Enzymatic synthesis of oleyl oleate in dense fluids

Esterification between oleic acid and oleyl alcohol, catalyzed by theMucor miehei immobilized lipase in a batch-stirred tank reactor with supercritical carbon dioxide as solvent produced higher reaction rates at supercritical conditions than in the solvent-free system. A continuous fixed-bed reactor was designed based on the results obtained from batch experiments. At 150 bar, 40°C, and with water activity 0.46% w/w, the activity of the enzyme preparation is practically unchanged when CO₂ was used as solvent. The addition of small amounts of water increases the conversion rate. The higher conversion also was observed at longer residence time. Whenn-butane was used as reaction medium, a decrease in conversion was observed.     

Sub-proteome approach to the knowledge of liver

In the recent years, global proteomics approaches have been widely used to characterize a number of tissue proteomes including plasma and liver; however, the elevated complexity of these samples in combination with the high abundance of some specific proteins make the study of the lowest abundant proteins difficult. This review is focused on different strategies that have been developed to extend the proteome focused on these two tissues, as, for example, the analysis of sub-cellular proteomes. In this regard, two special kind of extracellular vesicles--exosomes and membrane plasma shedding vesicles--are emerging as excellent biological source both to extend the liver and plasma proteomes and to be applied in the discovery of non-invasive liver-specific disease biomarkers.     

Understanding bottom-up continuous hydrothermal synthesis of nanoparticles using empirical measurement and computational simulation

Continuous hydrothermal synthesis was highlighted in a recent review as an enabling technology for the production of nanoparticles. In recent years, it has been shown to be a suitable reaction medium for the synthesis of a wide range of nanomaterials. Many single and complex nanomaterials such as metals, metal oxides, doped oxides, carbonates, sulfides, hydroxides, phosphates, and metal organic frameworks can be formed using continuous hydrothermal synthesis techniques. This work presents a methodology to characterize continuous hydrothermal flow systems both experimentally and numerically, and to determine the scalability of a counter current supercritical water reactor for the large scale production (>1,000 T·year^–1) of nanomaterials. Experiments were performed using a purpose-built continuous flow rig, featuring an injection loop on a metal salt feed line, which allowed the injection of a chromophoric tracer. At the system outlet, the tracer was detected using UV/Vis absorption, which could be used to measure the residence time distribution within the reactor volume. Computational fluid dynamics (CFD) calculations were also conducted using a modeled geometry to represent the experimental apparatus. The performance of the CFD model was tested against experimental data, verifying that the CFD model accurately predicted the nucleation and growth of the nanomaterials inside the reactor.

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Synthesis of Oleyl Oleate with Immobilized Lipase from Mucor miehei

The synthesis of oleyl oleate with immobilized 1,3-specific lipase from Mucor miehei is presented in this article. Oleyl alcohol was esterified with oleic acid in the presence of a Mucor miehei lipase (lipozyme^IM) to obtain oleyl oleate. The effects of various temperatures and various enzyme/substrate ratios have been investigated to determine optimal conditions for the esterification process. The highest conversion of oleic acid 86.9 % was obtained at 50°C. The optimal addition of lipase to substrates was determined to be 0.1 g per gram of reaction mixture. The esterification can be modeled successfully as a reverse second-order reaction. Thermodynamic properties of the reaction system at 50°C were also determined. Activation energy was 14.65 kJ/mol, entropy of activation –0.8 J/mol·K and free energy of activation was 98.568 kJ/mol.     

Kinetics of supercritical carbon dioxide extraction of borage and evening primrose seed oil

In the present work, high‐pressure extraction of borage (Borago officinalis L.) and evening primrose (Oenothera biennis L.) seed oil, containing the valuable γ‐linolenic acid (GLA), has been investigated. Extraction was performed with supercritical carbon dioxide on a semi‐continuous flow apparatus at pressures of 200 and 300 bar, and at temperatures of 40 and 60 °C. A constant flow rate of carbon dioxide in the range from 0.17 to 0.20 kg/h was maintained during extraction. The extraction yields obtained using dense CO₂ were similar to those obtained with conventional extraction using hexane as solvent. The composition of extracted crude oil was determined by GC analysis. The best results were obtained at 300 bar and 40 °C for both seed types extracted, where the quality of oil was highest with regard to GLA content. The evening primrose seed oil extracted with supercritical fluid extraction was particularly rich in unsaturated fatty acids: up to 89.7 wt‐% of total free fatty acids in the oil. The dynamic behavior of the extraction runs was analyzed using two mathematical models for describing the constant rate period and the subsequent falling rate period. Based on the experimental data, external mass transfer coefficients, diffusion coefficients and diffusivity in solid phase were estimated. Results showed good agreement between calculated and experimental data.     

Copper nanowires within the central channel of tobacco mosaic virus particles

Simple electrochemical deposition techniques can produce highly defined metal nanostructures in templates. Electroless deposition (ELD) can be effectively used for depositing metals on insulators such as biological or plastic surfaces. With biomolecular templates, metallization methods are often restricted to mild reductions, and the deposition of copper at pH values above 12 is usually not applicable. We produced copper nanowires of 3 nm in diameter and up to 150 nm in length by electroless deposition within the 4 nm wide channel of tobacco mosaic virus (TMV) particles. We employed a low pH (7.5) copper electroless deposition solution that is compatible with biomolecules. The fabrication process of the nanowires is based on sensitization of tobacco mosaic virus with Pd(II) prior to the electroless deposition. We analyzed the chemical composition of the nanowires by energy-filtering transmission electron microscopy, and used the method also for nickel and cobalt nanowires deposited within the viral channel.     

On the computation of linear model predictive control laws

Finite-time optimal control problems with quadratic performance index for linear systems with linear constraints can be transformed into Quadratic Programs (QPs). Model Predictive Control requires the on-line solution of such QPs. This can be obtained by using a QP solver or evaluating the associated explicit solution. The objective of this note is twofold. First, we shed some light on the computational complexity and storage demand of the two approaches when an active set QP solver is used. Second, we show the existence of alternative algorithms with a different tradeoff between memory and computational time. In particular, we present an algorithm which, for a certain class of systems, outperforms standard explicit solvers both in terms of memory and worst case computational time.