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101.
The Claisen rearrangement of the N‐protected, silylated allyl glycinates 11 and 12 led to the formation of allyl/silyl‐functionalized amino acids 13 and 14 in yields up to 80%. The diastereoisomer ratio varied from 2 : 1 to 29 : 1 for 11mb , and from 2 : 1 to 46 : 1 (syn/anti) for 12mb , depending on reaction conditions, as shown by X‐ray crystallographic analysis of 14mb . The relationship between the size of the alkyl groups on the chlorosilane reagent (Me2R″SiCl, R″=Cl, Me, t‐Bu, Ph) used as an enolate trap and the observed stereoselectivity was investigated in the case of the Ireland–Claisen variant. Me3SiCl gave the best results. However, the size of the alkyl groups on the silylated ester (Me2R″Si, R=Me, t‐Bu, Ph, i‐Pr) did not exert a significant effect on the diastereoselectivity or yield of the rearrangement. 相似文献
102.
Mohamed A. F. Elmosallamy Mohamed M. Ghoneim Hamada M. A. Killa Amr L. Saber 《Mikrochimica acta》2005,151(1-2):109-113
A potentiometric poly(vinyl chloride) membrane sensor for determination of saccharin is described. It is based on the use of Aliquat 336S-saccharinateion-pair as an electroactive material in plasticized PVC membranes with o-nitrophenyloctylether or dioctylphthalate. The sensor is conditioned for at least two days in 0.1 mol L−1 sodium saccharinate before use. It exhibits fast, stable and Nernstian response for saccharinate ions over the concentration range of 1.0 × 10−1–5.0 × 10−5 mol L−1 and pH range of 4.5–11. The sensor is used for determination of saccharin in some dosage forms. Results with an average recovery of 101% and a mean standard deviation of 0.2% are obtained which is compared favourably with data obtained using the British pharmacopoeia method. The sensor shows reasonable selectivity towards saccharin in presence of many anions and natural sweeteners. 相似文献
103.
A unique approach to non-covalent electron and energy transfer is described that is based on the formation of salt bridges between oppositely charged porphyrin units. A new class of electrostatically linked dimeric and pentameric porphyrins was synthesized by interaction of novel anionic boron containing porphyrins such as 5-(benzamidodecahydro-closo-dodecaborate)-10,15,20-triphenylporphyrin (N1) and meso-tetrakis-benzamidodecahydro-closo-dodecaborate)porphyrin (N2) and a variety of cationic meso-tetraarylporphyrin units. A bipyridine linked dimer (N1 · bpy · N1) was also prepared by employing N,N′-dimethyl-4,4′-bipyridinium (bpy) as a spacer between two mono-anionic species. A quinone-porphyrin dyad was also prepared for electron or energy transfer demonstration. All the synthesized assemblies were characterized by NMR, IR, UV-Vis, and mass spectroscopy. Significant spectral changes occurred in the absorption spectra of these non-covalent porphyrin assemblies compared to those of the reference monomers, indicating the presence of electronic interaction between the adjacent porphyrin units. Resonance light scattering was also used to study the formation of these assemblies in solution. 相似文献
104.
Balkis Al‐Saleh Morsy Ahmed El‐Apasery Rasha Safwat Abdel‐Aziz Mohamed Hilmy Elnagdi 《Journal of heterocyclic chemistry》2005,42(4):563-566
The 3‐anilinoenones 3a,b were prepared from the corresponding 3‐dimemyl‐aminopropenones. The reactivity of 3a,b towards a variety of carbon and nitrogen nucleophiles as well as naphthoquinones is reported. 相似文献
105.
Issam SM Mohamed G Dominique LM Thierry M Farid L Nejib M 《Applied biochemistry and biotechnology》2004,112(2):63-78
The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one beta-glucosidase (beta-glu x). The enzyme was purified to apparent homogeneity by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography (HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that beta-glu x may be a homodimer. For p-nitrophenyl beta-d-glucopyranoside hydrolysis, apparent Km and Vmax values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55-60 degrees C and pH 5.0, respectively. beta-Glu x was strongly inhibited by Fe2+ and activated about 35% by Ca2+. beta-Glu x possesses strong transglucosylation activity in comparison with commercially available beta-glucosidases. The production rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50 degrees C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 3C nuclear magnetic resonance spectroscopy. 相似文献
106.
Mohamed Y. El-Sheikh Abdel-Fattah M. Habib Fathy M. Ashmawy Ali H. Gemeay Ahmed B. Zaki 《Transition Metal Chemistry》1989,14(2):95-99
Summary The slow decomposition of H2O2 in the presence of Dowex-50 W resin in the form of an ethylenediaminecopper(II) complex ion in water is accompanied by an induction period. The reaction is first order with respect to [H2O2] and the rate constant (perg of dry resin) was deduced. Autocatalytic behaviour was found for the H2O2 decomposition with 2% crosslinked divinylbenzene. The induction period disappeared and the reaction rate increased when the decomposition was carried out with a resin in the form of a peroxo-copper complex, which proves that the formation of an intermediate (active species) retards the reaction rate. The precursor of the active species, formed during the induction period, was not the amine-copper(II) complex ion but a product of the latter with H2O2. It proved impossible to carry out the decomposition in acid or buffer solutions, in which the resin is regenerated. 相似文献
107.
H. F. Aly M. Raieh S. Mohamed A. A. Abdel-Rassoul 《Journal of Radioanalytical and Nuclear Chemistry》1979,49(2):213-224
The effect of ten pure diluents and different mixtures of nitrobenzene and toluene on the synergic extraction of Co2+ by the thenoyltrifluoroacetone (HTTA)-tribenzylamine (TBA) mixture is studied. The logarithm of the extraction constant of
Co(TTA)2 increases with increasing dielectric constant of the diluent, whereas the logarithm of the formation constant of the extracted
adduct Co(TTA)2TBA decreases with increasing dielectric constant of the diluent. This behaviour is explained by changes in the hydrophobic
character of the extracted species. The theory of regular solutions is successfully applied to the extracted adduct. Consideration
of the self-association of the amine salt is necessary in the treatment of the equilibria involved. 相似文献
108.
Hamza MS Zou X Banka R Brown KL van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2005,(4):782-787
Ligand substitution reactions of the vitamin B12 analog cyanoimidazolylcobamide, CN(Im)Cbl, with cyanide were studied. Cyanide substitutes imidazole (Im) in the alpha-position more slowly than it substitutes dimethylbenzimidazole in cyanocobalamin (vitamin B12). The kinetics of the displacement of Im by CN- showed saturation behaviour at high cyanide concentration; the limiting rate constant was found to be 0.0264 s(-1) at 25 degrees C and is characterized by the activation parameters: DeltaH(not =) = 111 +/- 2 kJ mol(-1), DeltaS(not =) = +97 +/- 6 J K(-1) mol(-1), and DeltaV(not =) = +9.3 +/- 0.3 cm3 mol(-1). These parameters are interpreted in terms of an I(d) mechanism. The equilibrium constant for the reaction of CN(Im)Cbl with CN- was found to be 861 +/- 75 M(-1), which is significantly less than that obtained for the reaction of cyanocobalamin with CN- (viz. 10(4) M(-1)). pKbase-off for the base-on/base-off equilibrium was determined spectrophotometrically and found to be 0.99 +/- 0.05, which is about 0.9 pH units higher than that obtained previously in the case of cyanocobalamin. In addition, the kinetics of the base-on/base-off reaction was studied using a pH-jump technique and the data obtained revealed evidence for an acid catalyzed reaction path. The results obtained in this study are discussed in reference to those reported previously for cyanocobalamin. 相似文献
109.
N. A. Mohamed Farook 《Journal of the Iranian Chemical Society》2006,3(4):378-386
Kinetics and mechanism of oxidation of substituted and unsubstituted 4-oxoacids (S) by N-bromosuccinimide (NBS) in aqueous acetic acid medium have been studied potentiometrically. The reaction follows first-order kinetics, each in 4-oxoacids, NBS and H+. The effect of changes in the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. Based on the kinetic results and the product analysis, a suitable mechanism has been proposed for the reaction of NBS with 4-oxoacids. 相似文献
110.
A. E. Mohamed R. M. Awadallah A. A. Hassan 《Journal of Radioanalytical and Nuclear Chemistry》1989,129(2):453-457
Multielement neutron activation analysis has been applied to the determination of macro, micro and trace amounts of Al, Br, Ca, Cl, Co, Cr, Cs, Fe, K, La, Mg, Mn, Na, Rb, Sc and V in molasses of Kom Ombo, Edfu, Armant, Naga Hammady and Abu Korkass cane sugar factories. The threshold element concentrations are acceptable and below the safety. Differences in element concentrations may be related to different botanic textures and structures, different compositions of sugar cane plants, corrosion of containers or changes in soil as a result of geochemical differentiation. The method is sensitive down to 0.038 ppm of V. The relative errors due to counting statistics are in the range of 0.2–11%. 相似文献