In this article, we review the recent progress that has been made in the field of Lewis-acid catalysis of carbon carbon-bond-forming reactions in aqueous solution. Since water hampers the hard hard interactions between the catalyst and the reactant, it often complicates catalysis. However, once coordination has taken place, water can have beneficial effects on rates and selectivities of Lewis acid catalysed Diels Alder reactions, aldol reactions, allylation reactions, Barbier and Mannich type reactions as well as Michael additions.
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In mijn vorige blog schreef ik dat ik "groene chemie" niet zo'n goede term vind. Dit bericht borduurt daar enigszins op voort en is mijn persoonlijke kritische noot bij de transitie naar een groene(re) economie die momenteel in volle gang is.
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Many origin of life theories argue that molecular self-organization explains the spontaneous emergence of structural and dynamical constraints. However, the preservation of these constraints over time is not well-explained because ofthe self-undermining and self-limiting nature of these same processes. A process called autogenesis has been proposed in which a synergetic coupling between self-organized processes preserves the constraints thereby accumulated. Thispaper presents a computer simulation of this process (the AutogenicAutomaton) and compares its behavior to the same self-organizing processes when uncoupled. We demonstrate that this coupling produces a second-order constraint that can both resist dissipation and become replicated in new substrates over time.
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The catalytic oxidation of potato starch by [MnIV2 (μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn =1,4,7-trimethyl-1,4,7-triazacyclononane) with H2O2, was recently introduced as a promising alternative to ubiquitous sodium hypochlorite (NaOCl). Here, we report an in-depth investigation into interactions of the catalyst with the starch granule. Pitted starches obtained by pre-treatment with high-frequency ultrasound (HFUS) were shown to result in a uniquely homogeneous oxidation. To study this further, fractionation of oxidised potato starch was done which showed a preference for the oxidation of smaller granules with a higher relative surface area. This result was corroborated by chemical surface gelatinisation of fractionated granules. These studies showed that the inside of the granules was oxidised, but that Mncat had a moderate preference for oxidation of the periphery. Together, these results allow for a better understanding of oxidation of starch by Mncat and how it differs from NaOCl oxidation making further optimisation of the process possible.
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The copper(II) catalyzed enantioselective 1,4-addition reactions of diethylzinc to cyclic enones in the presence of novel phosphorus amidite ligands, easily prepared from α,α,α',α'-tetraphenyl-2,2'-dimethyl-1,3- dioxolane-4,5-dimethanol (TADDOL) derivatives, resulted in e.e.s up to 71% for cyclohexenone and up to 62% for cyclopentenone. A remarkable enhancement of enantioselectivity was observed upon the addition of powdered molecular sieves to the reaction mixture.
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The scope of this thesis of Gerrit Bouwhuis, lecturer at Saxion Research Centre for Design and Technology in Enschede is the development of a new industrial applicable pre-treatment process for cotton based on catalysis. The pre-treatment generally consists of desizing, scouring and bleaching. These processes can be continuous or batch wise. Advances in the science of biocatalytic pre-treatment of cotton and catalytic bleaching formed the scientific basis for this work. The work of Agrawal on enzymes for bio-scouring and of Topalovic on catalytic bleaching led to the conclusion that reduced reaction temperatures for the pre-treatment processes of cotton are possible. A second reason for the present work is a persistent and strong pressure on the industry to implement ‘more sustainable’ and environmental friendlier processes. It was clear that for the industrial implementation of the newly developed process it would be necessary to ‘translate’ the academic knowledge based on the catalysts, into a process at conditions that are applicable in textile industry. Previous experiences learned that the transition from academic knowledge into industrial applicable processes often failed. This is caused by lack of experience of university researchers with industrial product and process development as well as a lack of awareness of industrial developers of academic research. This is especially evident for the so-called Small and Medium Enterprises (SME’s). To overcome this gap a first step was to organize collaboration between academic institutes and industries. The basis for the collaboration was the prospect of this work for benefits for all parties involved. A rational approach has been adopted by first gathering knowledge about the properties and morphology of cotton and the know how on the conventional pre-treatment process. To be able to understand the conventional processes it was necessary not only to explore the chemical and physical aspects but also to evaluate the process conditions and equipment that are used. This information has been the basis for the present lab research on combined bio-catalytic desizing and scouring as well as catalytic bleaching. For the measurement of the performance of the treatments and the process steps, the performance indicators have been evaluated and selected. Here the choice has been made to use industrially known and accepted performance indicators. For the new bio-catalytic pre-treatment an enzyme cocktail, consisting of amylase, cutinase and pectinase has been developed. The process conditions in the enzyme cocktail tests have been explored reflecting different pre-treatment equipment as they are used in practice and for their different operation conditions. The exploration showed that combined bio-catalytic desizing and scouring seemed attractive for industrial application, with major reduction of the reaction and the rinsing temperatures, leading to several advantages. The performance of this treatment, when compared with the existing industrial treatment showed that the quality of the treated fabric was comparable or better than the present industrial standard, while concentrations enzymes in the cocktail have not yet been fully optimized. To explore the application of a manganese catalyst in the bleaching step of the pre-treatment process the fabrics were treated with the enzyme cocktail prior to the bleaching. It has been decided not to use conventional pre-treatment processes because in that case the combined desizing and scouring step would not be integrated in the newly developed process. To explore catalytic bleaching it has been tried to mimic the existing industrial processes where possible. The use of the catalyst at 100°C, as occurs in a conventional steamer, leads to decomposition of the catalyst and thus no bleach activation occurs. This led to the conclusion that catalytic bleaching is not possible in present steamers nor at low temperatur
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Michael additions of α-nitroesters with enones and α,β-unsaturated aldehydes result in quantitative conversions to the corresponding 1,4-adducts by performing the reactions in water in the presence of ytterbium triflate as water-tolerant Lewis acid.
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The invention relates to the use of modified starch obtainable by treating amylose containing starch in aqueous medium with an enzyme from the group of the α-1,4-α-1,4-glucosyl transferases (EC 2.4.1.25) or an enzyme the activity of which corresponds to that of enzymes from the group just mentioned, as an agent for forming a thermoreversible gel. The invention also relates to products in the form of a thermoreversible gel having as gel-forming substance a modified starch as defined. The invention further relates to the use of a modified starch as defined in the form of an aqueous solution.
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