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991.
Sandra Hübner Dirk Michalik Dr. Haijun Jiao Dr. Helfried Neumann Dr. Stefan Klaus Dirk Strübing Dr. Anke Spannenberg Dr. Matthias Beller Prof. Dr. 《化学:亚洲杂志》2007,2(6):734-746
Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features. 相似文献
992.
The antioxidative effect of flavonols and their glycosides against the peroxidation of linoleic acid has been studied in homogeneous solution (tBuOH/H(2)O, 3:2) and in sodium dodecyl sulfate and cetyl trimethylammonium bromide micelles. The peroxidation was initiated thermally by the water-soluble initiator 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the reaction kinetics were studied by monitoring the formation of linoleic acid hydroperoxides. The synergistic antioxidant effect of the flavonols with alpha-tocopherol (vitamin E) was also studied by following the decay kinetics of alpha-tocopherol and the alpha-tocopheroxyl radical. Kinetic analysis of the antioxidative process demonstrates that the flavonols are effective antioxidants in solution and in micelles, either alone or in combination with alpha-tocopherol. The antioxidative action involves trapping the initiating radicals in solution or in the bulk-water phase of the micelles, trapping the propagating lipid peroxyl radicals on the surface of the micelles, and regenerating alpha-tocopherol by reducing the alpha-tocopheroxyl radical. It was found that the antioxidant activity of the flavonols and their glycosides depends significantly on the position and number of the hydroxy groups, the oxidation potential of the molecule, and the reaction medium. The flavonols bearing ortho-dihydroxy groups possess significantly higher antioxidative activity than those without such functionalities, and the glycosides are less active than their parent aglycones. The activity of the flavonols is higher in micelles than in solution, while the activity of alpha-tocopherol is lower in micelles than in solution. This is because the predominant factor for controlling the activity is the hydrogen-bonding interaction of the antioxidant with the micellar surface in the case of hydrophilic flavonols, while it is the inter- and intramicellar diffusion in the case of lipophilic alpha-tocopherol. 相似文献
993.
Macrodefect-free (MDF) materials are one example of “hot topics” in the field of cement-based materials and composites exerting
new possibilities of the exploitation of added value. These are formed through cross-linking reactions of atoms at the interfaces
of cement grains and functional polymers, when medium pressure and twin-rolling procedure are applied. The MDF-relevance of
the system of Portland cement + polyphosphate is reported, together with optimal synthesis conditions and limiting rules.
The chemistry knowledge about MDF materials has been shown critical for both procedure design and exploitation. Chemical shifts
in both 27Al and 31P MAS NMR spectra confirm Al(6)—O—P(4) cross-linking in virgin probes and indicate secondary hydrolysis during moisture uptake
in domains free of cross-links. Thermogravimetric identification of the contents of hydrated and cross-linked phases in virgin
and in moisture-attacked MDF probes displays that moisture uptake is accompanied by an increase in content of cementitious
hydrates and CaCO3. The key phenomena governing the moisture sensitivity/resistance are the density and compactness of interfacial Al(6)—O—P(4)
cross-links vs. the access of the moist environment to the unreacted cement residue.
The paper was presented at the 20 ICCBiC (International Conference on Coordination and Bioinorganic Chemistry) held on 5–10
June 2005 in Smolenice, Slovakia. 相似文献
994.
Shengqiang Fang Lian Fu Changang Pang 《Journal of Radioanalytical and Nuclear Chemistry》1996,203(1):143-149
The methods including collection method, extraction-collection method, and special extraction-collection method have been investigated for high speed and efficient recovery of palladium from high pH reprocessing waste of spent nuclear fuel. The equilibrium of the reactions can be obtained is less than 1 minute. The maximum percent recovery of Pd is about 89%, 96% and 97% for collection, extraction-collection, and special extraction-collection methods, respectively. Nearly 100% of back extraction of Pd in the organic phase can be attained by using 7.4M ammonia solution, with a phase ratio of 1:1. The purity of the Pd product is high. The percent recovery of Pd is constant, up to 5·103 Gy of irradiation dose. 相似文献
995.
996.
Dr. Ing. K. Baaz 《Colloid and polymer science》1970,236(2):154-163
Zusammenfassung Die tertiären n-aliphatischen Phosphine spreiten auf Wasser spontan zu einem monomolekularen Film aus. Die Kompressionsisothermen der untersuchten tertiären aliphatischen Phosphine in homologer Reihe mit der Kettenlänge von C4 bis C16 wurden ausgemessen und die dabei auftretenden Filmzustände identifiziert. Das tertiäre C5-Phosphin bildet realgasanaloge, die C6–C12-Phosphine flüssiganaloge und die längerkettigen Phosphine festanaloge Filme.Ein Übergang vom tertiären Phosphin zum Phosphinoxid hat auf die Filmbildung keinen Einfluß, es ergibt sich nur eine geringfügige Vergrößerung der molekularen Fläche von etwa 10%.Der auf den Filmdruck 0 extrapolierte molekulare Flächenbedarf wurde sowohl nach den herkömmlichen Verfahren aus denF/A-Diagrammen als auch mit einer anderen Methode aus denF·A/F-Isothermen berechnet: beide Werte zeigen sehr gute Übereinstimmung. Dabei zeigt der Vergleich mit dem aus den molekularen Abmessungen errechneten Flächenbedarf, daß die Phosphinmoleküle im komprimierten Film nicht vollständig in Pyramiden- bzw. Kegelform geordnet sind sondern daß die aliphatischen Ketten vom sechsten C-Atom an senkrecht auf der Substratoberfläche stehen. Der P-C-Winkel ist nicht für, die ganze Kette richtungsweisend, die flexiblen Kohlenwasserstoff ketten sind abgewinkelt. Mit zunehmender Kettenlänge wächst das Molekül nur noch senkecht in die Höhe, deshalb bleibt die molekulare Fläche ab C6 annähernd konstant.
Mit 8 Abbildungen und 5 Tabellen 相似文献
Summary Tertiäry n-aliphatic phosphines form on water surfaces spontanously monolayers. The force-area isotherms of a homologous series of phosphins with a chainlength varying from C4 to C16 were measured and the appearing states of the films were identified. The tertiary C5 phosphine forms real-gas analogous films, the C6 to C12 phosphines liquid, analogous films and phosphines with lange carbon chains solid analogous films.A transition from tertiäry phosphines to the corresponding phosphine oxide has no influence on the formation of the films, it results only in an insignificant (10 p. c.) increase of the molecular area.The molecular area from the extrapolation to the film pressure of 0 was calculated by the customery methods out of theF/A diagramms, and by an other methods out of theFA/F isotherms. Good accordance of both values is shown. The area calculated from the molecular dimensions shows in comparison, that the phosphine molecules in comprimated films are not exactly disposed in pyramidal or conic shape, but that each aliphatic chain changes its direction after the sixth C-atom and stands vertically to the liquid-air interface. The direction of the chains is not determined by the angle of the P–C bonding, because the flexible carbon changes are distorted. With increasing chainlength, beginning from the tertiäry C6 phosphin the carbon chains stand only vertically to the substrate. Therefore the need of molecular area remains almost constant.
Mit 8 Abbildungen und 5 Tabellen 相似文献
997.
Shen YF Fang CJ Peng ZH Li DC Zhou YH 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):132-139
The molecular structure and binding, as well as infrared and electronic spectroscopic properties for the title complex Cu(mnt)(dmbpy)(mnt(2-)=maleonitriledithiolate, dmbpy=4,4'-dimethyl-2,2'-bipyridine) were studied in this paper. With semi-empirical PM3 and non-empirical DFT (B3LYP/6-311G*) methods, the molecular geometry of the complex was optimized and corresponding vibrational spectra in the gaseous state were obtained. The calculated results derived from DFT were more reasonable than those from PM3. The point group of Cu(mnt)(dmbpy) in isolated gaseous state was C(2), in which Cu(II) adopted a distorted tetrahedral geometry and the dihedral angle between the N(2)Cu and S(2)Cu planes was about 29.814 degrees. And a complete assignment to the IR spectra of such a complicated molecule was exhibited. With ZINDO/S method an electronic spectrum was calculated. The results showed that the calculated values generally agreed with the observed ones. And a detailed explain was made on its electronic spectra. 相似文献
998.
医用聚氯乙烯膜的等离子体表面改性 总被引:4,自引:0,他引:4
用两种不同气氛的辉光放电等离子体工艺对医用软质聚氯乙烯(PVC)膜进行了表面改性研究。结果表明,聚合性气氛的等离子体改性效果明显优于非聚合性气氛。平整致密的聚合膜对PVC增塑剂——邻苯二甲酸二辛酯的迁移和扩散起了阻挡作用,也使膜表面亲水性和表面张力极性成份增大,液固相界面张力减小,生物相容性得以改善。 相似文献
999.
Dr. Jan Koppelmann 《Colloid and polymer science》1963,189(1):1-6
Zusammenfassung Auf Grund theoretischer Überlegungen ist es bei der Bestimmung des Relaxationsverhaltens hochpolymerer Stoffe bei verschiedenen Beanspruchungsarten sinnvoll, zur Bestimmung der Relaxationszeiten die Maxima der Imaginärteile der elastischen Moduln und der reziproken Dielektrizitätskonstanten auszuwerten und die in Abhängigkeit von der Frequenz bei konstanter Temperatur gemessenen Dispersionskurven in die Anteile der Hauptund Nebendispersionsgebiete zu zerlegen. Durch Anwendung dieses Verfahrens auf die an Polyvinylchlorid gewonnenen Ergebnisse wird nachgewiesen, daß bei diesem Stoff die mechanisch und dielektrisch gemessenen Relaxationszeiten identisch sind und daß somit die vonThurn undWolf (1) vorgeschlagene Deutung der Unterschiede zwischen mechanischem und dielektrischem Relaxationsverhalten keine allgemeine Gültigkeit hat. Ein verbessertes Verfahren zur Bestimmung der Ultraschallgeschwindigkeit und der Ultraschalldämpfung in hochpolymeren Stoffen wird angegeben. 相似文献
1000.
Wang Y Deng K Gui L Tang Y Zhou J Cai L Qiu J Ren D 《Journal of colloid and interface science》1999,213(1):270-272
Nanoscopic particles of oxovanadium phthalocyanine (VOPc, phase-II) with different particle sizes are prepared by aggregation of VOPc molecules in the presence of surfactants for the first time. A size effect in the region of nanoscale was observed in the UV-visible spectra. The photoconductivity of the nanoscopic VOPc is much higher than that of bulk VOPc. Copyright 1999 Academic Press. 相似文献