全文获取类型
收费全文 | 1043篇 |
免费 | 6篇 |
国内免费 | 11篇 |
专业分类
化学 | 694篇 |
晶体学 | 9篇 |
力学 | 27篇 |
数学 | 180篇 |
物理学 | 150篇 |
出版年
2021年 | 4篇 |
2020年 | 8篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 13篇 |
2015年 | 14篇 |
2014年 | 7篇 |
2013年 | 40篇 |
2012年 | 54篇 |
2011年 | 71篇 |
2010年 | 33篇 |
2009年 | 34篇 |
2008年 | 63篇 |
2007年 | 68篇 |
2006年 | 58篇 |
2005年 | 62篇 |
2004年 | 54篇 |
2003年 | 58篇 |
2002年 | 44篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1997年 | 26篇 |
1996年 | 18篇 |
1995年 | 11篇 |
1994年 | 16篇 |
1993年 | 11篇 |
1992年 | 15篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 3篇 |
1987年 | 10篇 |
1986年 | 3篇 |
1985年 | 17篇 |
1984年 | 10篇 |
1983年 | 12篇 |
1982年 | 11篇 |
1981年 | 19篇 |
1980年 | 15篇 |
1979年 | 7篇 |
1978年 | 20篇 |
1977年 | 11篇 |
1976年 | 13篇 |
1975年 | 10篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1971年 | 3篇 |
排序方式: 共有1060条查询结果,搜索用时 31 毫秒
31.
Thomas Merakis Annette Murphy Leone Spiccia Alan Beguin Werner Marty 《Helvetica chimica acta》1989,72(5):993-995
Crystalline salts of the hydrolytic dimer of Cr(III), [Cr2(μ-OH)2(H2O)8]X4·n H2O (X = p-toluenesulfonate (tos) or mesitylene-2-sulfonate (dmtos)) have been prepared in good yields via a simple two-step procedure: H+ oxidation of Cr metal to give Cr2+ (T ≈? 70°) followed by O2 oxidation, of Cr2+ to give the dimer (T ≈? 25°). The mechanism of conversion of Cr2+ into the dimer is discussed. 相似文献
32.
33.
Delangle P Dutasta JP Van Oostenryck L Tinant B Declercq JP 《The Journal of organic chemistry》1996,61(25):8904-8914
The semirigid phosphonamide ligands 1-5 have been synthesized from the macrocyclic precursors 6-9 by reaction with 1,3-propanediol ditosylate or 1,2-dichloroethane. For the thiophosphoryl compounds 1 and 2, and the phosphoryl derivative 5, the reactions were carried out in biphasic aqueous NaOH solutions. The phosphoryl derivatives 3 and 4 were better obtained from NaH in anhydrous tetrahydrofuran. The conformations of the hosts in solution were deduced from low-temperature NMR and NOE difference experiments. Conformational equilibria between exo and endo forms are observed for the 18-membered macrocycles 1 and 3. The exo conformer predominates in solution for the 21-membered macrocycle 2, whereas 4 exists as rapidly exchanging conformers. The X-ray crystal structures of macrocycles 1, 2, and 5 have been determined as well as the complexes 1.Hg(SCN)(2) and 5.LiNO(3). In the Hg(2+) complex the metal ion is located out of the macrocyclic cavity and is coordinated to the thiophosphoryl unit. In 5.LiNO(3)()()the Li(+) cation is located inside the macrocyclic cavity and is coordinated to a tetrahedral array of oxygen donors. Free energies of complexation (DeltaG degrees ) of the phosphorylated ligands 3-5 with alkali metal and ammonium cations were determined in CHCl(3) saturated with H(2)O by picrate extraction experiments. The -DeltaG degrees values are greatest for 4 complexing K(+) and NH(4)(+) (7.3 and 8.0 kcal/mol, respectively). The relationships between structure and binding are discussed. 相似文献
34.
Nilsson YI Aranyos A Andersson PG Bäckvall JE Parrain JL Ploteau C Quintard JP 《The Journal of organic chemistry》1996,61(5):1825-1829
Total syntheses of theaspirone (A and B) and vitispirane (A and B) are described. The key step in the syntheses is the palladium(II)-catalyzed intramolecular oxaspirocyclization of diene alcohol 4 to either vitispirane or the allylic alcohol 9. The outcome of the oxaspirocyclization is very much dependent on the solvent employed. In water-acetic acid (4:1) a 1:1 mixture of the diastereomeric alcohols 9A and 9B was exclusively formed. In water with 8 equiv of a strong non-nucleophilic acid, vitispiranes A and B (1:1) were obtained. An alternative procedure to obtain vitispirane with the use of LiCl and K(2)CO(3) is described. In the latter reaction vitispirane B is formed preferentially. This result is explained by an equilibrium between the two possible pi-allyl complexes 5A and 5B, the kinetically favored 5B being transformed into vitispirane 3B before isomerization to 5A occurs. 相似文献
35.
Acetylcholinesterase (AChE) (EC 3.1.1.7) was modified with activated monomethoxypolyethylene glycol (mPEG). A decrease of 50% in the catalytic activity was measured during the coupling reaction and the change in the surface properties of AChE was used to separate by hydrophobic interaction chromatography the native and the modified enzyme. The native and the modified enzymes were found to have the same optimalcatalytic conditions. Moreover, the Michaelis constant of both enzymes were similar, whereas theV m and the bimolecular-velocity constant calculated for organophosphorus inhibitors were slightly higher for the modified AChE. Finally, the modification with mPEG did not improve the thermal stability, whereas the stability in a few organic solvents increased. 相似文献
36.
By number-theoretical methods we give a result generalizingthose of J. O. Shallit, one particular case of which reads asfollows:
...=2;, where a(n) is equal to 1 if the sum of the digits of n in basetwo is even, and 1 if this sum is odd. Moreover we provea conjecture of Shallit concerning a way of approximating 2 相似文献
37.
38.
Axially disymmetric tertiary amines or quaternary ammonium salts are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines , substituted by a binaphthyl unit, with high yields and absence of racemization. 相似文献
39.
The bicyclic monoselenoacetal 7 , easily obtained from (±)-7-oxabicyclo[2.2.1]hept-5-en-2-one ( 6 ) via a radical addition-acyl migration sequence, was converted to racemic 12-epiprostaglandins 3 and 4 . The key intermediate was the all-cis-formyllactone 2b related to Corey lactone (see 12 ; Scheme 1). The presence of a (tert-butyl)-dimethylsilyl protective group for the 11-OH substituent (prostaglandin numbering) was found to be crucial in avoidingβ -elimination and epimerization during the Wittig-Horner reaction (Scheme 2). Epimerization at C(12) at the formyllactone stage (see 2b ) was also possible and gave the known precursor 1b of naturally occurring prostaglandins and analogs. 相似文献
40.
[reaction: see text]. A procedure for the chemical synthesis of [3-15N]-labeled pseudouridine and a methylated derivative was developed. A suitably protected pseudouridine precursor was nitrated at N3 followed by treatment with 15NH4Cl to afford the 15N-labeled product in six steps with a 20% yield. This methodology will allow for the production of RNAs with [3-15N]pseudouridine and [3-15N-methyl]pseudouridine at specific locations. 相似文献