全文获取类型
收费全文 | 591篇 |
免费 | 32篇 |
国内免费 | 2篇 |
专业分类
化学 | 386篇 |
晶体学 | 6篇 |
力学 | 20篇 |
数学 | 48篇 |
物理学 | 165篇 |
出版年
2023年 | 6篇 |
2022年 | 14篇 |
2021年 | 16篇 |
2020年 | 11篇 |
2019年 | 18篇 |
2018年 | 13篇 |
2017年 | 12篇 |
2016年 | 21篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 59篇 |
2012年 | 42篇 |
2011年 | 42篇 |
2010年 | 24篇 |
2009年 | 7篇 |
2008年 | 28篇 |
2007年 | 27篇 |
2006年 | 33篇 |
2005年 | 31篇 |
2004年 | 15篇 |
2003年 | 19篇 |
2002年 | 13篇 |
2001年 | 8篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1979年 | 7篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1972年 | 2篇 |
1930年 | 2篇 |
1927年 | 1篇 |
排序方式: 共有625条查询结果,搜索用时 11 毫秒
1.
Vandana Singh Ashutosh TiwariDevendra Narayan Tripathi Tulika Malviya 《Tetrahedron letters》2003,44(39):7295-7297
O-Methylation is of outstanding importance in structural polysaccharide chemistry. A novel method for the methylation of polysaccharides using microwave (MW) irradiation is described. Seed gum from Cyamopsis tetragonolobus (Guar) was fully methylated with dimethyl sulphate and sodium hydroxide using 100% microwave power for 4 min in 68% yield. The completely methylated seed gum thus obtained was hydrolyzed by 70% formic acid followed by 0.5N H2SO4 under full microwave power for 1.16 and 1.66 min, respectively. The partially methylated monosaccharides were separated and identified. 相似文献
2.
Multiple-zero multiple-pole optical filter transfer functions may be implemented more efficiently in an integrated optics architecture if higher order N × M optical couplers are utilized. For example, a coherent ring resonator made from two 3×3 couplers offers some advantages over the three mirror Fabry-Perot etalon, which is its analog. To this end we develop the formalism for obtaining the transfer functions and scattering matrices of ring resonators made from two N × M couplers. We then present a methodology for analyzing serial and parallel systems of N × M optical coupler ring resonators. 相似文献
3.
The catalytic activity of Chromobacterium viscosum lipase (CV-lipase) was estimated across varying surfactant tail lengths (C-10-C-18) in water-in-oil (w/o) microemulsions of cationic surfactants containing four different hydroxyethyl-substituted head groups. An attempt to find a correlation, if any, between the activity of interfacially solubilized lipase and the varying surfactant tails was made for the first time in micellar enzymology. The second-order rate constant, k2, in lipase-catalyzed hydrolysis of p-nitrophenyl-n-hexanoate at pH 6.0 and 25 degrees C shows an improvement in enzyme activity (approximately 30-140%) across different head groups of amphiphiles with increasing tail lengths in varying solution compositions. Improvement of enzyme activity is prominent in ascending from C-10 to C-14/C-16, depending on the nature of polar head group. The hydrolytic activity of lipase in different surfactant (50 mM)/water/isooctane/n-hexanol with varying z= [alcohol]/[surfactant] (6.4 or 4.8) was amplified by 25-250% with increment in surfactant tail length in comparison with widely used cationic w/o microemulsions having solution compositions (z=16). As a notable outcome of this research, we found w/o microemulsions of 25 mM tetradecyltrimethylammonium bromide/water/isooctane/n-hexanol (z=8) producing the highest ever activity of lipase in any w/o microemulsions. 相似文献
4.
Thermodynamic studies were performed on 12 pairs of N-trifluoroacetyl-O-alkyl nipecotic acid ester enantiomers on diluted permethylated beta-cyclodextrin stationary phase (CP Chirasil-Dex CB). The influence of ester alkyl group structure on interaction with permethylated beta-cyclodextrin (Me-CD) and enantioselectivity was studied. The types of alkyl groups studied included n-alkyl (C1-C5) and groups containing branching at differing locations relative to the chiral center of the molecule. The results show that for a given molecular weight, the n-alkyl esters have stronger interactions with Me-CD than esters containing branched alkyl groups. However, although having weaker interactions with Me-CD, esters containing alpha-branched alkyl groups exhibit higher enantioselectivity than the corresponding n-alkyl or beta-branched isobutyl esters. From the retention data, thermodynamic parameters were estimated using the retention increment method and enthalpy-entropy compensation plots (ln R' versus deltaH) were constructed. The results suggest that ester enantiomers with branching at the alpha-carbon of the ester alkyl group have additional and/or different types of enantioselective interactions with Me-CD than the C1-C5 n-alkyl esters or beta-branched isobutyl ester. In order to obtain a qualitative sense of the interaction with Me-CD, structures of the diastereomeric complexes formed between Me-CD and some of the ester enantiomers were modeled using simulated annealing molecular dynamics. 相似文献
5.
Amino Acid based cationic surfactants in aqueous solution: physicochemical study and application of supramolecular chirality in ketone reduction 总被引:2,自引:0,他引:2
Roy S Das D Dasgupta A Mitra RN Das PK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10398-10404
The present study provides a molecular understanding of the origin of the chirality in aqueous micelles and its correlation with the proficiency of stereoselective ketone reduction. The effects of varied headgroup architecture on the surface-active properties as well as on other microstructural parameters were studied and correlated to the structural differences of these naturally occurring amino acid containing surfactants (1-4). Micropolarity sensed by pyrene showed that the micelles prepared using 1-4 are mostly hydrated; particularly large headgroup size surfactant produces more polar environment. A theoretical study was done to quantify the varied spatial dissymmetry for all four surfactants. Asymmetric reduction of prochiral ketones was carried out at the aqueous micellar interface of these chiral amphiphiles by exploiting the supramolecular chirality as evidenced from a circular dichroism study. The enantioselectivity of the reduction process is rationally improved through increase in spatial dissymmetry and steric constraint imposed at the micellar interface by the polar head of surfactants. 相似文献
6.
Sumit Bhaduri Krishna R. Sarma Bikshandarkovil A. Narayan 《Transition Metal Chemistry》1981,6(4):206-210
Summary Four-coordinate nickel nitrosyl complexes of the general formula Ni(NO)X(Dppe) (Dppe=Ph2PCH2CH2PPh2) have been prepared byin situ formation of Ni(NO2)X(Dppe), (X= Cl, Br, I or SCN) followed by reduction with triphenylphosphine, or carbon monoxide, and/or DMF. Oxygenation of the nitrosyl complexes gives the corresponding nitro products and as indicated by u.v.-vis spectroscopy involves formation of an intermediate. The oxygenation rate increases markedly in the presence of light or of a catalytic amount of benzoyl peroxide and a tentative explanation is offered for these observations. Ionic adducts are formed in reactions between the nitrosyl complexes and donor molecules.Paper presented in part at the XXth ICCC Conference. 相似文献
7.
A convenient, novel synthesis of alkyl cyclopropyl ketones based on Z-1-bromo-1-alkenylboronate esters is developed. α-Bromo-(Z)-1-alkenylboronate esters readily available from literature procedures smoothly undergo a reaction with cyclopropylmagnesium bromide in tetrahydrofuran to provide the corresponding ‘ate’ complexes. These ‘ate’ complexes undergo intramolecular nucleophilic substitution reactions to provide the corresponding (E)-1-alkenylboronate esters containing cylcopropyl moiety for the first time in good isolated yields (68-82%). The carbon skeleton present in these intermediates is confirmed by oxidation with hydrogen peroxide and sodium acetate to afford the corresponding alkyl cyclopropyl ketones in good yields (72-85%). 相似文献
8.
9.
Roland Prewo Jost H. Bieri Subhendu Narayan Ganguly Max Viscontini 《Helvetica chimica acta》1982,65(3):1094-1099
The Configuration at C(6) of Natural 5,6,7,8-Tetrahydro-L-biopterin and of its Pentaacetate The structure of (6.R)-pentaacetyl-5,6,7,8-tetrahydro-L-biopterin, one of two diastereoisomers obtained by catalytic hydrogenation and subsequent acetylation of L-biopterin, has been determined by X-ray diffraction analysis. The space group is P212121, a=8,053(l), b=14,955(3), c= 21,502 (4) Å. The asymmetric unit contains one molecule of the biopterin derivative and one of ethyl acetate. The R-configuration can be assigned to C(6) by reference to the known configurations of the other asymmetric C-atoms. As hydrolysis of this diastereoisomer yields the natural 5, 6,7,8-tetrahydro-L-biopterin, the latter also possesses the (6 R)-configuration. 相似文献
10.
A simple, novel diastereoselective synthesis of both (E)- and (Z)-allylsilanes via organoboranes is developed. (E)-1-Alkenylboronate esters easily prepared from the corresponding terminal alkynes via hydroboration with dibromoborane-methyl sulfide complex followed by treatment with 1,3-propane diol readily react with trimethylsilylmethyllithium at −78 °C in methanol followed by reaction with iodine in methanol to produce the corresponding (Z)-allylsilanes in high yields (72-80%) and in high stereochemical purities (98% as evidenced by CMR spectral data). Similarly, the (Z)-1-alkenylboronate esters react with trimethylsilylmethyllithium at −78 °C in methanol followed by treatment with iodine in methanol to produce the corresponding (E)-allylsilanes in moderate yields (57-65%) in high stereochemical purities (>98% as revealed by CMR spectral data). 相似文献