New Solvent-Free Melting-Assisted Preparation of Energetic Compound of Nickel with Imidazole for Combustion Synthesis of Ni-Based Materials

In this work two approaches to the synthesis of energetic complex compound Ni(Im)6(NO3)2 from imidazole and nicklel (II) nitrate were applied: a traditional synthesis from solution and a solvent-free melting-assisted method. According to infrared spectroscopy, X-ray diffraction, elemental and thermal analysis data, it was shown that the solvent-free melt synthesis is a faster, simpler and environmentally friendly method of Ni(Im)6(NO3)2 preparation. The results show that this compound is a promising precursor for the production of nanocrystalline Ni-NiO materials by air-assisted combustion method. The combustion of this complex together with inorganic supports makes it possible to synthesize supported nickel catalysts for different catalytic processes.

Pigments—the palette of organic colourants in wall paintings

The present contribution deals with the use of organic colourants in wall paintings, polychrome pottery and painted stone artworks, i.e. painted artworks on inorganic supports. The term organic colourants is referred to the chemical nature of these compounds but not to the way of application; therefore, organic colourants can be dyes, lakes or pigments. The use of organic colourants in wall paintings has been given little attention in the past, perhaps on the assumption that they were rarely used by ancient artists. Recent diagnostic studies, however, brought evidence that their use was not fragmentary; on the contrary, there seems to be continuity in the centuries, at least with regard to the most widely used such as madder, Tyrian purple and indigo. Sources, alteration phenomena, identification methods and analytical evidence is given for the main organic colourants with concern to red, yellow, green, purple and blue hues. Drawbacks and issues are discussed with concern to the identification techniques.

3D printed ceramics as solid supports for enzyme immobilization: an automated DoE approach for applications in continuous flow

In recent years, 3D printing has emerged in the field of chemical engineering as a powerful manufacturing technique to rapidly design and produce tailor-made reaction equipment. In fact, reactors with complex internal geometries can be easily fabricated, optimized and interchanged in order to respond to precise process needs, such as improved mixing and increased surface area. These advantages make them interesting especially for catalytic applications, since customized structured bed reactors can be easily produced. 3D printing applications are not limited to reactor design, it is also possible to realize functional low cost alternatives to analytical equipment that can be used to increase the level of process understanding while keeping the investment costs low. In this work, in-house designed ceramic structured inserts printed via vat photopolymerization (VPP) are presented and characterized. The flow behavior inside these inserts was determined with residence time distribution (RTD) experiments enabled by in-house designed and 3D printed inline photometric flow cells. As a proof of concept, these structured inserts were fitted in an HPLC column to serve as solid inorganic supports for the immobilization of the enzyme Phenolic acid Decarboxylase (bsPAD), which catalyzes the decarboxylation of cinnamic acids. The conversion of coumaric acid to vinylphenol was chosen as a model system to prove the implementation of these engineered inserts in a continuous biocatalytic application with high product yield and process stability. The setup was further automated in order to quickly identify the optimum operating conditions via a Design of Experiments (DoE) approach. The use of a systematic optimization, together with the adaptability of 3D printed equipment to the process requirements, render the presented approach highly promising for a more feasible implementation of biocatalysts in continuous industrial processes.

Green Procedure for Aerobic Oxidation of Benzylic Alcohols with Palladium Supported on Iota-Carrageenan in Ethanol

The search for selective heterogeneous catalysts for the aerobic oxidation of alcohols to ketones and aldehydes has drawn much attention in the last decade. To that end, different palladium-based catalysts have been proposed that use various organic and inorganic supports. In addition, supports that originate from a biological and renewable source that is also nontoxic and biodegradable were found to be superior. We heterogenized palladium chloride or acetate complexes with triphenylphosphine trisulfonate on iota-carrageenan xerogel by simple mixing of the complex and the polysaccharide in water. The resulting polysaccharide-catalyst mixture then underwent deep freeze and lyophilization, after which the catalyst was characterized by TEM, XPS and SEM-EDS and tested in aerobic oxidation. The new heterogeneous catalysts were successfully used for the first time in the aerobic oxidation of benzylic alcohols. Moreover, they were easily removed from the reaction mixture and recycled, yielding an increase in activity with each subsequent reuse. As determined by TEM and XPS, the reduction in palladium and the formation of nanoparticles during the reaction in ethanol yielded more active species and, therefore, higher conversion rates. A SEM-EDS analysis indicated that the palladium was thoroughly dispersed in the xerogel catalysts. Moreover, the xerogel catalyst was observed to undergo a structural change during the reaction. To conclude, the new heterogeneous catalyst was prepared by a simple and straightforward method that used a non-toxic, renewable and biodegradable support to yield an active, selective and recyclable heterogeneous system.

Heterogeneous Biocatalysts for the Final Stages of Deep Processing of Renewable Resources into Valuable Products

Heterogeneous biocatalysis is a part of biotechnology and it has commercial potential for industrial implementation, in particular the final stages of deep processing of renewable raw materials. The commercially attractive heterogeneous biocatalysts are prepared by immobilizing practically valuable enzymatic active substances onto solid inorganic supports. Heterogeneous biocatalytic processes of the target conversion of substrate into valuable market product are carried out in periodic or continuous modes using traditional batch and packed-bed reactors, as well as novel types of vortex reactors in accordance with the principles of green chemistry. Heterogeneous biocatalysts for the final stages of deep processing of vegetable raw materials such as starch and oils are described here. One of the biocatalysts is glucoamylase immobilized by adsorption on mesoporous carbon support Sibunit™ type. This glucoamylase-active biocatalyst is used at the stage of starch saccharification, i.e., hydrolysis of dextrin to treacle and glucose syrups used in food and confectionary industries. The second of the biocatalysts is recombinant T. lanuginosus lipase immobilized on mesoporous silica KSK™ type and macroporous carbon aerogel. These lipase-active biocatalysts can effectively compete with traditional organic synthesis catalysts, and they are used in low-temperature processes carried out in unconventional anhydrous media such as interesterification of vegetable oils’ triglycerides with ethyl acetate for producing ethyl esters of fatty acids (biodiesel and vitamin F) and esterification of fatty acids with aliphatic alcohols for synthesis of various esters used as fragrances, flavorings, odors, emollients, and nonionic surfactants in perfume and cosmetics industries. The prepared heterogeneous biocatalysts due to their high enzymatic activity and operational stability are promising for practical implementation.

Amino acids and Peptides Organocatalysts: A Brief Overview on Its Evolution and Applications in Organic Asymmetric Synthesis

: This review highlights the application of biopolymers of natural α-amino acids and its derived wild type peptides employed as an organocatalysis for the asymmetric synthesis published by researchers across the globe is described. The α-amino acids with L-stereochemistry are available commercial in pure form are played crucial role in enantioselective chiral molecule synthesis. Out of twenty natural amino acids, only one secondary amine containing proline amino acid exhibited revolution in the field of orgnocatalysis, because of its rigid structure and formation of an imine like transition state during the reaction lead more stereoselectivity. Hence, it is referred to as a simple enzyme in organocatalyst. Further discussed chiral organic molecule synthesis by employing oligopeptides derived from the natural amino acids as a robust biocatalyst replaced enzyme catalysts. The peptide includes di-, tri, tetra-, penta- and oligopeptide derived demonstrated as a potential organocatalysts, whose reaction activity and mechanistic pathways are reviewed. Several choice of families of these organocatalysts permit chemist to achieve facile and efficient stereoselective synthesis of many complex natural products with optically pure isomer. Subsequently, researcher developed green and sustainable heterogeneous catalytic system containing organocatalyst immobilized onto solid inorganic supports or porous materials, and is responsible for accelerating the reaction through heterogeneous phase. The developed heterogeneous organocatalysts-MOFs found to be used easier and employed for bulk production and flow reactor synthesis. This review compiled many outstanding discoveries in organocatalysts derived amino acids and it’s heterogenized on to MOFs together role of the organocatalysis in many organic transformations in academic and industrial applications are covered.

Extraction Chromatography Materials Prepared with HDEHP on Different Inorganic Supports for the Separation of Gadolinium and Terbium

Bis(2-ethylhexyl)phosphoric acid (HDEHP) is frequently used as an extractant in the separation and recovery of lanthanides by solvent extraction and extraction chromatography, where HDEHP (stationary phase) is fixed on an inert support and the mobile phase is an aqueous solution. Because the results of extraction chromatography strongly depend on the support material, in this study, we aim to prepare solid extractants (extraction chromatography materials) with different inorganic supports impregnated with HDEHP for the adsorption of Gd and Tb from HCl solutions, putting emphasis on the effect of the supports on the solid extractant behavior. Gd and Tb partition data were determined in HCl solutions from the prepared extraction chromatography materials using elution analysis. Solid extractants were characterized by X-Ray diffraction, electron microscopy, and infrared spectroscopy in order to determine their properties and to explain their extraction behavior. The characterization of the solid extractants showed a heterogeneous distribution of the HDEHP on the surfaces of the different supports studied. The irregular shape of the support particles produces discontinuous and heterogenous silanization and HDEHP coatings on the support surface, affecting the retention performance of the solid extractant and the chromatographic resolution.