全文获取类型
收费全文 | 367篇 |
免费 | 9篇 |
专业分类
化学 | 309篇 |
晶体学 | 3篇 |
力学 | 3篇 |
数学 | 35篇 |
物理学 | 26篇 |
出版年
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 4篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 5篇 |
2014年 | 6篇 |
2013年 | 13篇 |
2012年 | 15篇 |
2011年 | 26篇 |
2010年 | 14篇 |
2009年 | 16篇 |
2008年 | 21篇 |
2007年 | 25篇 |
2006年 | 25篇 |
2005年 | 17篇 |
2004年 | 12篇 |
2003年 | 9篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 3篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 8篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1972年 | 2篇 |
1966年 | 3篇 |
1965年 | 2篇 |
1955年 | 2篇 |
1947年 | 3篇 |
1941年 | 6篇 |
1940年 | 2篇 |
1939年 | 8篇 |
1937年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有376条查询结果,搜索用时 15 毫秒
1.
2.
Haitao Qian Edith Mathiowitz 《Journal of polymer science. Part A, Polymer chemistry》2007,45(24):5899-5915
We succeeded in developing the acyl chloride‐facilitated condensation polymerization method for the synthesis of new poly(anhydride‐ester)s with aromatic side groups, which cannot be polymerized by the classic melt condensation polymerization method. Using chlorinated and acylated carboxylic acids as the intermediates, the polymerization was carried out at low temperatures of 120 or 135 °C to yield pure poly(anhydride‐ester)s of molecular weights as high as 1.55 × 105 with minimal side‐reactions. A homogeneous route of preparation was developed and optimized, using butyric anhydride as the acylating reagent and oxalyl chloride as the chlorinating reagent. A comparison of the mechanisms of the classic method and the new method indicates that the effects of transacylation—cyclization and oligomer formation—were greatly reduced due to the high reactivity of carboxylic acid chloride and the steric effect of bulky acyl groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5899–5915, 2007 相似文献
3.
Ccile Nouvel Philippe Dubois Edith Dellacherie Jean‐Luc Six 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2577-2588
The whole controlled synthesis of novel amphiphilic polylactide (PLA)‐grafted dextran copolymers was achieved. The control of the architecture of such biodegradable and potentially biocompatible copolymers has required a three‐step synthesis based on the “grafting from” concept. The first step consisted of the partial silylation of the dextran hydroxyl groups. This protection step was followed by the ring‐opening polymerization of D ,L ‐lactide initiated from the remaining OH functions of the partially silylated polysaccharide. The third step involved the silylether group deprotection under very mild conditions. Based on previous studies, in which the control of the first step was achieved, this study is focused on the last two steps. Experimental conditions were investigated to ensure a controlled polymerization of D ,L ‐lactide, in terms of grafting efficiency, graft length, and transesterification limitation. After polymerization, the final step was studied in order to avoid degradation of both polysaccharide backbone and polyester grafts. The chemical stability of dextran backbone was checked throughout each step of the synthesis. PLA‐grafted dextrans and PLA‐grafted (silylated dextrans) were proved to adopt a core‐shell conformation in various solvents. Furthermore, preliminary experiments on the potential use of these amphiphilic grafted copolymers as liquid/liquid interface stabilizers were performed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2577–2588, 2004 相似文献
4.
Edith Gößnitzer Ales Krbavcic Winfried Wendelin Marija Krbavcic 《Monatshefte für Chemie / Chemical Monthly》2002,133(9):1177-1185
Summary. Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N
7-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N
6-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding
5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of 1H, 13C, 15N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low
acute toxicity with a LD
50 > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N
7- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model.
Corresponding author. E-mail: edith.goessnitzer@uni-graz.at
Received March 20, 2002; accepted April 3, 2002 相似文献
5.
Helmut Spreitzer Edith Rodinger Andrea Pichler Gerhard Buchbauer 《Monatshefte für Chemie / Chemical Monthly》1990,121(11):955-961
Summary The bicyclo[2.2.1]- and [2.2.2]-systems are part of numerous biological active substances. Continuing our syntheses in the isocamphane series the homologous isocamphanes of mecamylamine (1 a) and of the fungicidal bicyclic compound2 were synthesized. Furthermore the syntheses ofE-homoisosantalene (15) andE,E-homoisosantalol (16) are described. 相似文献
6.
A new C,O-cyclodialkylation of dilithiated cyclic beta-keto esters and beta-keto sulfones with 1,4-dibromo-2-butene is reported which results in regio- and diastereoselective formation of 2-vinyl-2,3,3a,4,5,6-hexahydro-2,3-benzofurans. The products could be efficiently transformed into functionalized bicyclo[3.2.1]octan-8-ones by a palladium-catalyzed rearrangement reaction. In case of sulfone derivatives, this rearrangement proceeds with high stereospecifity to give exclusively the endo-configured diastereomers. The bicyclo[3.2.1]octane skeleton is present in a large number of pharmacologically important natural products. 相似文献
7.
Edith Mrki-Fischer Richard Buchecker Conrad Hans Eugster 《Helvetica chimica acta》1984,67(8):2143-2154
Reinvestigation of the Carotenoids from Rosa foetida, structures of 12 Novel Carotenoids; Stereoisomeric Luteoxanthins, Auroxanthins, Latoxanthins and Latochromes From petals of the yellow Rosa foetida HERRM ., more than 35 individual carotenoids were isolated and identified. Thereof, 87% belong to the expoxycarotenes. Structures were assigned for the first time to 4 auroxanthins ((8R,8′S), 6 ; (8S,8′S), 7 ; (8R,8′R), 8 ; (9Z,8R,8′R), 12 ), to 4 luteoxanthins ((8′R), 4 ; (8′S), 5 ; (9Z,8′R), 9 ; (9Z,8′S) 10(e) ) and to novel latoxanthins and latochromes, very polar carotenoids having (3S,5R,6R)-trihydroxy β-end groups (latoxanthins 13 and 16 , latochromes 14 and 15 ). 相似文献
8.
Isolation of 10′-Apo-β-carotene-10′-ol and (3R)-10′-Apo-β-carotene-3,10′-diol (Galloxanthin) from Rose Flowers The novel (all-E)-10′-apol-β-carotene-10′-ol ( 2 ) and (all-E,3R)-10′-apo-β-carotene-3,10′-diol ( 5 ) have been isolated from petals of one yellow species and various whitish or yellow blend varieties of rose cultivars. Each (all-E)-compound is accompanied by a (Z)-isomer, probably the (9Z)-isomer. Diol 5 proved to be identical with galloxanthin, an apo-10′-carotenol previously isolated from the retina of chicken. 相似文献
9.
Edith Mrki-Fischer Urs Marti Richard Buchecker Conrad Hans Eugster 《Helvetica chimica acta》1983,66(2):494-513
Carotenoids from Hips of Rosa pomifera: Discovery of (5Z)-Neurosporene; Synthesis of (3R, 15Z)-Rubixanthin Extensive chromatographic separations of the mixture of carotenoids from ripe hips of R. pomifera have led to the identification of 43 individual compounds, namely (Scheme 2): (15 Z)-phytoene (1) , (15 Z)-phytofluene (2) , all-(E)-phytofluene (2a) , ξ-carotene (3) , two mono-(Z)-ξ-carotenes ( 3a and 3b ), (6 R)-?, ψ-carotene (4) , a mono-(Z)-?, ψ-carotene (4a) , β, ψ-carotene (5) , a mono-(Z)-β, ψ-carotene (5a) , neurosporene (6) , (5 Z)-neurosporene (6a) , a mono-(Z)-neurosporene (6b) , lycopene (7) , five (Z)-lycopenes (7a–7e) , β, β-carotene (8) , two mono-(Z)-β, β-carotenes (probably (9 Z)-β, β-carotene (8a) and (13 Z)-β, β-carotene (8b) ), β-cryptoxanthin (9) , three (Z)-β-cryptoxanthins (9a–9c) , rubixanthin (10) , (5′ Z)-rubixanthin (=gazaniaxanthin; 10a ), (9′ Z)-rubixanthin (10b) , (13′ Z)- and (13 Z)-rubixanthin (10c and 10d , resp.), (5′ Z, 13′ Z)- or (5′ Z, 13 Z)-rubixanthin (10e) , lutein (11) , zeaxanthin (12) , (13 Z)-zeaxanthin (12b) , a mono-(Z)-zeaxanthin (probably (9 Z)-zeaxanthin (12a) ), (8 R)-mutatoxanthin (13) , (8 S)-mutatoxanthin (14) , neoxanthin (15) , (8′ R)-neochrome (16) , (8′ S)-neochrome (17) , a tetrahydroxycarotenoid (18?) , a tetrahydroxy-epoxy-carotenoid (19?) , and a trihydroxycarotenoid of unknown structure. Rubixanthin (10) and (5′ Z)-rubixanthin (10a) can easily be distinguished by HPLC. separation and CD. spectra at low temperature. The synthesis of (3 R, 15 Z)-rubixanthin (29) is described. The isolation of (5 Z)-neurosporene (6a) supports the hypothesis that the ?-end group arises by enzymatic cyclization of precursors having a (5 Z)- or (5′ Z)-configuration. 相似文献
10.
Wong EL Chow E Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6957-6965
The effect of the surface chemistry of DNA recognition interfaces on DNA hybridization at a gold surface was investigated using both electrochemistry and the quartz crystal microbalance (QCM) technique. Different DNA recognition interfaces were prepared using a two-component self-assembled monolayer consisting of thiolated 20-mer probe single-stranded DNA (ss-DNA) containing either a 3'-mercaptopropyl or a 3'-mercaptohexyl linker group and an alcohol-terminated diluent layer with 2-, 6-, or 11-carbon length. The influence of the interfacial design on the hybridization efficiency, the affinity constant (Ka) describing hybridization, and the kinetics of hybridization was assessed. It was found that the further the DNA was above the surface defined by the diluent layer the higher the hybridization efficiency and Ka. The kinetics of DNA hybridization was assessed using both a QCM and an electrochemical approach to ascertain the influence of the interface on both the initial binding of target DNA to the surface and the formation of a complete duplex. These measurements showed that the length of the diluent layer has a large impact on the time taken to form a perfect duplex but no impact on the initial recognition of the target DNA by the immobilized probe DNA. 相似文献