全文获取类型
收费全文 | 1150篇 |
免费 | 27篇 |
国内免费 | 3篇 |
专业分类
化学 | 913篇 |
晶体学 | 16篇 |
力学 | 24篇 |
数学 | 60篇 |
物理学 | 167篇 |
出版年
2023年 | 6篇 |
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 15篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 15篇 |
2015年 | 21篇 |
2014年 | 16篇 |
2013年 | 47篇 |
2012年 | 45篇 |
2011年 | 48篇 |
2010年 | 29篇 |
2009年 | 34篇 |
2008年 | 55篇 |
2007年 | 73篇 |
2006年 | 71篇 |
2005年 | 66篇 |
2004年 | 66篇 |
2003年 | 60篇 |
2002年 | 55篇 |
2001年 | 19篇 |
2000年 | 25篇 |
1999年 | 15篇 |
1998年 | 24篇 |
1997年 | 19篇 |
1996年 | 20篇 |
1995年 | 18篇 |
1994年 | 9篇 |
1993年 | 13篇 |
1992年 | 18篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 27篇 |
1984年 | 21篇 |
1983年 | 7篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 5篇 |
1979年 | 9篇 |
1978年 | 15篇 |
1977年 | 17篇 |
1976年 | 14篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1972年 | 4篇 |
排序方式: 共有1180条查询结果,搜索用时 15 毫秒
21.
Yohei Hashimoto Masataka Moriyasu Eiko Kato Masaru Endo Naohiko Miyamoto Hiroshi Uchida 《Mikrochimica acta》1978,70(1-2):159-167
Summary A new type of detector for high-pressure liquid chromatography has been designed. This detector is equipped with a RC resonance circuit, and is similar to the capacitance detector previously reported. It is operated as a capacitance detector with nonpolar eluents; while with polar solvents, it behaves as a conductance detector. Electrolytes such as salts, acids and bases are sensitively detected. The detector was successfully used for the detection of fatty acids and alkaloids.
Zusammenfassung Ein neuartiger Detektor für die Hochdruck-Flüssigchromatographie wurde entwickelt. Dieser ist mit einem Resonanzstromkreis ausgestattet und ähnelt dem kürzlich beschriebenen Kapazitanz-Detektor. Als solcher funktioniert er mit nichtpolaren Eluenten, während er sich mit polaren Lösungsmitteln wie ein Leitfähigkeitsdetektor verhält. Salze, Säuren und Basen werden empfindlich nachgewiesen. Das Gerät wurde zum Nachweis von Fettsäuren und Alkaloiden verwendet.相似文献
22.
The percutaneous absorption of ketoprofen (KPF) from gel patches containing d-limonene and ethanol was investigated in rats. Plasma levels of KPF varied with the kind of polymers which constitute the gel patch, and the highest level was observed when the copolymer of ethylacrylate (EA) and diethyleneglycolmethacrylate (DEGMA) was used as a vehicle. The amount of KPF permeating through the rat skin from the gel patch was well correlated with that of ethanol. Permeations were enhanced with increase in the amount of d-limonene distributed from the vehicle to the skin tissue. The amount of d-limonene accumulated in the skin varied greatly with the kind of polymers; the highest accumulation was observed with the EA-DEGMA copolymer, and decreased with increasing affinity of d-limonene to the polymers. The reason EA-DEGMA copolymer showed the highest percutaneous absorption of KPF from gel patches containing d-limonene may be the hydrophilic nature of this polymer which showed the lowest affinity to d-limonene. 相似文献
23.
Optically active o-substituted diphenyl N-substituted sulphilimines are readily synthesised by the reaction of the corresponding sulphides and t-butyl hypochlorite in the presence of l-menthol and amide anions. (−)-N-p-Tolylsulphonylsulphilimines (1, 2) obtained were converted to the corresponding (−)-N-unsubstituted sulphilimines (8, 9) by treating them with concentrated sulphuric acid. When (−)-S-o-anisyl S-phenyl N-(unsubstituted) sulphilimine (8) was treated with acylating agents or acrylonitrile, the corresponding optically active (−)-N-substituted sulphilimines were prepared with complete retention at sulphur. The absolute configuration of (−)-S-o-anisyl S-phenyl N-p-tolylsulphonylsulphilimine (1) was determined by converting it to (+)-S-o-anisyl sulphoxide (17). CD curves of (−)-o-substituted diarylsulphilimines exhibited a negative Cotton effect at around 270–285 nm, which was assigned to (S)-configuration at sulphur by comparing with the analogous sulphoxides. The substituent on the imino group of the sulphilimine gave no appreciable effect on the CD behavior and the lack of substituent effect was considered to be due to the semi-polar character of the S(IV)-N bond. Unusual effect of o-methoxy group on the CD curves was discussed in connection with solvent effect. Mechanism of this asymmetric synthesis has been investigated, and it has become apparent that the diastereomeric menthoxysulphonium chloride was an excess of (RR)-configuration was formed initially and the amide anion attacks the S atom of the salt with net inversion. 相似文献
24.
Masaru Kurihara Naoya Yoda 《Journal of polymer science. Part A, Polymer chemistry》1967,5(7):1765-1781
Fully aromatic polyquinazolinediones of high molecular weight were prepared by the cyclopolycondensation reaction of 4,4′-diamino-3,3′-biphenyldicarboxylic acid with aromatic diisocyanates. The poly(phosphoric acid) solution polymerization techniques yielded tractable poly(urea acid), which was converted to polyquinazolinediones by thermal cyclodehydration at 300–400°C. under reduced pressure. The polyquinazolinediones thus obtained have excellent thermal stability both in nitrogen and in air. The poly(urea acid) is soluble in dimethyl sulfoxide, and films can be cast from the polymer solution of poly(urea acid) (ηinh = 0.8 to 1.8). The films are made tough by being heated in nitrogen or under reduced pressure at 300–400°C. The polymerization mechanism of the cyclopolycondensation reaction was studied, and it was established that the polymerization proceeded through the formation of tractable poly(urea acid), Structure (I), of high molecular weight, followed by cyclodehydration, yielding poly(1,2-dihydro-2-imino-4H-3,1-benzoxazin-4-one), Structure (II). On subsequently being heated this undergoes intramolecular rearrangement along the polymer chain, giving the thermodynamically stable polyquinazolinedione, Structure (III). 相似文献
25.
Masaru Mitsuda 《Tetrahedron letters》2006,47(46):8073-8077
Kinetic resolution of N-benzoylated vic-amino alcohols was achieved by benzoylation in the presence of copper triflate and (R,R)-Ph-BOX as catalysts. The observed enantioselectivity was moderate to high. The method was applied to a kinetic resolution of racemic prolinol and piperidinemethanol derivatives as well as an asymmetric desymmetrization of 2-amino-1,3-diol derivatives. 相似文献
26.
Hiroshi Maruoka Kenji Yamagata Fumi Okabe Yukihiko Tomioka 《Journal of heterocyclic chemistry》2005,42(4):717-721
A series of cyclic sulfonium ylides 4a‐h reacted with titanium( IV ) chloride in the presence of triethyl‐amine to give the corresponding fused 2,3‐dihydro‐1H‐thieno[3,4‐b]pyrroles 5a‐h , via a ring opening and recyclization. In contrast, treatment of compounds 4a, 4b, 4e and 4f with titanium(IV) chloride, triethy‐lamine and dimethylamine hydrochloride gave the corresponding thiophenes 6a, 6b, 6e and 6f . Furthermore, compounds 6a and 6b easily underwent cyclization with sodium hydride to afford the corresponding 5a and 5b . 相似文献
27.
Yamamoto T Mukai SR Endo A Nakaiwa M Tamon H 《Journal of colloid and interface science》2003,264(2):532-537
Growth of colloidal particles formed during the sol-gel transition of a resorcinol-formaldehyde (RF) solution was simulated based on the population balance equation by using the discrete-sectional model (DSM). During the early stage of the sol-gel transition, the transient change of sizes of colloidal particles estimated by this method agreed well with the previous experimental observation by dynamic light scattering (DLS), which confirmed the influence of the catalyst concentration of a starting RF solution on the growth rate of the particles. From the size distribution of colloidal particles predicted at the gelation time, the surface area of a RF hydrogel after the completion of the sol-gel transition was estimated, which coincided with the BET surface area of a RF aerogel because the porous structure of a hydrogel was maintained and few micropores were formed during supercritical drying. 相似文献
28.
Kashiwada Y Chiyo J Ikeshiro Y Nagao T Okabe H Cosentino LM Fowke K Morris-Natschke SL Lee KH 《Chemical & pharmaceutical bulletin》2000,48(9):1387-1390
3-Alkylamido-3-deoxy-betulinic acids were synthesized and evaluated for anti-HIV activity as part of the structure-activity relationship study of the potent anti-HIV agent 3-O-(3',3'-dimethyl)-succinyl-betulinic acid (DSB) (2). 3Alpha-diglycorylamide-3-deoxy-betulinic acid demonstrated relatively potent anti-HIV activity (EC50 0.24 microm, TI 728). However, replacing the ester group at C-3 in 2 and its analogues with an amido group yielded inactive or much less potent compounds against HIV replication, indicating that the ester group at C-3 in 2-4 is essential for potent anti-HIV activity. 相似文献
29.
Hidenobu Shimizu Tomonari Shiraishi Risei Wada Masaru Okabe 《Colloid and polymer science》2006,285(1):107-111
Soap-free emulsion copolymerization of 2, 2, 2-trifluoroethyl acrylate (3FEA) with styrene was carried out by using potassium persulfate as an initiator, and the effects of the weight fraction of 3FEA in the monomer feed on the kinetics and the particle size were investigated. Monomer conversions were followed by a gravimetric method, revealing that the overall polymerization rate increased exponentially with an increase in the weight fraction of 3FEA. According to dynamic light scattering measurement, the final particle size was found to decrease with an increase in the weight fraction of 3FEA. The number of particles for 3FEA homopolymerization was roughly twice as large as that at the fraction of 0.9, although both fractions had the almost same polymerization rates. These results indicate that soap-free emulsion homopolymerization of 3FEA would proceed not only inside the polymer particles but also in the aqueous phase throughout the polymerization. 相似文献
30.
1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens… 相似文献