Engineering faster transglycosidases and their acceptor specificity
Transglycosidases are enzymes that have the potential to catalyze the synthesis of a wide range of high-value compounds starting from biomass-derived feedstocks. Improving their activity and broadening the substrate range are important goals to enable the widespread application of this family of biocatalysts. In this work, we engineered 20 mutants of the rice transglycosidase Os9BGlu31 and evaluated their catalysis in 462 reactions over 18 different substrates. This allowed us to identify mutants that expanded their substrate range and showed high activity, including W243L and W243N. We also developed double mutants that show very high activity on certain substrates and exceptional specific…
Numerical study of the accuracy of temperature measurement by thermocouples in small-scale reactors
Proper temperature measurement is imperative in any laboratory study if reliable data are to be obtained, particularly in the field of chemical kinetics. In this paper we analyze in silico some typical thermowell configurations used in small-scale reactors by coupling computational fluid dynamics (CFD) with conjugated heat transfer phenomena. This allows us to identify deviations in measurements arising from thermal radiation and self-conductivity in mid and high temperature ranges, in addition to radial temperature gradients. A novel design is proposed and optimized by additional simulation, showing potential for faster and more accurate temperature measurements.
Research frontiers in energy-related materials and applications for 2020-2030
Abstract: This article delineates the state of the art for several materials used in the harvest, conversion, and storage of energy, and analyzes the challenges to be overcome in the decade ahead for them to reach the market and benefit society. The materials covered have had a special interest in recent years and include perovskites, materials for batteries and supercapacitors, graphene, and materials for hydrogen production and storage. Looking at the common challenges for these different systems, scientists in basic research should carefully consider commercial requirements when designing new materials. These include cost and ease of synthesis, abundance of precursors, recyclability of s…
Biodegradability Prediction of Fragrant Molecules by Molecular Topology
Biodegradability is a key property in the development of safer fragrances. In this work we present a green methodology for its preliminary assessment. The structure of various fragrant molecules is characterized by computing a large set of topological indices. Those relevant to biodegradability are selected by means of a hybrid stepwise selection method to build a linear classifier. This model is compared with a more complex artificial neural network trained with the indices previously found. After validation, the models show promise for time and cost reduction in the development of new, safer fragrances. The methodology presented could easily be adapted to many quasi-big data problems in R…
Engineering Zeolites for Catalytic Cracking to Light Olefins
Propene is a key building block for the petrochemical industry whose demand is increasing strongly in recent years, even faster than that of ethene. The availability of propene is limited, and therefore, efforts to optimize its production are being pursued. On the occasion of the 75th anniversary of the first FCC unit, we analyze some recent advances that have been achieved in the understanding and development of zeolites aiming to increase the production of light olefins as petrochemical building blocks by means of catalytic cracking. We discuss a selected group of emerging strategies in zeolite engineering that have great prospects for research and that we consider could impact the sector…
Converting olefins to propene: Ethene to propene and olefin cracking
ABSTRACTDemand for propene as a petrochemical building block keeps growing, while its availability has been decreased by the adoption of shale gas resources, among others. Efforts to optimize its production by conventional means (including modified fluid catalytic cracking) and new on-purpose production technologies (including ethene to propene (ETP) and olefin cracking) are being pursued. This work reviews the progress made on olefin conversion processes, including the ETP reaction, which is still under development, and the cracking of butenes and higher olefins (C5–C8). The factors analyzed include the catalytic performance of different zeolite materials and their modifications to increas…
Histamine, an effective initiator for the synthesis of polysulfides
The synthesis of polysulfides from thioepoxides traditionally makes use of toxic organometallic initiators. We demonstrate the use of histamine as an efficient initiator. The polymerization can be carried out under solvent-free and metal-free conditions at mild temperature to obtain high-quality polysulfides. A synergistic acid and base catalysis mechanism is proposed. The results enable a safer and cleaner production of next-generation polymers.
Enzyme-modified electrodes for biosensors and biofuel cells
In biosensors and biofuel cells, it is often desirable to accelerate the electron transfer rate between the enzyme and electrode surface to improve the performance of the devices (sensitivity or power output). To this end, in this review, we focus on three important strategies available to improve the performance of enzyme-modified electrodes: the use of protein engineering, designer polymers, and the introduction of nanomaterials. Engineering the protein or proteins that constitute the biocatalytic elements allow tuning their stability, activity, and specificity. It can also allow changing the enzyme immobilization efficiency (adsorption vs. covalent immobilization, for example). If direct…
Machine learning study of the molecular drivers of natural product prices
The price of chemicals is a very complex variable. It can be impacted by production costs but also by market and managerial factors, which may have complex relationships with molecular characteristics and the state of technology and society. In this work, we explore the extent to which molecular characteristics can help explain natural product prices with the aid of machine learning tools. We interpret models trained on molecular descriptors and molecular fingerprints. These models can explain a notable proportion of the variation in prices, suggesting that production and separation costs are a major contributor to current natural product prices. Some molecular properties stand out as key p…
Influences of Chemical Functionalities on Crystal Structures and Electrochemical Properties of Dihydro-benzoxazine Dimer Derivatives
Dihydro-1,3,2H-benzoxazine dimer derivatives or dihydro-benzoxazine dimers are a class of compounds typically prepared by ring-opening reactions between dihydro-benzoxazines and phenols. Dihydro-benzoxazine dimers act as chelating agents for several transition and rare-earth cations. To better understand the chelating properties, it is necessary to examine their structural features and electrochemical characteristics thoroughly. However, the electrochemical properties of dihydro-benzoxazine dimers have not been tremendously examined. Herein, eight derivatives of dihydro-benzoxazine dimers possessing different substituents on the benzene ring and the tertiary-amine nitrogen were synthesized …
Bio-inspired Ni dinuclear complexes as heterogeneous catalysts for hydrogen evolution
Abstract A major challenge in the sustainable production of hydrogen is lowering the electrochemical overpotential and the activation energy of the hydrogen evolution reaction. Some enzymes have two metallic Ni centers and catalyze this reaction with high activity. Taking inspiration from them, we have developed two novel dinuclear Ni(II) complexes, Ni-PATIO and Ni-PACO, with promise as molecular catalysts. Ni-PACO exhibits a square-planar geometry for both Ni(II) and two-fold rotational symmetry both in solid and solution states, whereas Ni-PATIO displays one square-planar Ni(II) center and one octahedral Ni(II) configuration, which confer it magnetic properties. We show that both complexe…
Theta-1 zeolite catalyst for increasing the yield of propene when cracking olefins and its potential integration with an olefin metathesis unit
[EN] There is a need for on-purpose propene production technologies beyond energy-intensive steam cracking. Hexene is a compound with limited value that can be found in several streams in the refinery and can readily crack on zeolites at lower temperatures and shorter contact times than those used for cracking alkanes. Cracking over ZSM-5 zeolite yields high selectivity to light olefins. These results are improved by Theta-1 zeolite, which can yield a remarkable propene molar selectivity of 180% (90 wt%) at 90% conversion, close to the maximum thermodynamic yield. Moreover, crystal engineering allowed its TOF to increase by more than 50%. Based on these results we also identified some prosp…
CCDC 2065593: Experimental Crystal Structure Determination
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CCDC 2092708: Experimental Crystal Structure Determination
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