaller activation barrier than direct dissociation of CO. The reaction steps with high activation barriers are eliminated. Based on this elimination two sets of elementary steps for formation of C1 and C2 alkenes and alkanes in the Fischer-Tropsch synthesis are established: one based on hydrogen assisted CO dissociation (carbide mechanism) and one based on CO hydrogenation (CO insertion mechanism). In addition, one mechanism of producing CO2 from the water-gas shift reaction is proposed. The resulting mechanisms are combined and used in the microkinetic model, which are fitted to experimental results at methanation conditions (T = 483 K or 493 K, p = 1.85 bar and H2/CO = 10) over a Co/Al2O3 Fischer-Tropsch catalyst. A good tuning is obtained by adjusting the C-Co and H-Co binding strengths. The microkinetic modelling based on these assumptions indicates that CO is mainly converted through hydrogenation of CO and that C2 compounds are mainly produced by insertion of CO into a metal-methyl bond. Thus, from the surface coverages and reaction rates predicted by the microkinetic modelling the mechanism can be further reduced to only include the CO insertion mechanism. Hydrogenation of CHO to CH2O is found to be the rate determining initiation step, and insertion of CO into a metal-methyl bond is found to be the rate determining step for chain growth. By using the UBI-QEP method for calculation of activation energies, the activation barriers for dissociation of CO and hydrogenation of surface carbon are found to be too large for the carbide mechanisms to occur. However, experimental data or another theoretical method is necessary in order to support or disprove the calculated activation energies in this work. 相似文献
8.
Regioselective allylation reactions using crotyl Grignard reagent-CeCl3 systems are described. Regioselectivity depends on the lanthanide salts: α-product was predominantly produced with light rare earth elements such as La, Ce, Pr, Nd, whereas γ-product was formed when heavy rare earth elements were used. 相似文献
9.
Roxana S. Timofte 《Tetrahedron letters》2004,45(1):39-42
High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)3Si(CH2)3FG (FG=NH2, NHMe, Cl, NHC(O)NH2, OC(O)CMe(CH2), NCO, NEt2). High loadings (0.66-2.15 mmol g−1) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state 13C NMR studies on individual pellets. 相似文献
10.
Ilga Mutule 《Tetrahedron letters》2004,45(20):3909-3912
Arylzinc reagents were readily prepared from aryl iodides using a Zn-Cu couple in a microwave environment. A sequential arylzinc formation-Negishi cross-coupling protocol suitable for parallel high-throughput synthesis has been developed. 相似文献