全文获取类型
收费全文 | 4322篇 |
免费 | 60篇 |
国内免费 | 7篇 |
专业分类
化学 | 3004篇 |
晶体学 | 78篇 |
力学 | 45篇 |
数学 | 588篇 |
物理学 | 674篇 |
出版年
2021年 | 25篇 |
2017年 | 25篇 |
2016年 | 50篇 |
2015年 | 46篇 |
2014年 | 45篇 |
2013年 | 108篇 |
2012年 | 84篇 |
2011年 | 102篇 |
2010年 | 70篇 |
2009年 | 92篇 |
2008年 | 127篇 |
2007年 | 138篇 |
2006年 | 133篇 |
2005年 | 134篇 |
2004年 | 124篇 |
2003年 | 114篇 |
2002年 | 134篇 |
2001年 | 71篇 |
2000年 | 87篇 |
1999年 | 77篇 |
1998年 | 73篇 |
1997年 | 63篇 |
1996年 | 68篇 |
1995年 | 81篇 |
1994年 | 73篇 |
1993年 | 75篇 |
1992年 | 68篇 |
1991年 | 68篇 |
1990年 | 69篇 |
1989年 | 93篇 |
1988年 | 62篇 |
1987年 | 78篇 |
1986年 | 80篇 |
1985年 | 105篇 |
1984年 | 81篇 |
1983年 | 72篇 |
1982年 | 69篇 |
1981年 | 72篇 |
1980年 | 79篇 |
1979年 | 87篇 |
1978年 | 88篇 |
1977年 | 95篇 |
1976年 | 82篇 |
1975年 | 68篇 |
1974年 | 61篇 |
1973年 | 58篇 |
1972年 | 38篇 |
1971年 | 39篇 |
1970年 | 28篇 |
1968年 | 36篇 |
排序方式: 共有4389条查询结果,搜索用时 15 毫秒
41.
Khoroshen'kov G. V. Fag A. A. Bochkarev M. N. Dechert S. Schumann H. 《Russian Chemical Bulletin》2003,52(8):1715-1719
The reactions of LnI2 (Ln = Nd (1) or Dy (2)) with cyclopentadiene (CpH) in THF at 0 °C afforded the CpLnI2(THF)3 complexes in 65—67% yields. The reaction of thulium diiodide (3) with an excess of CpH at 60 °C produced CpTmI2(THF)3, Cp2TmI(THF)2, and TmI3(THF)3 in 21, 58, and 63% yields, respectively. The reactions of 1 and 2 with pentamethylcyclopentadiene (Cp*H) in THF were accompanied by disproportionation giving rise to the Cp*2LnI(THF)2 and LnI3(THF)
x
complexes. Neodymium triiodide was isolated in the ionic form [NdI2(THF)5]+[NdI4(THF)2]–. Its structure and the structure of CpTmI2(THF)3 were established by X-ray diffraction analysis. 相似文献
42.
cis- and trans-3,4-Dichlorocyclobutene (I) react with Ni(CO)4 and AlCl3 to give (C4H4)NiCl2 · AlCl3 (II), while the bromo- and iodo-substituted cyclobutenes (III) without AlCl3 yield the complexes (C4H4)NiX2 (IVa, X Br; IVb, X I). Properties of II and IV are discussed and the presence of a C4H4 ring attached to nickel is likely from the results obtained. 相似文献
43.
Heinz Harnisch 《Angewandte Chemie (International ed. in English)》1976,15(8):468-475
With the aid of selected examples an overview is given of the development trends in phosphoruscarbon chemistry over the past few years. An attempt is made to demonstrate the relationships between various parameters and properties such as constitution, basicity, substitution by functional groups, reaction behavior etc. of the compounds. In the case of basis compounds containing methylphosphorus groups the state of development of industrially interesting processes is also outlined. In addition, the synthesis of a few bifunctional phosphorus-carbon compounds which can be employed as comonomers in the production of polymers is described. 相似文献
44.
Dr. Heinz Berner Hellmuth Reinshagen 《Monatshefte für Chemie / Chemical Monthly》1975,106(5):1059-1069
The synthesis of imidazo[4,5-b]pyridines and of [1,2,4]-triazolo[1,5-a]pyridines is described, and their biological activity in relation to the standard antiviral substance, 2-(α-hydroxybenzyl)benzimidazol, is discussed. 相似文献
45.
Peter Wipf Roland Prevo Jost H. Bieri Gabriel Germain Heinz Heimgartner 《Helvetica chimica acta》1988,71(5):1177-1190
Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile Ylides Thermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6 , at 110–155° in the presence of dipolarophiles with activated C≡C, C?C, C?O, C?S, and N?N bonds, led to 5-membered cyclo-adducts and CO2 (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate ( 19 ) and ethyl pyridine-3-carboxylate( 22 ), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20 . The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8). 相似文献
46.
3-(Dimethylamino)-2,2-dimethyl-2H,-azirine as an α-Aminoisobutyric-Acid (Aib) Equivalent: Cyclic Depsipeptides via Direct Amid Cyclization In MeCN at room temperature, 3-(dimethylamino)-2,2-dimethyl-2H-azirine ( 1 ) and α-hydroxycarboxylic acids react to give diamides of type 8 (Scheme 3). Selective cleavage of the terminal N,N-dimethylcarboxamide group in MeCN/H2O leads to the corresponding carboxylic acids 13 (Scheme 4). In toluene/Ph SH , phenyl thioesters of type 11 are formed (see also Scheme 5). Starting with diamides 8 , the formation of morpholin-2,5- diones 10 has been achieved either by direct amide cyclization via intermediate 1,3-oxazol-5(4H)-ones 9 or via base-catalyzed cyclization of the phenyl thioesters 11 (Scheme 3). Reaction of carboxylic acids with 1 , followed by selective amide hydrolysis, has been used for the construction of peptides from α-hydroxy carboxylic acids and repetitive α-aminoisobutyric-acid (Aib) units (Scheme 4). Cyclization of 14a, 17a , and 20a with HCI in toluene at 100° gave the 9-, 12-, and 15-membered cyclic depsipeptides 15, 18 , and 21 , respectively. 相似文献
47.
The luminescence properties of about twentyfive model compounds representing the three main partial structures of bile pigments (namely pyrromethenes, pyrromethenones and methylenepyrrolylmethylenepyrrolinones) as well as tripyrrines and the geometrical isomers of aetiobiliverdin-IV- are reported. In these compounds there is usually only a very faint or even no fluorescence and phosphorescene as the pathway of deexcitation. Vibrational internal conversion and photoisomerizations at the exocyclic double bonds are the main anaerobic paths of radiationless decay of the excited states.
H. Falk, K. Grubmayr, E. Haslinger, T. Schlederer undK. Thirring, Mh. Chem.109, 1451 (1978). 相似文献
48.
4,4-Dimethyl-2-phenyl-2-thiazolin-5-thione () reacts with 2,3-diphenylcyclopropenone () at 145°C and with benzonitrilio-2-propanide () at room temperature to yield the 1,6-dithia-spiro[4.4]nonadienes and , respectively. 相似文献
49.
Prof. Dr. Heinz Falk Alfred Leodolter Georg Schade 《Monatshefte für Chemie / Chemical Monthly》1978,109(1):183-192
The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.
Mit 1 Abbildung 相似文献
Mit 1 Abbildung 相似文献
50.
Karl Heinz Neeb 《Fresenius' Journal of Analytical Chemistry》1966,215(3):161-175
Zusammenfassung Die für die Bestimmung geringer Gehalte an Phosphor, Silicium, Fluor, Chlor, Lithium, Natrium, Calcium und Kohlenstoff in UO2-Kernbrennstoff angewandten chemischen Analysenverfahren werden beschrieben. Durch Kombination einfacher und blindwertfreier Abtrennungsverfahren (Extraktionen und Pyrohydrolysen) mit empfindlichen physikalischchemischen Bestimmungsmethoden (Spektralphotometrie, Flammenphotometrie, coulometrische Titration) lassen sich Nachweisgrenzen zwischen 0,1 und 10 ppm bei Probeneinwaage von 0,5–1 g UO2 erreichen. Der Zeitaufwand für die Analysen kann durch simultane Bestimmung zweier oder dreier Elemente in einem Arbeitsgang niedriggehalten werden. Die beschriebenen Verfahren haben sich bei Reinheitskontrollen von Kernbrennstoffen gut bewährt.
Herrn Dr. W. Gebauhr danken wir für wertvolle Anregungen und Diskussionen. 相似文献
Summary Analytical methods have been developed for the determination of trace amounts of phosphorus, silicon, fluorine, chlorine, lithium, sodium, calcium, and carbon in UO2 of nuclear purity. By combination of simple and rapid separation procedures (extraction, pyrohydrolysis) with highly sensitive methods of determination (spectrophotometry, flame photometry, coulometric titration) detection limits of 0.1–10 ppm have been obtained with sample sizes of 0.5–1 g. In order to reduce the time needed for analysis, some of the above elements are determined simultaneously. The methods described have been successfully applied to the purity control of nuclear fuels.
Herrn Dr. W. Gebauhr danken wir für wertvolle Anregungen und Diskussionen. 相似文献