全文获取类型
收费全文 | 1200篇 |
免费 | 25篇 |
国内免费 | 52篇 |
专业分类
化学 | 1167篇 |
晶体学 | 4篇 |
数学 | 23篇 |
物理学 | 83篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 13篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 7篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 81篇 |
2013年 | 63篇 |
2012年 | 53篇 |
2011年 | 125篇 |
2010年 | 108篇 |
2009年 | 106篇 |
2008年 | 86篇 |
2007年 | 106篇 |
2006年 | 99篇 |
2005年 | 120篇 |
2004年 | 106篇 |
2003年 | 78篇 |
2002年 | 18篇 |
2001年 | 1篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1992年 | 7篇 |
1991年 | 1篇 |
1989年 | 3篇 |
1987年 | 3篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1277条查询结果,搜索用时 15 毫秒
1.
Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity. 相似文献
2.
Xuyuan GuScott Cowell Jinfa YingXuejun Tang Victor J. Hruby 《Tetrahedron letters》2003,44(31):5863-5866
(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings. 相似文献
3.
Peptidosulfonamides are an emerging group of peptidomimetics with a variety of applications in medicinal chemistry. We present a novel approach to the synthesis of peptidosulfonamides, and apply it to a series of new potential inhibitors of the bacterial peptidoglycan biosynthesis enzymes MurD and MurE. The synthesis was conducted via N-phthalimido β-aminoethanesulfonyl chlorides, which are new building blocks for the synthesis of peptidosulfonamides. In the most crucial step, sulfonic acids or their sodium salts were converted into the corresponding sulfonyl chlorides using an excess of either SOCl2 or SOCl2/DMF, and then coupled to the C-protected amino acid. None of the compounds significantly inhibited MurD, however, some inhibited MurE; one had an IC50 below 200 μM, which constitutes a promising starting point for further development. Molecular modelling simulations were performed on two analogues to investigate the absence of inhibitory activity of the sulfonamide compounds on MurD. 相似文献
4.
Valérie Michaut Jean-Marc Paris Jean-Christophe Plaquevent 《Journal of fluorine chemistry》2007,128(8):889-895
Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure. 相似文献
5.
Roberto Ballini Dennis Fiorini Maria Victoria Gil Alessandro Palmieri 《Tetrahedron》2004,60(12):2799-2804
Nitroalkanes have been found to give good yields in Michael and nitroaldol (Henry) reactions by the use of a catalytic amount (10 mol%) of CTAOH, at room temperature and under solvent free conditions and in very short reaction times. The methods do not need a large excess of the nitroalkanes and show good chemoselectivity toward further functionalities. 相似文献
6.
1-Propyl-3-methylimidazolium chloride ([C3MIm]Cl) ionic liquid and sulfamic acid (NH2SO3H), as a synergetic catalytic medium, were used for the transesterification of acetoacetate with alcohols of different structures. It shows the good ability for the chemoselective transesterificatin of β-ketoesters and maintains its catalytic activity in the reuse. 相似文献
7.
Benjamin M. NugentAmie L. Williams E.N. PrabhakaranJeffrey N. Johnston 《Tetrahedron》2003,59(45):8877-8888
The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy. 相似文献
8.
The preparation of polyhydroxylated 6-oxa-nor-tropane glycomimetics structurally related to the glycosidase inhibitor family of the calystegines is reported. The synthetic strategy involves the furanose→piperidine rearrangement of 5-deoxy-5-ureido-l-idose precursors, followed by intramolecular glycosylation involving the primary hydroxyl group. Inversion of the configuration at C-3 in the resulting 6-oxa-(+)-calystegine B2 analogue allows accessing the elusive 3-epi-6-oxa-(+)-calystegine B2 skeleton. Acid-catalyzed opening of the nor-tropane bicycle was observed, however, which could be avoided by careful neutralization of the reaction mixture. The inhibition results suggest that (+)-calystegine B2 derivatives and the corresponding C-3 epimers can be seen as glucomimetics and galactomimetics, respectively, pointing to a 1-azasugar mode of action for this family of alkaloids. 相似文献
9.
Noëlle Martine Gosselet Horacio NaranjoEstelle Renard Catherine AmielBernard Sebille 《European Polymer Journal》2002,38(4):649-654
An acrylic polymer with pendent adamantyl groups was synthesized and its properties in an aqueous solution with a β-cyclodextrin (βCD) epichlorhydrin polymer examined. Viscosity properties of precursor and modified polymers show differences at low concentrations, but not at higher concentration probably due to very important hydrogen bonds which prevent the formation of intermolecular hydrophobic bonds. The association of both complementary polymers through the inclusion of adamantyl groups is evidenced by phases separation occurrence. Phase diagrams were established at two different concentrations of polymers. We have shown a maximal association of both polymers at these two concentrations, for the same ratio βCD moles/adamantyl groups: 2.4. Salt addition favors this association and displaces the two phases zone to smaller concentrations of modified polymer. Further, 4-nitrophenol can be extracted by the concentrated phase resulting from mixture of solutions of guest and host polymers, pointing out the availability of the associated phase to trap organic molecules. 相似文献
10.
Haijun HaoHerbert W. Roesky Yuqiang DingChunming Cui Mark SchormannHans-Georg Schmidt Mathias NoltemeyerBoris ?emva 《Journal of fluorine chemistry》2002,115(2):143-147
β-Diketiminato magnesium fluoride [{CH(CMeNAr)2}Mg(μ-F)(THF)]2·toluene (Ar=2,6-i-Pr2C6H3, 2·toluene) was synthesized. The molecular structure of 2 revealed for the first time, the double fluoro bridge feature between the two magnesium atoms with a typical MgF bond length (average 1.95 Å). 相似文献