全文获取类型
收费全文 | 43篇 |
免费 | 2篇 |
专业分类
化学 | 24篇 |
数学 | 4篇 |
物理学 | 17篇 |
出版年
2021年 | 1篇 |
2016年 | 1篇 |
2015年 | 1篇 |
2014年 | 2篇 |
2013年 | 2篇 |
2012年 | 1篇 |
2011年 | 1篇 |
2010年 | 1篇 |
2009年 | 1篇 |
2007年 | 2篇 |
2006年 | 1篇 |
2004年 | 1篇 |
2002年 | 1篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1990年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1962年 | 1篇 |
1960年 | 1篇 |
1928年 | 1篇 |
1923年 | 2篇 |
1920年 | 1篇 |
1897年 | 1篇 |
排序方式: 共有45条查询结果,搜索用时 265 毫秒
1.
Total Synthesis of (+)-D-Homoestrone 3-methyl ether A novel total synthesis of (+)-D-homoestrone 3-methyl ether ( 21 ) is described starting from (S)-8a-methyl-3,4,8,8a-tetrahydro-2H, 7H-naphthalene-1,6-dione ( 1 ) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m-methoxyphenacyl bromide ( 4 ) as an AB-building block to give the dioxo-secosteroid 5 . Hydrogenation of 5 affords the trans-decalone 11 . As by-products the epimeric cis-decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ9(11)-tetraene 14 . Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21 . It was found that 14 and also the derived Δ8-isomer 15a add hydrogen from the α-face of the molecule to an extent of about 80%. The 8α-D-homoestrone derivatives 20a and 23 as well as the 9β-isomers 19a and 22 were characterized. 相似文献
2.
Synthesis of β-D -Glucopyranosides of some Hydroxylated Vitamin-D Compounds Cholesta-5, 7-diene-1α, 3β-diol (1a) was glycosylated with ‘α-acetobromoglucose’ (2) as well as with ‘α-acetobromocellobiose’ (4) to yield the 3-(glycosides) 1b and 1c , respectively. Irradiation of these products with UV light followed by thermal isomerization led to the corresponding vitamin-D derivatives 3a and 3c. Direct glucosylation of vitamin D3 (3f) and vitamin D2 (5a) with 2 gave the derivatives 3g and 5b , respectively. With 25-hydroxycholecalciferol ( = calcidiol; 6a ) as substrate, besides the 3-(glucoside) 6b small amounts of the C(25)-analog 6c were formed. The reaction of 1α, 25-dihydroxycholecalciferol ( = calcitriol; 6e ) with 2 furnished the 3- and the 1-(glucoside) ( 6f and 6g , respectively) as the major components and the C(25)-analog 6h in minor quantity. From the acetylated 3-(glucosides) 3a, 3g, 5b, 6b , and 6f , the free glucopyranosides 3b, 3h, 5c, 6d , and 6i , respectively, were prepared as well as the free glucopy-ranosyl-glucopyranoside 3d from the acetylated disaccharide 3c. 相似文献
3.
Xiao-Dan Wang Kyle J. Horning Francesca M. Notarangelo Robert Schwarcz 《Analytical and bioanalytical chemistry》2013,405(30):9747-9754
d-Kynurenine (d-KYN), a metabolite of d-tryptophan, can serve as the bioprecursor of kynurenic acid (KYNA) and 3-hydroxykynurenine, two neuroactive compounds that are believed to play a role in the pathophysiology of several neurological and psychiatric diseases. In order to investigate the possible presence of d-KYN in biological tissues, we developed a novel assay based on the conversion of d-KYN to KYNA by purified d-amino acid oxidase (d-AAO). Samples were incubated with d-AAO under optimal conditions for measuring d-AAO activity (100 mM borate buffer, pH 9.0), and newly produced KYNA was detected by high-performance liquid chromatography (HPLC) with fluorimetric detection. The detection limit for d-KYN was 300 fmol, and linearity of the assay was ascertained up to 300 pmol. No assay interference was noted when other d-amino acids, including d-serine and d-aspartate, were present in the incubation mixture at 50-fold higher concentrations than d-KYN. Using this new method, d-KYN was readily detected in the brain, liver, and plasma of mice treated systemically with d-KYN (300 mg/kg). In these experiments, enantioselectivity was confirmed by determining total kynurenine levels in the same samples using a conventional HPLC assay. Availability of a sensitive, specific, and simple method for d-KYN measurement will be instrumental for evaluating whether d-KYN should be considered for a role in physiology and pathology. 相似文献
4.
Andor Ferenczy 《Monatshefte für Chemie / Chemical Monthly》1897,18(1):673-685
Ohne Zusammenfassung 相似文献
5.
6.
Andor Frenkel 《Foundations of Physics》2002,32(5):751-771
In the existing expositions of the Károlyházy model, quantum mechanical uncertainties are mimicked by classical spreads. It is shown how to express those uncertainties through entities of the future unified theory of general relativity and quantum theory. 相似文献
7.
R. Schwarcz W. Fried F. Pittner Prof. Dr. O. Hoffmann-Ostenhof 《Monatshefte für Chemie / Chemical Monthly》1974,105(2):445-451
With the help of affinity chromatography on NAD-Sepharose it was possible to findmyo-inositol-1-phosphate synthase (EC 5.5.1.4) in blood of anaemic chicken and to obtain a relatively active preparation of the enzyme. In the blood of normal chicken, which had no reticulocytes, no activity of this enzyme could be detected. The same method was also successfully applied for the concentration of an enzyme of the same specificity fromLemna gibba (duckweed).
Mit 2 Abbildungen
31. Mitt.:W. Woloszczuk undO. Hoffmann-Ostenhof, Z. physiol. Chem. (im Druck). 相似文献
Mit 2 Abbildungen
31. Mitt.:W. Woloszczuk undO. Hoffmann-Ostenhof, Z. physiol. Chem. (im Druck). 相似文献
8.
Properties of E′ centres of high geological age in flint from different locations have been studied. ESR spectra of γ-irradiated samples of heated and unheated Silurian and Eocene flint show thermally unstable components. The spectrum of one species could be simulated using the g values: 2.00164, 2.00059, and 2.00046. Two others deliver ESR-signals at g=2.0015 and 2.0012, respectively. These unstable components cannot be identified with any known E′ centres. About 50% of the ESR intensity of the E′ centres in unheated flint induced by artificial γ-rays is thermally stable. This effect is probably due to a steady state and might be useful for dating of unburned flint tools (“skinflint dating”). 相似文献
9.
Athanassios Tzikas Christoph Tamm Arthur Boller Andor Fürst 《Helvetica chimica acta》1976,59(5):1850-1866
20, 21-Aziridine Steroids: Reaction of Derivatives of the Oximes of 5-Pregnen-20-one, 9β, 10α-5-Pregnen-20-one and 9β, 10α-5,7-Pregnadiene-20-one with Lithium Aluminium Hydride, and of 3β-Hydroxy-5-pregnen-20-one Oxime with Grignard Reagents. Reduction of 3β-hydroxy-5-pregnen-20-one oxime ( 2 ) with LiAlH4 in tetrahydrofuran yielded 20α-amino-5-pregnen-3β-ol ( 1 ), 20β-amino-5-pregnen-3β-ol ( 3 ), 20β, 21-imino-5-pregnen-3β-ol ( 6 ) and 20β, 21-imino-5-pregnen-3β-ol ( 9 ). The aziridines 6 and 9 were separated via the acetyl derivatives 7 and 10 . The reaction of 6 and 9 with CS2 gave 5-(3β-hydroxy-5-androsten-17β-yl)-thiazolidine-2-thione ( 8 ). Treatment of the 20-oximes 12 and 15 of the corresponding 9β,10α(retro)-pregnane derivatives with LiAlH4 gave the aziridines 13 and 16 , respectively. Their deamination led to the diene 14 and triene 17 , respectively. Reduction of isobutyl methyl ketone-oxime with LiAlH4 in tetrahydrofuran yielded 2-amino-4-methyl-pentane ( 19 ) as main product, 1, 2-imino-4-methyl-pentane ( 22 ) as second product and the epimeric 2,3-imino-4-methyl-pentanes 20 and 21 as minor products. – 3β-Hydroxy-5-pregnen-20-one oxime ( 2 ) was transformed by methylmagnesium iodide in toluene to 20α, 21-imino-20-methyl-5-pregnen-3β-ol ( 23 ) and 20β, 21-imino-20-methyl-5-pregnen-3β-ol ( 26 ). Acetylation of these aziridines was accompanied by elimination reactions leading to 3β-acetoxy-20-methylidene-21-N-acetylamino-5-pregnene ( 30 ) and 3β-acetoxy-20-methyl-21-N-acetylamino-5,17-pregnadiene ( 32 ). The reaction of oxime 2 with ethylmagnesium bromide in toluene gave 20α, 21-imino-20-ethyl-5-pregnen-3β-ol ( 24 ) and 20α,21-imino-20-ethyl-5-pregnen-3β-ol ( 27 ). Acetylation of 24 and 27 led to 3β-acetoxy-20-ethylidene-21-N-acetylamino-5-pregnene ( 31 ), 3β-acetoxy-20-ethyl-21-N-acetylamino-5,17-pregnadiene 33 and 3β, 20-diacetoxy-20-ethyl-21-N-acetylamino-5-pregnene ( 37 ). With phenylmagnesium bromide in toluene the oxime 2 was transformed to 20β, 21-imino-20-phenyl-5-pregnen-3β-ol ( 25 ) and 20β,21-imino-20-phenyl-5-pregnen-3β-ol ( 28 ). Acetylation of 25 and 28 yielded 3β-acetoxy-20-phenyl-21-N-acetylamino-5, 17-pregnadiene ( 34 ) and 3β,20-diacetoxy-20-phenyl-21-N-acetylamino-5-pregnene ( 39 ). LiAlH4-reduction of 39 gave 3β, 20-dihydroxy-20-phenyl-21-N-ethylamino-5-pregnene ( 41 ). – The 20, 21-aziridines are stable to LiAlH4. Consequently they are no intermediates in the formation of the 20-amino derivatives obtained from the oxime 2 . 相似文献
10.