全文获取类型
收费全文 | 3135篇 |
免费 | 66篇 |
国内免费 | 294篇 |
专业分类
化学 | 1985篇 |
晶体学 | 4篇 |
力学 | 272篇 |
综合类 | 1篇 |
数学 | 762篇 |
物理学 | 471篇 |
出版年
2024年 | 9篇 |
2023年 | 140篇 |
2022年 | 40篇 |
2021年 | 71篇 |
2020年 | 75篇 |
2019年 | 91篇 |
2018年 | 88篇 |
2017年 | 80篇 |
2016年 | 58篇 |
2015年 | 61篇 |
2014年 | 134篇 |
2013年 | 300篇 |
2012年 | 106篇 |
2011年 | 189篇 |
2010年 | 135篇 |
2009年 | 203篇 |
2008年 | 192篇 |
2007年 | 221篇 |
2006年 | 195篇 |
2005年 | 155篇 |
2004年 | 144篇 |
2003年 | 78篇 |
2002年 | 65篇 |
2001年 | 44篇 |
2000年 | 51篇 |
1999年 | 46篇 |
1998年 | 79篇 |
1997年 | 41篇 |
1996年 | 41篇 |
1995年 | 31篇 |
1994年 | 44篇 |
1993年 | 59篇 |
1992年 | 33篇 |
1991年 | 28篇 |
1990年 | 24篇 |
1989年 | 19篇 |
1988年 | 14篇 |
1987年 | 21篇 |
1986年 | 9篇 |
1985年 | 7篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1975年 | 2篇 |
1972年 | 2篇 |
1970年 | 4篇 |
1968年 | 2篇 |
排序方式: 共有3495条查询结果,搜索用时 15 毫秒
101.
Yuehai ShenJianxun Wen 《Journal of fluorine chemistry》2002,113(1):13-15
A new and efficient route has been developed to synthesize 17β-(1-methyl-3-perfluoroalkyl)propyl-3β-androsterol (1) in nine steps from hyodeoxycholic acid via selective addition of 1-perfluoroalkyl iodide to 24-norchola-5,22-dien-3β-ol. From (1), the first series of steroidal liquid crystalline aliphatic esters (smectic A) with fluorocarbon side chains has been prepared. 相似文献
102.
α-甲基丙烯酸烯丙酯的合成及其自由基、阴离子聚合的研究 总被引:1,自引:0,他引:1
合成了α-甲基丙烯酸烯丙酯(AMA),并对其自由基、阴离子聚合进行了探讨。结果发现,该单体难以进行选择性自由基聚合,但可用作多种单体自由基聚合的交联剂。用1,1′-二苯基己基锂在THF中引发AMA,可顺利地进行α位双键的选择性阴离子聚合,分子量实测值与计算值基本一致。在较低温度下(≤-60℃),可得窄分布PAMA(Mw/Mn=1.12~1.15)。随聚合温度升高,间同和无规聚合物含量分别呈下降和上升趋势。GPC、1HNMR及FTIR鉴定表明,用阴离子聚合法可得到溶于多种溶剂、每个重复单元上均定量带有烯丙基双键的窄分布官能性PAMA。 相似文献
103.
Nikolay T. Tzvetkov 《Tetrahedron letters》2005,46(45):7751-7755
Bicyclic cyclopentafuranols were formed by photoinitiated radical cyclization of allyl- and propinyloxymethyl substituted cyclopentanones with high regioselectivity. The irradiations were carried out at a wavelength of 300 nm in aprotic solvents such as benzene and acetonitrile. We could also show that reductive photoinduced electron transfer (PET) of the propynyloxymethyl substituted cyclopentanone 5 does not lead to any cyclization. The starting materials were synthesized in good yields following known procedures. 相似文献
104.
Diego Ardura 《Tetrahedron letters》2004,45(47):8691-8694
UB3LYP/6-311++G(d,p) and ROMP2/6-311++G(d,p)//UB3LYP/6-311++G(d,p) calculations including the effect of benzene solvent through the PCM-UAHF method render a concerted mechanism without fragmentation as the most favourable one for the Dowd-Beckwith radical ring expansion of the bromomethyl adduct of methyl cyclopentanone-2-carboxylate to yield methyl cyclohexanone-3-carboxylate. The corresponding concerted TS is a bicyclic alcoxy radical. 相似文献
105.
本文报道了四种2-亚甲基-1,3-二氧己烷类单体:4-甲基-2-亚甲基-1,3-二氧己烷(Ⅱ)、4,6-二甲基-2-亚甲基-1,3-二氧己烷(Ⅳ)、5,5-二甲基-2-亚甲基-1,3-二氧己烷(Ⅵ)和5,5-二乙基-2-亚甲基-1,3-二氧己烷(V Ⅲ)的合成以及自由基开环聚合。结果表明,上述单体在聚合过程中出现异构化开环现象。Ⅲ和Ⅳ的甲基位置在环上氧原子的α-碳原子上时,显示对异构化反应的影响比Ⅵ及Ⅷ的甲基和乙基在β-碳原子上时更显著。上述现象与异构化开环形成仲碳自由基中间体的倾向更大有关。 Ⅳ在苯溶液中及过氧化二叔丁基存在下,120℃反应,得到全部是聚-δ-戊内酯骨架结构的聚合物。提出了一种合成聚-δ-戊内酯类链结构的聚酯的新的途径和方法。 相似文献
106.
Oxolane was fluoroalkylated by its photoadditions under atmospheric pressure. Monofluoro-alkylations were carried out with hexafluoropropene (1) and perfluorovinyl ethers C3F7O-[CF(CF3)CF2O]n-CF = CF2 (24, n = 0–2) by direct photoexcitation of the olefins to give high yields of addition products 9–12 (81–94%). The reactions were completely regioselecti ve at the oxolane molecule and almost completely regioselective (93–99%) at the double bond of fluoro-olefins; no bis-fluoroalkylated oxolanes were detected. The completely selective introduction of a second fluoroalkyl into position 5 of the oxolane molecule was accomplished by acetone-sensitised photoaddition of 2fluoroalkylated oxolanes 9,10 to fluoro-olefins 1 and 2. Byproducts from reactions of the dimethylketyl radical which is formed in the initiation step were isolated and have given some evidence about the reaction mechanism that is discussed. 相似文献
107.
Corinne De Dobbeleer 《Tetrahedron letters》2005,46(22):3889-3893
Functionalised medium-ring systems of various sizes can be efficiently prepared by a novel approach that embodies a radical-induced fragmentation of bicyclic β-hydroxy ketones, followed by a second radical-coupling reaction. The unexpected reactivity of α-keto radicals is also discussed. 相似文献
108.
Hideki Sugimoto 《Tetrahedron letters》2004,45(22):4213-4216
Enantioselective intramolecular radical cyclization of benzimidazolyl iodoalkenyl and iodoalkadienyl sulfones using chiral Lewis acids gave products with good enantioselectivity. Newly formed chiral centers could be induced effectively by enantioselective coordination to one of the sulfonyl oxygens. 相似文献
109.
Hans-René Bjørsvik José Angel Vedia Merinero Lucia Liguori 《Tetrahedron letters》2004,45(47):8615-8620
A new catalytic oxidation method for the preparation of aromatic carboxylic acids from methyl aryl ketones is reported. The method is an alternative to the haloform reaction; it is benign and affords the desired product without production of any harmful side products. The catalytic cycle is based on the use of an electron-deficient nitroarene as catalyst with either of the two cheap and green oxidants sodium percarbonate or sodium perborate. The method gives a good yield (87%) and shows excellent selectivity when the model substrate (acetophenone) is oxidized. A series of benzoic acids of industrial interest were prepared by means of this method. 相似文献
110.
Pedro J.?Silva Pedro A.?Fernandes Maria J.?RamosEmail author 《Theoretical chemistry accounts》2003,110(5):345-351
Prostaglandin H synthase catalyzes the oxygenation of arachidonic acid into the cyclic endoperoxide, prostaglandin G2 (PGG2), and the subsequent reduction of PGG2 to the corresponding alcohol, prostaglandin H2 (PGH2), the precursor of all prostaglandins and thromboxanes. Both radical abstraction by a neighboring tyrosyl radical and combined radical/carbocationic models have been proposed to explain the cyclooxygenase part of this reaction. We have used density functional theory calculations to study the mechanism of the formation of the cyclooxygenated product PGG2. We found an activation free energy for the initial hydrogen abstraction by the tyrosine radical of 15.6 kcal/mol, and of 14.5 kcal/mol for peroxo bridge formation, in remarkable agreement with the experimental value of 15.0 kcal/mol. Subsequent steps of the radical-based mechanism were found to happen with smaller barriers. A combined radical/carbocation mechanism proceeding through a sigmatropic hydrogen shift was ruled out, owing to its much larger activation free energy of 36.5 kcal/mol. Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00214-003-0476-9. Electronic Supplementary MaterialSupplementary material is available in the online version of this article at
Electronic Supplementary Material: Supplementary material is available in the online version of this article at 相似文献