984 resultados para michael-addition-reactions
Resumo:
The aim of the present work is to investigate the effects of blending and chemical interesterification reactions on the softening and melting behavior of chicken fat, its stearin and medium chain triacylglycerols, and blends thereof in various ratios. Chemical interesterification is a promising alternative to the current processes of modifying the physical properties of fats. In the experimental design 7 samples corresponding to 7 different blend proportions were used. The results were represented in triangular diagrams. The addition of stearin influenced the softening and melting points. The mixture response surface methodology proved to be an extremely useful tool for the optimization of the fat mixtures.
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This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III) tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules.
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The stereoselective addition of the titanium (IV) enolates derived from (S)-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8) and from (S)-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9) to N-Boc-2-methoxypyrrolidine (5b) afforded the addition products (+)-10 and (+)-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+)-isoretronecanol (1) and (+)-5-epi-tashiromine (2) in 43% and 49% overall yield, respectively.
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Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%). The most active prepared catalyst, PdNi(1%), was more selective than the Lindlar catalyst.
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The theoretical aspects of Voltammetry of Immobilized Microparticles (VIM) were discussed. The immobilization of microparticles on electrode surface, the electrode cleaning processes and the electrode materials were analyzed. The three-phase electrode model and the possible reactions between the immobilized particle and the electrolytic solution were discussed. In addition, this work discusses some selected applications of VIM published in the last years.
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The present paper describes the effect of metals ions on the in vitro availability of enoxacin (a second generation quinolone antibiotic) owing to drug-metal interaction. These interaction studies were performed at 37 °C in different pH environments simulating human body compartments and were studied by UV spectroscopic technique. In order to determine the probability of these reactions different kinetic parameters (dissolution constants (K) and free energy change (ΔG)) for these reactions were also calculated. It is proposed that the structure of enoxacin contains various electron donating sites which facilitate its binding with metallic cations forming chelates. Hence taking food products, nutritional supplements or multivitamins containing multivalent cations at the same time as enoxacin, could reduce the absorption of the drug into the circulation and thus would decrease the effectiveness of the drug. In addition, the MIC of enoxacin for various microorganisms before and after interaction with metal ions was calculated which in most cases was increased which possibly could impair the clinical efficacy of the drug.
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A neural network procedure to solve inverse chemical kinetic problems is discussed in this work. Rate constants are calculated from the product concentration of an irreversible consecutive reaction: the hydrogenation of Citral molecule, a process with industrial interest. Simulated and experimental data are considered. Errors in the simulated data, up to 7% in the concentrations, were assumed to investigate the robustness of the inverse procedure. Also, the proposed method is compared with two common methods in nonlinear analysis; the Simplex and Levenberg-Marquardt approaches. In all situations investigated, the neural network approach was numerically stable and robust with respect to deviations in the initial conditions or experimental noises.
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In esterification of oleic acid with methanol at 25 °C HPA displayed the highest activity. Moreover the HPA could be reused after being transformed into its cesium salt. In the reaction of etherification of glycerol HPA and Amberlyst 35W showed similar initial activity levels. The results of acid properties demonstrate that HPA is a strong protonic acid and that both surface and bulk protons contribute to the acidity. Because of its strong affinity for polar compounds, HPA is also seemingly dissolved in both oleic acid and methanol. The reaction in this case proceeds with the catalyst in the homogenous phase.
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Tämän työn tarkoituksena oli tutkia hiilidioksidin talteenottoon soveltuvan anioninvaihtohartsin valmistusmenetelmiä, kokeilla eri menetelmiä käytännössä ja tutkia sekä itse valmistettujen että valmiina saatujen hartsien adsorptiokykyä ja muita ominaisuuksia. Kemiallinen adsorptio amiiniryhmän omaavien hartsien avulla on yksi tapa sitoa hiilidioksidia ilmasta. Primäärinen amiiniryhmä sitoo hiilidioksidia parhaiten. Primäärisen amiiniryhmän omaava anioninvaihtohartsi voidaan valmistaa pohjapolymeeristä halogeenialkyloimalla ja aminoimalla, aminoalkyloimalla tai suoraan aminoimalla. Aminoalkylointi voidaan suorittaa erilaisilla reagensseilla ja katalyyteillä. Tässä työssä hartseja valmistettiin aminoimalla polymetyyliakrylaattidivinyylibentseenipohjaista polymeeriä etyylidiamiinilla ja propyylidiamiinilla. Lisäksi suoritettiin polystyreeni-divinyylibentseenipohjaisen polymeerin aminoalkylointi bis(ftaali-imidometyyli)eetterin avulla. Reaktio tehtiin kahdella eri katalyytillä; rikkitrioksidilla ja rautakloridilla. Aminoalkylointireaktioissa tarvittava eetteri piti ennen varsinaista reaktiota valmistaa N-hydroksymetyyliftaali-imidistä. Myös tämän reagenssin syntetisointia ftaali-imidistä kokeiltiin. Kaikki synteesit onnistuivat melko hyvin, paitsi aminoalkylointi rautakloridikatalyytillä. Hartsien valmistuksen lisäksi itse valmistettuja primäärisen amiiniryhmän omaavia hartseja sekä erilaisia amiiniryhmiä omaavia valmiita hartseja karakterisoitiin eri tavoin. Erityisesti haluttiin tutkia hiilidioksidin adsorptiokapasiteettia ja hartsien termistä kestävyyttä. Kaikista tutkituista hartseista lähimpänä haluttuja ominaisuuksia olivat kaksi kaupallista primäärisen amiiniryhmän omaavaa PS-DVBpohjaista makrohuokoista hartsia. Rakenteeltaan samanlainen itse valmistettu hartsi (rikkitrioksidikatalyytin läsnä ollessa aminoalkyloitu) oli myös ominaisuuksiltaan lupaava. Valmistusmenetelmää pitää kuitenkin tutkia ja kehittää lisää vielä parempien tulosten aikaansaamiseksi. Myös kaupallinen polyetyleeni-imiinirakenteen omaava silikapohjainen hartsi oli ominaisuuksiltaan hyvä.
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Chitosan, poly[β-(1-4)-linked-2-amino-2-deoxy-D-glucose], is the N-deacetylated product of chitin which is a major component of arthropod and crustacean shells such as lobsters, crabs, shrimps, and cuttlefishes. In addition, chitosan has many significant biological and chemical properties such as biodegradability, biocompatibility and bioactivity as well as polycationic properties. Thus, it has been widely used in many industrial and biomedical applications including wastewater treatment, chromatographic support, carriers for controlled drug delivery and enzyme immobilization. This review is an insight into the exploitation of utilization of chitosan based-supports in different geometrical configurations on the immobilization of enzymes by different protocols for further application in biotransformation reactions.
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Methanol steam reforming reaction was studied over Cu(5 wt.%)/CeO2 with and without the presence of Zn. The Zn addition decreased the Cu+2 reducibility and increased the oxygen mobility of ceria. The main products were CO2 and H2 with small amount of CO. Selectivity to CO decreased with the Zn addition and it was lower at lower reaction temperatures and lower space velocities. At 230 ºC and W/F MeOH = 648 g min mol-1 selectivities to H2 and to CO2 were 100% on Zn/Cu/Ce. The catalytic results indicated that CO was mainly a secondary product formed from reverse water gas shift reaction.
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This review describes the use of two biomass-derivate butenolides as intermediates in organic synthesis, mucobromic acid and its reduced derivative 3,4-dibromofuran-2(5H)-one. The ambiphilic and ambident character of such butenolides make them versatile starting materials in the synthesis of natural and/or bioactive compounds. Thus, the reactions of mucobromic acid with C-nucleophiles and heteronucleophiles are described, as well as the nucleophilic addition to carbonyl reactions of 3,4-dibromofuran-2(5H)-one. Besides, both compounds are active in diverse metal cross-coupling reactions, manly with palladium in Suzuki and Sonogashira reactions.
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Common student misunderstandings regarding chemical equilibrium are reported taking into account the response of freshman students to some typical questions involving acid-base reactions. Language has been shown to be one of the main issues associated with students' difficulties on this subject, such as in the case of concentration and amount of substance (mol). Another usual problem was observed in questions involving buffer solutions after addition of a reagent. A number of recommendations have emerged from the results presented in this work as an attempt to enhance the learning of this topic in general chemistry courses given to first-year students.
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In this work the degradation of textile dyes were evaluated, using Fenton, photo-Fenton and electro-Fenton processes. Under optimized conditions Fenton and photo-Fenton processes showed high decolorization capacity of the model dyes. The electro-Fenton process was carried out in an undivided electrochemical reactor (1000 mL) equipped with a carbon-felt cathode (253 cm²) and a platinum gauze anode (6 cm²). Under optimal conditions (J: 1.6 mA cm-2, Na2SO4: 0.075 mol L-1, pH: 3) H2O2 concentration of about 60 mg L-1 was observed. The addition of Fe2+ (15 mg L-1) induces Fenton reactions that permit almost total decolorization of textile dyes.