Journal articles: 'Enzymatic catalysi'

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Zeynalov, Eldar, and Tofik Nagiev. "Enzymatic Catalysis of Hydrocarbons Oxidation “in vitro” (Review)." Chemistry & Chemical Technology 9, no. 2 (May 15, 2015): 157–64. http://dx.doi.org/10.23939/chcht09.02.157.

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Sarkar, Abhra, and Siddharth Pandey. "Applications of Ionic Liquids in Green Catalysis: A Review of Recent Efforts." Current Catalysis 10, no. 3 (December 2021): 165–78. http://dx.doi.org/10.2174/2211544710666211119095007.

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: Ionic Liquids (ILs) in their neoteric form have emerged to be a potential ‘green’ alternative to traditional Volatile Organic Compounds (VOCs) as solvents in different fields of industries and academia. Recent investigations on the development of multi-faceted applications of ionic liquids have revealed that they really stand for “environmentally-benign” solvents as far as their impact on the ecology is concerned. This caused them to be an exciting and lucrative subject to explore more and more, and many research groups are involved in the manifestation of their inherent undisclosed legacy. Recently, there has been a huge jump in search of an alternative to conventional metal catalysts in academia as well as in industries due to their pollution-evoking roles. Scientists have explored multiple numbers of homogeneous or heterogeneous mixtures of catalysts incorporating ionic liquids to reduce the extent of contamination in our global environment produced due to catalytic synthesis and chemical transformations. In this review, we have put our concentration on some beneficial and recently explored aspects of the successful implementation of Ionic Liquids in different forms in several fields of catalysis as a ‘green’ alternative catalyst/co-catalyst/solvent for catalysis to replace or minimize the lone and hazardous use of metal and metallic compounds as catalysts as well as chemicals like mineral acids or VOCs as solvents. Here, our study focuses on the inevitable role of ILs in several catalytic reactions like cycloaddition of CO2, electrolytic reduction of CO2, biocatalytic or enzymatic reactions, some of the important organic conversions, and biomass to biofuel conversion as catalysts, cocatalysts, catalyst activator, and solvents.

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Khan, Haris Mahmood, Tanveer Iqbal, Saima Yasin, Muhammad Irfan, Muhammad Mujtaba Abbas, Ibham Veza, Manzoore Elahi M. Soudagar, Anas Abdelrahman, and Md Abul Kalam. "Heterogeneous Catalyzed Biodiesel Production Using Cosolvent: A Mini Review." Sustainability 14, no. 9 (April 22, 2022): 5062. http://dx.doi.org/10.3390/su14095062.

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Biodiesel is gaining recognition as a good replacement for typical diesel owing to its renewability, sustainability, and eco-friendly nature. Transesterification is the leading route for biodiesel generation, which occurs during homogeneous/heterogeneous/enzymatic catalysis. Besides this, the usage of heterogeneous catalysts is considered more advantageous over homogeneous catalysts due to the easy catalyst recovery. Consequently, numerous heterogeneous catalysts have been synthesized from multiple sources with the intention of making the manufacturing process more efficient and cost-effective. Alongside this, numerous researchers have attempted to improve the biodiesel yield using heterogeneous catalysts by introducing cosolvents, such that phase limitation between oil and alcohol can be minimized. This short review is aimed at examining the investigations performed to date on heterogeneously catalyzed biodiesel generation in the presence of different cosolvents. It encompasses the techniques for heterogeneous catalyst synthesis, reported in the literature available for heterogeneous catalyzed biodiesel generation using cosolvents and their effects. It also suggests that the application of cosolvent in heterogeneously catalyzed three-phase systems substantially reduces the mass transfer limitation between alcohol and oil phases, which leads to enhancements in biodiesel yield along with reductions in values of optimized parameters, with catalyst weight ranges from 1 to 15 wt. %, and alcohol/oil ratio ranges from 5.5 to 20. The reaction time for getting the maximum conversion ranges from 10 to 600 min in the presence of different cosolvents. Alongside this, most of the time, the biodiesel yield remained above 90% in the presence of cosolvents.

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Selvi, E. Thamarai, G. Kavinilavu, and A. Subramani. "Recent Advances Review on Iron Complexes as Catalyst in Oxidation Reactions of Organic Compounds." Asian Journal of Chemistry 34, no. 8 (2022): 1921–38. http://dx.doi.org/10.14233/ajchem.2022.23704.

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The complexes of iron are found to be too reactive and are too diverse in their reactivity, when compared to the other neighbouring metals in the group. Iron complexes are used in various catalytic reactions such as oxygenation of C–H bonds, the oxidation of alcohols to aldehydes, ketones (or) carboxylic acids, the epoxidation or dihydroxylation of alkenes and oxidative coupling reactions. Efforts are taken to avoid certain disadvantages taking place during enzymatic catalysis such as the temperature and solvent sensitivity, narrow substrate scope, restricted accessibility and so on observed while using other catalysts via iron enzymes. This helped in the various synthesis of complex molecules by increase in the number of iron catalyst systems for the oxidation reactions.

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Köhler, Valentin, and Nicholas J. Turner. "Artificial concurrent catalytic processes involving enzymes." Chemical Communications 51, no. 3 (2015): 450–64. http://dx.doi.org/10.1039/c4cc07277d.

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Calderini, Elia, Philipp Süss, Frank Hollmann, Rainer Wardenga, and Anett Schallmey. "Two (Chemo)-Enzymatic Cascades for the Production of Opposite Enantiomers of Chiral Azidoalcohols." Catalysts 11, no. 8 (August 17, 2021): 982. http://dx.doi.org/10.3390/catal11080982.

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Multi-step cascade reactions have gained increasing attention in the biocatalysis field in recent years. In particular, multi-enzymatic cascades can achieve high molecular complexity without workup of reaction intermediates thanks to the enzymes’ intrinsic selectivity; and where enzymes fall short, organo- or metal catalysts can further expand the range of possible synthetic routes. Here, we present two enantiocomplementary (chemo)-enzymatic cascades composed of either a styrene monooxygenase (StyAB) or the Shi epoxidation catalyst for enantioselective alkene epoxidation in the first step, coupled with a halohydrin dehalogenase (HHDH)-catalysed regioselective epoxide ring opening in the second step for the synthesis of chiral aliphatic non-terminal azidoalcohols. Through the controlled formation of two new stereocenters, corresponding azidoalcohol products could be obtained with high regioselectivity and excellent enantioselectivity (99% ee) in the StyAB-HHDH cascade, while product enantiomeric excesses in the Shi-HHDH cascade ranged between 56 and 61%.

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Shteinman, Albert A. "Metallocavitins as Advanced Enzyme Mimics and Promising Chemical Catalysts." Catalysts 13, no. 2 (February 15, 2023): 415. http://dx.doi.org/10.3390/catal13020415.

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The supramolecular approach is becoming increasingly dominant in biomimetics and chemical catalysis due to the expansion of the enzyme active center idea, which now includes binding cavities (hydrophobic pockets), channels and canals for transporting substrates and products. For a long time, the mimetic strategy was mainly focused on the first coordination sphere of the metal ion. Understanding that a highly organized cavity-like enzymatic pocket plays a key role in the sophisticated functionality of enzymes and that the activity and selectivity of natural metalloenzymes are due to the effects of the second coordination sphere, created by the protein framework, opens up new perspectives in biomimetic chemistry and catalysis. There are two main goals of mimicking enzymatic catalysis: (1) scientific curiosity to gain insight into the mysterious nature of enzymes, and (2) practical tasks of mankind: to learn from nature and adopt from its many years of evolutionary experience. Understanding the chemistry within the enzyme nanocavity (confinement effect) requires the use of relatively simple model systems. The performance of the transition metal catalyst increases due to its retention in molecular nanocontainers (cavitins). Given the greater potential of chemical synthesis, it is hoped that these promising bioinspired catalysts will achieve catalytic efficiency and selectivity comparable to and even superior to the creations of nature. Now it is obvious that the cavity structure of molecular nanocontainers and the real possibility of modifying their cavities provide unlimited possibilities for simulating the active centers of metalloenzymes. This review will focus on how chemical reactivity is controlled in a well-defined cavitin nanospace. The author also intends to discuss advanced metal–cavitin catalysts related to the study of the main stages of artificial photosynthesis, including energy transfer and storage, water oxidation and proton reduction, as well as highlight the current challenges of activating small molecules, such as H2O, CO2, N2, O2, H2, and CH4.

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Monkcom, Emily C., Pradip Ghosh, Emma Folkertsma, Hidde A. Negenman, Martin Lutz, and Robertus J. M. Klein Gebbink. "Bioinspired Non-Heme Iron Complexes: The Evolution of Facial N, N, O Ligand Design." CHIMIA International Journal for Chemistry 74, no. 6 (June 24, 2020): 450–66. http://dx.doi.org/10.2533/chimia.2020.450.

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Iron-containing metalloenzymes that contain the 2-His-1-Carboxylate facial triad at their active site are well known for their ability to activate molecular oxygen and catalyse a broad range of oxidative transformations. Many of these reactions are synthetically challenging, and developing small molecular iron-based catalysts that can achieve similar reactivity and selectivity remains a long-standing goal in homogeneous catalysis. This review focuses on the development of bioinspired facial N,N,O ligands that model the 2-His-1-Carboxylate facial triad to a greater degree of structural accuracy than many of the polydentate N-donor ligands commonly used in this field. By developing robust, well-defined N,N,O facial ligands, an increased understanding could be gained of the factors governing enzymatic reactivity and selectivity.

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Timson, David J. "Four Challenges for Better Biocatalysts." Fermentation 5, no. 2 (May 9, 2019): 39. http://dx.doi.org/10.3390/fermentation5020039.

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Biocatalysis (the use of biological molecules or materials to catalyse chemical reactions) has considerable potential. The use of biological molecules as catalysts enables new and more specific syntheses. It also meets many of the core principles of “green chemistry”. While there have been some considerable successes in biocatalysis, the full potential has yet to be realised. This results, partly, from some key challenges in understanding the fundamental biochemistry of enzymes. This review summarises four of these challenges: the need to understand protein folding, the need for a qualitative understanding of the hydrophobic effect, the need to understand and quantify the effects of organic solvents on biomolecules and the need for a deep understanding of enzymatic catalysis. If these challenges were addressed, then the number of successful biocatalysis projects is likely to increase. It would enable accurate prediction of protein structures, and the effects of changes in sequence or solution conditions on these structures. We would be better able to predict how substrates bind and are transformed into products, again leading to better enzyme engineering. Most significantly, it may enable the de novo design of enzymes to catalyse specific reactions.

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Karukurichi, Kannan R., Xiang Fei, Robert A. Swyka, Sylvain Broussy, Weijun Shen, Sangeeta Dey, Sandip K. Roy, and David B. Berkowitz. "Mini-ISES identifies promising carbafructopyranose-based salens for asymmetric catalysis: Tuning ligand shape via the anomeric effect." Science Advances 1, no. 6 (July 2015): e1500066. http://dx.doi.org/10.1126/sciadv.1500066.

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This study introduces new methods of screening for and tuning chiral space and in so doing identifies a promising set of chiral ligands for asymmetric synthesis. The carbafructopyranosyl-1,2-diamine(s) and salens constructed therefrom are particularly compelling. It is shown that by removing the native anomeric effect in this ligand family, one can tune chiral ligand shape and improve chiral bias. This concept is demonstrated by a combination of (i) x-ray crystallographic structure determination, (ii) assessment of catalytic performance, and (iii) consideration of the anomeric effect and its underlying dipolar basis. The title ligands were identified by a new mini version of the in situ enzymatic screening (ISES) procedure through which catalyst-ligand combinations are screened in parallel, and information on relative rate and enantioselectivity is obtained in real time, without the need to quench reactions or draw aliquots. Mini-ISES brings the technique into the nanomole regime (200 to 350 nmol catalyst/20 μl organic volume) commensurate with emerging trends in reaction development/process chemistry. The best-performing β-d-carbafructopyranosyl-1,2-diamine–derived salen ligand discovered here outperforms the best known organometallic and enzymatic catalysts for the hydrolytic kinetic resolution of 3-phenylpropylene oxide, one of several substrates examined for which the ligand is “matched.” This ligand scaffold defines a new swath of chiral space, and anomeric effect tunability defines a new concept in shaping that chiral space. Both this ligand set and the anomeric shape-tuning concept are expected to find broad application, given the value of chiral 1,2-diamines and salens constructed from these in asymmetric catalysis.

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Ansanay, Yane, Praveen Kolar, Ratna Sharma-Shivappa, Jay Cheng, Sunkyu Park, and Consuelo Arellano. "Pre-treatment of biomasses using magnetised sulfonic acid catalysts." Journal of Agricultural Engineering 48, no. 2 (June 1, 2017): 117. http://dx.doi.org/10.4081/jae.2017.594.

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There is a significant interest in employing solid acid catalysts for pre-treatment of biomasses for subsequent hydrolysis into sugars, because solid acid catalysts facilitate reusability, high activity, and easier separation. Hence the present research investigated pretreatment of four lignocellulosic biomasses, namely Switchgrass (Panicum virgatum L ‘Alamo’), Gamagrass (Tripsacum dactyloides), Miscanthus (Miscanthus × giganteus) and Triticale hay (Triticale hexaploide Lart.) at 90°C for 2 h using three carbon-supported sulfonic acid catalysts. The catalysts were synthesized via impregnating p-Toluenesulfonic acid on carbon (regular) and further impregnated with iron nitrate via two methods to obtain magnetic A and magnetic B catalysts. When tested as pre-treatment agents, a maximum total lignin reduction of 17.73±0.63% was observed for Triticale hay treated with magnetic A catalyst. Furthermore, maximum glucose yield after enzymatic hydrolysis was observed to be 203.47±5.09 mg g–1 (conversion of 65.07±1.63%) from Switchgrass treated with magnetic A catalyst. When reusability of magnetised catalysts were tested, it was observed that magnetic A catalyst was consistent for Gamagrass, Miscanthus × Giganteus and Triticale hay, while magnetic B catalyst was found to maintain consistent yield for switchgrass feedstock. Our results suggested that magnetised solid acid catalyst could pre-treat various biomass stocks and also can potentially reduce the use of harsh chemicals and make bioenergy processes environment friendly.

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Crawford, Jennifer, and Matthew Sigman. "Conformational Dynamics in Asymmetric Catalysis: Is Catalyst Flexibility a Design Element?" Synthesis 51, no. 05 (January 8, 2019): 1021–36. http://dx.doi.org/10.1055/s-0037-1611636.

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Traditionally, highly selective low molecular weight catalysts have been designed to contain rigidifying structural elements. As a result, many proposed stereochemical models rely on steric repulsion for explaining the observed selectivity. Recently, as is the case for enzymatic systems, it has become apparent that some flexibility can be beneficial for imparting selectivity. Dynamic catalysts can reorganize to maximize attractive non-covalent interactions that stabilize the favored diastereomeric transition state, while minimizing repulsive non-covalent interactions for enhanced selectivity. This short review discusses catalyst conformational dynamics and how these effects have proven beneficial for a variety of catalyst classes, including tropos ligands, cinchona alkaloids, hydrogen-bond donating catalysts, and peptides.1 Introduction2 Tropos Ligands3 Cinchona Alkaloids4 Hydrogen-Bond Donating Catalysts5 Peptide Catalysts6 Conclusion

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Alissandratos, Apostolos, and Christopher J. Easton. "Biocatalysis for the application of CO2as a chemical feedstock." Beilstein Journal of Organic Chemistry 11 (December 1, 2015): 2370–87. http://dx.doi.org/10.3762/bjoc.11.259.

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Biocatalysts, capable of efficiently transforming CO2into other more reduced forms of carbon, offer sustainable alternatives to current oxidative technologies that rely on diminishing natural fossil-fuel deposits. Enzymes that catalyse CO2fixation steps in carbon assimilation pathways are promising catalysts for the sustainable transformation of this safe and renewable feedstock into central metabolites. These may be further converted into a wide range of fuels and commodity chemicals, through the multitude of known enzymatic reactions. The required reducing equivalents for the net carbon reductions may be drawn from solar energy, electricity or chemical oxidation, and delivered in vitro or through cellular mechanisms, while enzyme catalysis lowers the activation barriers of the CO2transformations to make them more energy efficient. The development of technologies that treat CO2-transforming enzymes and other cellular components as modules that may be assembled into synthetic reaction circuits will facilitate the use of CO2as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy.

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Nikiema, J., and M. Heitz. "Le biodiesel. II. Production — une synthèse." Canadian Journal of Civil Engineering 35, no. 1 (January 2008): 107–17. http://dx.doi.org/10.1139/l07-122.

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Biodiesel is a biofuel obtained from vegetable or animal oils and fats. These are mainly composed of triglycerides but can contain significant amounts of water and free fatty acids, depending on their origin. Biodiesel is generally produced by transesterification, with or without catalyst, by enzymatic interesterification, by microemulsification, or by pyrolysis. Transesterification (with acid, basic, or enzymatic homogeneous or heterogeneous catalysts) is the most frequently used reaction. The operating parameters, including the types and concentrations of alcohol and catalyst, the reaction temperature and duration as well as the agitation intensity, must be optimized for successful application. In general, biodiesel is characterized by a higher viscosity and a lower heating value than those of petrodiesel. To improve these physical properties, petrodiesel or additives can be added to biodiesel.

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Zhang, Shengming, Tiehan Mei, Chonghao Zhu, Huimin Shang, Shushan Gao, Liyuan Qin, and Haitao Chen. "A Combination Method of Liquid Hot Water and Phosphotungstic Acid Pretreatment for Improving the Enzymatic Saccharification Efficiency of Rice Straw." Energies 15, no. 10 (May 16, 2022): 3636. http://dx.doi.org/10.3390/en15103636.

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Chemical pretreatment can significantly improve the enzymatic hydrolysis efficiency of lignocellulosic biomass, thereby improving the yield of sugar materials for the production of cellulosic ethanol, but commonly used acid–base catalysts are difficult to recover and reuse. In this work, a combination method of liquid hot water (LHW) and phosphotungstic acid (PTA) pretreatment was performed to improve the saccharification efficiency of rice straw, and we attempted to evaluate the reuse effect of PTA catalysts. The rice straw was first treated with LHW at 180 °C for 90 min, and then treated with 20 mM PTA at 130 °C for 60 min. After pretreatment, the cellulose hydrolysis efficiency and glucose recovery of the rice straw increased by 201.85% and 164.25%, respectively. Glucose accounted for 96.8% of the total reducing sugar in the final enzymatic hydrolysate. After each PTA pretreatment, approximately 70.8–73.2% of the PTA catalyst could be recycled. Moreover, the catalytic activity of the PTA catalyst that had been used five times did not decrease. The improved enzymatic saccharification efficiency was attributed to the removal of 89.24% hemicellulose and 21.33% lignin from the lignocellulosic substrate. The two-step LHW-PTA pretreatment could pretreat biomass in the field of cellulosic ethanol production.

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Ye, Rong, Tyler J. Hurlburt, Kairat Sabyrov, Selim Alayoglu, and Gabor A. Somorjai. "Molecular catalysis science: Perspective on unifying the fields of catalysis." Proceedings of the National Academy of Sciences 113, no. 19 (April 25, 2016): 5159–66. http://dx.doi.org/10.1073/pnas.1601766113.

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Colloidal chemistry is used to control the size, shape, morphology, and composition of metal nanoparticles. Model catalysts as such are applied to catalytic transformations in the three types of catalysts: heterogeneous, homogeneous, and enzymatic. Real-time dynamics of oxidation state, coordination, and bonding of nanoparticle catalysts are put under the microscope using surface techniques such as sum-frequency generation vibrational spectroscopy and ambient pressure X-ray photoelectron spectroscopy under catalytically relevant conditions. It was demonstrated that catalytic behavior and trends are strongly tied to oxidation state, the coordination number and crystallographic orientation of metal sites, and bonding and orientation of surface adsorbates. It was also found that catalytic performance can be tuned by carefully designing and fabricating catalysts from the bottom up. Homogeneous and heterogeneous catalysts, and likely enzymes, behave similarly at the molecular level. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis.

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Sumaiyah, Selvia Wiliantari, and Karsono. "Preparation and Characterization of Dextrin in Xanthosoma sagittifolium (L.) Schott Starch with Acid Catalyst and Enzymatic Methods." Indonesian Journal of Pharmaceutical and Clinical Research 1, no. 2 (December 31, 2018): 48–54. http://dx.doi.org/10.32734/idjpcr.v1i2.346.

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Abstract. Taro produces carbohydrate. It has the potential as a substitute material for wheat and rice or as diversification into food and raw materials for pharmaceutical industrial. The aim of this study is to prepare and characterize dextrin in Xanthosoma sagittifolium starch with acid catalyst and enzymatic methods. Xanthosoma sagittifolium was mashed and decanted with distilled water. Dextrin was made by acid catalyst method using HCl 1 N and enzymatic method using α-amylase enzyme. Dextrin was characterized and tested according to the Indonesian National Standard (SNI) 01-2593-1992. The results showed that the yield from acid catalyst and enzymatic methods are 41.73 % and 67.10 %, respectively. The color test showed that dextrin from acid catalyst method is yellowish whereas the enzymatic method gives white dextrin. The qualitative test with lugol solution gives brownish purple dextrin. The characteristic of 80 mesh fineness for dextrin fabricated by acid and enzymatic methods are 94.7 % ± 0.06 and 93.96 % ± 0.02 respectively. Dextrin obtained from acid catalyst has higher water content (8.79 % ± 0.15) than dextrin from enzymatic methods (7.62 % ± 0.23) as well as dextrin from acid catalyst has higher the ash content (0.45 % ± 0.02) than dextrin from enzymatic method (0.42 % ± 0.04). Dextrin made from enzymatic method has higher solubility in cold water (63.09 % + 0.1) than dextrin from acid catalyst method (57.47 % ± 0.25). Dextrose equivalent for dextrin produced is 13.65 ± 0.36 and 15.31 ± 0.46 for acid catalyst and enzymatic methods. Melting points for dextrin obtained from acid catalyst and enzymatic methods are 185 oC ± 0.57 and 182 cC ± 0.57 respectively. Acidity degree of dextrin fabricated from acid catalyst and enzymatic methods are 2.86 ± 0.23 and 4.39 ± 0.4. The research shows that the characterization of dextrin by acid catalyst and enzymatic methods meet the quality requirements for Indonesia National Standard (SNI) 01-2593-1992. Key words: Taro, dextrin, acid catalyst method, enzymatic method

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Kelaiya, S. V., P. M. Chauhan, and S. H. Akbari. "Fuel Property of Biodiesel Made from Microalgae (Chlorella Sp.)." Current World Environment 10, no. 3 (December 25, 2015): 912–19. http://dx.doi.org/10.12944/cwe.10.3.21.

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Microalgae chlorella is an organism capable of photosynthesis that is less than 2mm in diameter. The biodiesel extracted from algae using chloroform/methanol extraction solvent system then undergone three different transesterification processes based on three different catalysts viz. Alkali catalyst, Acid catalyst and Enzymatic catalyst with two temperature (50°C and 60 °C) and with 1:5 methanol to bio-oil ratio. After transesterification using different catalysts, the fuel properties were measured. All the properties were compared with standard value of ASTM D 6751 standards. Alkali catalyst yield highest biodiesel (92 %) at 60 °C temperature. Also, the closest value of different fuel properties found at par with standard value of ASTM D 6751 standards viz. moisture content, carbon residue, calorific value, specific gravity, acid value, flash point, viscosity, density, viscosity were found to be 0.01%, 0.04%, 40.41 MJ/kg, 0.83, 0.23 mg KOH/g, 143.67 °C, 5.16 mm2/s, 0.83 g/cm3 respectively in the biodiesel which was yield by transesterification done using Alkali catalyst (0.56 % NaOH) at 60 °C temperature.

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Ramos, Maria J., and Pedro A. Fernandes. "Computational Enzymatic Catalysis." Accounts of Chemical Research 41, no. 6 (June 2008): 689–98. http://dx.doi.org/10.1021/ar7001045.

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Bilaničová, D., V. Mastihuba, M. Mastihubová, J. Bálešová, and Š. Schmidt. "Improvements in enzymatic preparation of alkyl glycosides." Czech Journal of Food Sciences 28, No. 1 (February 18, 2010): 69–73. http://dx.doi.org/10.17221/188/2008-cjfs.

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Three glycosides of middle chain aliphatic alcohols (hexanol and heptanol) were prepared by enzymatic glycosidation. The preparation of hexyl β-D-glucopyranoside was achieved in moderate yields via reverse hydrolysis catalysed by defatted meals from almond, apricot, and peach kernels. The apricot meal as a cheap source of β-glucosidase was found to have catalytic efficiency resembling to that of the almond meal. Hexyl and heptyl β-D-galactopyranosides were prepared from D-lactose by transgalactosidation catalysed by commercial β-galactosidases from <I>Aspergillus oryzae</I> in two-phase system. The improvement of the product yields was achieved by a simple replacement of the organic phase (serving as a pool of acceptor alcohol and extracted product) with a fresh portion of the acceptor.

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Ralser, Markus. "The RNA world and the origin of metabolic enzymes." Biochemical Society Transactions 42, no. 4 (August 1, 2014): 985–88. http://dx.doi.org/10.1042/bst20140132.

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An RNA world has been placed centre stage for explaining the origin of life. Indeed, RNA is the most plausible molecule able to form both a (self)-replicator and to inherit information, necessities for initiating genetics. However, in parallel with self-replication, the proto-organism had to obtain the ability to catalyse supply of its chemical constituents, including the ribonucleotide metabolites required to replicate RNA. Although the possibility of an RNA-catalysed metabolic network has been considered, it is to be questioned whether RNA molecules, at least on their own, possess the required catalytic capacities. An alternative scenario for the origin of metabolism involves chemical reactions that are based on environmental catalysts. Recently, we described a non-enzymatic glycolysis and pentose phosphate pathway-like reactions catalysed by metal ions [mainly Fe(II)] and phosphate, simple inorganic molecules abundantly found in Archaean sediments. While the RNA world can serve to explain the origin of genetics, the origin of the metabolic network might thus date back to constraints of environmental chemistry. Interestingly, considering a metal-catalysed origin of metabolism gives rise to an attractive hypothesis about how the first enzymes could have formed: simple RNA or (poly)peptide molecules could have bound the metal ions, and thus increased their solubility, concentration and accessibility. In a second step, this would have allowed substrate specificity to evolve.

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Heba, Monika, Anna Wolny, Anna Kastelik-Hryniewiecka, Dominika Stradomska, Sebastian Jurczyk, Anna Chrobok, and Nikodem Kuźnik. "Green Dynamic Kinetic Resolution—Stereoselective Acylation of Secondary Alcohols by Enzyme-Assisted Ruthenium Complexes." Catalysts 12, no. 11 (November 9, 2022): 1395. http://dx.doi.org/10.3390/catal12111395.

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Dynamic kinetic resolution allows for the synthesis of enantiomerically pure asymmetric alcohols. Cyclopentadienyl-derived ruthenium catalysts were immobilized with an ionic liquid, [BMIM][NTf2], on multiwall carbon nanotubes and used for the racemization of chiral secondary alcohols. This successful approach was combined with the enantioselective enzymatic acylation of secondary alcohols (1-phenylethanol and 1-(1-naphthyl)ethanol) using Novozyme® 435. The resulting catalytic system of the ruthenium racemization catalysts and enzymatic acylation led to chiral esters being obtained by dynamic kinetic resolution. The immobilized catalytic system in the ionic liquid gave the same activity of >96% yield within 6 h and a selectivity of 99% enantiomeric excess as the homogeneous system, while allowing for the convenient separation of the desired products from the catalyst. Additionally, the process can be regarded as green, since the efficient reuse of the catalytic system was demonstrated.

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Matienko, L. I., V. I. Binyukov, E. M. Mil, and G. E. Zaikov. "Supramolecular Macrostructures in the Mechanisms of Catalysis with Nickel or Iron Heteroligand Complexes." Current Organocatalysis 6, no. 1 (April 24, 2019): 36–43. http://dx.doi.org/10.2174/2213337206666181231120410.

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Background: The AFM-techniques have been used for the research of the role of intermolecular H-bonds and stable supramolecular nanostructures, based on effective catalysts of oxidation processes, which are also models of Ni(Fe)ARD Dioxygenases, in mechanisms of catalysis. Methods and Results: The role of Histidine and Tyrosine ligands in the mechanisms of catalysis by FeARD on model systems is discussed based on AFM and UV-Spectroscopy data. Conclusion: We first offer the new approach – method of atomic force microscopy (AFM) – to study the possibility of the formation of supramolecular nanostructures, and also for assessing of role the intermolecular hydrogen bonds (and the other intermolecular non-covalent interactions) in mechanisms of homogeneous and enzymatic catalysis with nickel and iron complexes.

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Pu, Shujin, Xuan Zhang, Han Huang, Chengli Yang, Dali Li, Junfang Yang, Jie Ouyang, Xing Chen, Sidra Naseer, and Ruofu Shi. "A System of Photocatalysis for NAD+ Regeneration of Product of (S)-1-Pheylethanol by Enzymic Catalysis." Bulletin of Chemical Reaction Engineering & Catalysis 14, no. 2 (August 1, 2019): 421. http://dx.doi.org/10.9767/bcrec.14.2.3930.421-426.

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In this study, a system of photocatalysis for NAD+ regeneration of enzymatic catalysis was constructed. The optimal conditions for the coupling reaction of photocatalysis and biocatalysis were explored. Blue light was chosen for the efficient reaction and the optimal concentration of VB2 (vitamin B2, riboflavin) was determined. NAD+-dependent (R)-1-phenylethanol dehydrogenase was used in the reaction for transforming (R)-1-phenylethanol to acetophenone. The byproducts of the reaction were just H2O and O2 by means of catalase. The coupling reaction of catalysis and photocatalysis can be used for obtaining (S)-1-phenylethanol through racemization of 1-phenylethanol. Copyright © 2019 BCREC Group. All rights reserved

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Yusuff, A. S., O. D. Adeniyi, M. A. Olutoye, and U. G. Akpan. "A Review on Application of Heterogeneous Catalyst in the Production of Biodiesel from Vegetable Oils." Journal of Applied Science & Process Engineering 4, no. 2 (October 3, 2017): 142–57. http://dx.doi.org/10.33736/jaspe.432.2017.

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Biodiesel has been considered as one of the interesting alternative and environmentally benign fuels. The development of environmental friendly heterogeneous catalyst for the esterification/transesterification process seems to be promising route and the reason why it is more preferred to conventional homogeneous and enzymatic catalyzed reactions is discussed. However, investigation on heterogeneous catalyst for biodiesel production is extensively carried out based on previous research studies. In order to reduce cost of biodiesel production, evaluation and characterization of heterogeneous catalytic materials before and after its preparation provide facts on the process that have significant impact on the desired activity and selectivity properties. This review study provides a comprehensive overview of common process techniques usually employ in producing biodiesel. Different materials that serve as sources of heterogeneous catalysts to transesterify oils or fats for production of biodiesel with emphasis on selection criteria of solid catalytic materials are also highlighted. The potential heterogeneous catalyst that could be derived from anthill, various methods of preparing solid catalysts, as well as reusability and leaching analysis are discussed in details

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Ao, Supongsenla, and Samuel Lalthazuala Rokhum. "Recent Advances in the Valorization of Biodiesel By-Product Glycerol to Solketal." Journal of Chemistry 2022 (May 31, 2022): 1–18. http://dx.doi.org/10.1155/2022/4938672.

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The exponential rise of the biodiesel production has resulted in a considerable amount of glycerol as a by-product, which must be valorized to ensure the sector’s long-term viability. As a result, cost-effective glycerol conversions for significant value-added chemicals are essential for the biodiesel production in the long run. Solketal, a glycerol by-product, is obtained as a potential fuel additive in the biodiesel industry. Recently, several heterogeneous acid-catalysts stand out as a promising catalyst for solketal production where biomass-based catalyst gained attraction owing to their biodegradability, eco-friendly, and abundant availability. Furthermore, magnetic nanoparticles-derived catalysts along with sulfonated functionalized catalyzed, zeolites, resins, enzymatic, etc. have proved their efficiency in solketal production. In this review, a wider study on the recent advances of the catalysts has been discussed along with their preparation, various reaction parameters, its application, and efficiency for biodiesel industry. This study opens up incredible prospects for us to use renewable energy sources, which will benefit the industry, the environment, and the economy.

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Gadda, Giovanni. "Cofactor assisted enzymatic catalysis." Archives of Biochemistry and Biophysics 544 (February 2014): 1. http://dx.doi.org/10.1016/j.abb.2014.01.012.

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Gimbernat, Alexandra, Marie Guehl, Nicolas Lopes Ferreira, Egon Heuson, Pascal Dhulster, Mickael Capron, Franck Dumeignil, Damien Delcroix, Jean Girardon, and Rénato Froidevaux. "From a Sequential Chemo-Enzymatic Approach to a Continuous Process for HMF Production from Glucose." Catalysts 8, no. 8 (August 17, 2018): 335. http://dx.doi.org/10.3390/catal8080335.

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Notably available from the cellulose contained in lignocellulosic biomass, glucose is a highly attractive substrate for eco-efficient processes towards high-value chemicals. A recent strategy for biomass valorization consists on combining biocatalysis and chemocatalysis to realise the so-called chemo-enzymatic or hybrid catalysis. Optimisation of the glucose conversion to 5-hydroxymethylfurfural (HMF) is the object of many research efforts. HMF can be produced by chemo-catalyzed fructose dehydration, while fructose can be selectively obtained from enzymatic glucose isomerization. Despite recent advances in HMF production, a fully integrated efficient process remains to be demonstrated. Our innovative approach consists on a continuous process involving enzymatic glucose isomerization, selective arylboronic-acid mediated fructose complexation/transportation, and chemical fructose dehydration to HMF. We designed a novel reactor based on two aqueous phases dynamically connected via an organic liquid membrane, which enabled substantial enhancement of glucose conversion (70%) while avoiding intermediate separation steps. Furthermore, in the as-combined steps, the use of an immobilized glucose isomerase and an acidic resin facilitates catalyst recycling.

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Anggoro, Didi Dwi, and Kamsi Nur Oktavia. "The Potential of Cellulose as a Source of Bioethanol using the Solid Catalyst: A Mini-Review." Bulletin of Chemical Reaction Engineering & Catalysis 16, no. 3 (July 6, 2021): 661–72. http://dx.doi.org/10.9767/bcrec.16.3.10635.661-672.

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One of the most important biofuels is cellulose ethanol which is a popular material for bioethanol production. The present cellulosic ethanol production is through the cellulolytic process and this involves the splitting of complex cellulose into simple sugars through the hydrolysis process of the lignocellulose pretreated with acids and enzymes after which the product is fermented and distilled. There are, however, some challenges due to the enzymatic and acid processes based on the fact that acid hydrolysis has the ability to corrode equipment and cause unwanted waste while the enzymatic hydrolysis process requires a longer time because enzymes are costly and limited. This means there is a need for innovations to minimize the problems associated with these two processes and this led to the application of solid catalysts as the green and effective catalyst to convert cellulose to ethanol. Solid catalysts are resistant to acid and base conditions, have a high surface area, and do not cause corrosion during the conversion of the cellulose due to their neutral pH. This review, therefore, includes the determination of the cellulose potential as feedstock to be used in ethanol production as well as the preparation and application of solid catalyst as the mechanism to convert cellulose into fuel and chemicals. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

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Khan, Haris Mahmood, Tanveer Iqbal, M. A. Mujtaba, Manzoore Elahi M. Soudagar, Ibham Veza, and I. M. Rizwanul Fattah. "Microwave Assisted Biodiesel Production Using Heterogeneous Catalysts." Energies 14, no. 23 (December 4, 2021): 8135. http://dx.doi.org/10.3390/en14238135.

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As a promising renewable fuel, biodiesel has gained worldwide attention to replace fossil-derived mineral diesel due to the threats concerning the depletion of fossil reserves and ecological constraints. Biodiesel production via transesterification involves using homogeneous, heterogeneous and enzymatic catalysts to speed up the reaction. The usage of heterogeneous catalysts over homogeneous catalysts are considered more advantageous and cost-effective. Therefore, several heterogeneous catalysts have been developed from variable sources to make the overall production process economical. After achieving optimum performance of these catalysts and chemical processes, the research has been directed in other perspectives, such as the application of non-conventional methods such as microwave, ultrasonic, plasma heating etc, aiming to enhance the efficiency of the overall process. This mini review is targeted to focus on the research carried out up to this date on microwave-supported heterogeneously catalysed biodiesel production. It discusses the phenomenon of microwave heating, synthesis techniques for heterogeneous catalysts, microwave mediated transesterification reaction using solid catalysts, special thermal effects of microwaves and parametric optimisation under microwave heating. The review shows that using microwave technology on the heterogeneously catalysed transesterification process greatly decreases reaction times (5–60 min) while maintaining or improving catalytic activity (>90%) when compared to traditional heating.

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WILLIAMS, G. S. BLAIR, AFTAB M. HOSSAIN, SHIYING SHANG, DAVID E. KRANBUEHL, and CAREY K. BAGDASSARIAN. "EVOLUTION OF A CATALYTICALLY EFFECTIVE MODEL ENZYME: THE IMPORTANCE OF TUNED CONFORMATIONAL FLUCTUATIONS." Journal of Theoretical and Computational Chemistry 02, no. 03 (September 2003): 323–34. http://dx.doi.org/10.1142/s0219633603000586.

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Possible causal connections between the dynamics of a thermally fluctuating model enzyme molecule and catalysis are explored. The model is motivated by observations from experiment and simulation that amino acid residues residing in different enzymatic domains may show markedly different degrees of conformational freedom. Consequently, we are interested in the catalytic efficacy of an enzyme as a function of long-range many-atom cooperative effects resulting from strong, moderate, and weak interactions between enzymatic residues. Here we show and quantify through molecular dynamics simulations how the number and distribution of these interactions affects an enzyme's conformational fluctuation dynamics and its effectiveness as a catalyst. For any given distribution of "stiff" and "loose" enzymatic domains, catalytic fitness is defined as the number of chemical events — specifically the number of times a catalytic residue and substrate surmount a chemical reaction barrier — during molecular dynamics simulation. Through mutation, recombination, and a selection procedure following the ideas of Darwinian evolution, a genetic algorithm drives a population of enzyme molecules to greater catalytic fitness by modifying the mix of stiff and loose interactions. Approximately 30,000 different enzyme molecules are generated by the genetic algorithm — each with a unique number and distribution of strong, moderate, and weak inter-residue interactions. While the catalytically least fit enzyme exhibits 16 chemical events, the fittest boasts 253. That point mutations far from the active-site chemistry in the fittest enzyme have a strong effect on the number of chemical events suggests that catalysis depends, in part, on long-range many-atom globally correlated dynamical fluctuations.

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Brun, Nicolas, Hervé Deleuze, and Rénal Backov. "Enzyme-based Biohybrid Foams Designed for Biodiesel Production and Continuous Flow Heterogeneous Catalysis." MRS Proceedings 1492 (2013): 183–88. http://dx.doi.org/10.1557/opl.2013.371.

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ABSTRACTThe one pot-synthesis and use of monolithic biohybrid foams in a continuous flow device reported inhere presents the advantages of covalent stabilization of the enzymes, together with a low steric hindrance between proteins and substrates, an optimized mass transport due to the interconnected macroporous network and a rather simplicity in regard of the column in-situ synthetic path. Those features, concerning transesterification (biodiesel production) enzyme- based catalyzed reaction, provide high enzymatic activity addressed with bio-hybrid catalysts bearing unprecedented endurance of continuous catalysis for a two months period of time.

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Krakor, Eva, Isabel Gessner, Michael Wilhelm, Veronika Brune, Johannes Hohnsen, Lars Frenzen, and Sanjay Mathur. "Selective degradation of synthetic polymers through enzymes immobilized on nanocarriers." MRS Communications 11, no. 3 (April 26, 2021): 363–71. http://dx.doi.org/10.1557/s43579-021-00039-7.

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Abstract In order to develop new sustainable and reusable concepts for the degradation of omnipresent industrial plastics, immobilization of (bio)catalysts on nanocarriers offers unique opportunities for selective depolymerization and catalyst recovery. In this study, enzymes (lipase and cutinase) were covalently immobilized on carrier nanoparticles (SiO2 and Fe3O4@SiO2) through 3-(aminopropyl)trimethoxysilane and glutaraldehyde linkers forming a stable bond to enzyme molecules. The presence of enzymes on the surface was confirmed by zeta potential and XPS measurements, while their degradation activity and long-term stability of up to 144 h was demonstrated by the conversion of 4-nitrophenyl acetate to 4-nitrophenol. Furthermore, enzymatic decomposition (hydrolysis/oxidation) of electrospun polycaprolactone fiber mats was verified through morphological (SEM) and weight loss studies, which evidently showed a change in the fiber morphology due to enzymatic degradation and accordingly a weight loss. Graphic abstract

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34

Keller, Markus A., Andre Zylstra, Cecilia Castro, Alexandra V. Turchyn, Julian L. Griffin, and Markus Ralser. "Conditional iron and pH-dependent activity of a non-enzymatic glycolysis and pentose phosphate pathway." Science Advances 2, no. 1 (January 2016): e1501235. http://dx.doi.org/10.1126/sciadv.1501235.

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Little is known about the evolutionary origins of metabolism. However, key biochemical reactions of glycolysis and the pentose phosphate pathway (PPP), ancient metabolic pathways central to the metabolic network, have non-enzymatic pendants that occur in a prebiotically plausible reaction milieu reconstituted to contain Archean sediment metal components. These non-enzymatic reactions could have given rise to the origin of glycolysis and the PPP during early evolution. Using nuclear magnetic resonance spectroscopy and high-content metabolomics that allowed us to measure several thousand reaction mixtures, we experimentally address the chemical logic of a metabolism-like network constituted from these non-enzymatic reactions. Fe(II), the dominant transition metal component of Archean oceanic sediments, has binding affinity toward metabolic sugar phosphates and drives metabolism-like reactivity acting as both catalyst and cosubstrate. Iron and pH dependencies determine a metabolism-like network topology and comediate reaction rates over several orders of magnitude so that the network adopts conditional activity. Alkaline pH triggered the activity of the non-enzymatic PPP pendant, whereas gentle acidic or neutral conditions favored non-enzymatic glycolytic reactions. Fe(II)-sensitive glycolytic and PPP-like reactions thus form a chemical network mimicking structural features of extant carbon metabolism, including topology, pH dependency, and conditional reactivity. Chemical networks that obtain structure and catalysis on the basis of transition metals found in Archean sediments are hence plausible direct precursors of cellular metabolic networks.

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35

Fiore, Michele, and René Buchet. "Symmetry Breaking of Phospholipids." Symmetry 12, no. 9 (September 10, 2020): 1488. http://dx.doi.org/10.3390/sym12091488.

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Either stereo reactants or stereo catalysis from achiral or chiral molecules are a prerequisite to obtain pure enantiomeric lipid derivatives. We reviewed a few plausibly organic syntheses of phospholipids under prebiotic conditions with special attention paid to the starting materials as pro-chiral dihydroxyacetone and dihydroxyacetone phosphate (DHAP), which are the key molecules to break symmetry in phospholipids. The advantages of homochiral membranes compared to those of heterochiral membranes were analysed in terms of specific recognition, optimal functions of enzymes, membrane fluidity and topological packing. All biological membranes contain enantiomerically pure lipids in modern bacteria, eukarya and archaea. The contemporary archaea, comprising of methanogens, halobacteria and thermoacidophiles, are living under extreme conditions reminiscent of primitive environment and may indicate the origin of one ancient evolution path of lipid biosynthesis. The analysis of the known lipid metabolism reveals that all modern cells including archaea synthetize enantiomerically pure lipid precursors from prochiral DHAP. Sn-glycerol-1-phosphate dehydrogenase (G1PDH), usually found in archaea, catalyses the formation of sn-glycerol-1-phosphate (G1P), while sn-glycerol-3-phosphate dehydrogenase (G3PDH) catalyses the formation of sn-glycerol-3-phosphate (G3P) in bacteria and eukarya. The selective enzymatic activity seems to be the main strategy that evolution retained to obtain enantiomerically pure lipids. The occurrence of two genes encoding for G1PDH and G3PDH served to build up an evolutionary tree being the basis of our hypothesis article focusing on the evolution of these two genes. Gene encoding for G3PDH in eukarya may originate from G3PDH gene found in rare archaea indicating that archaea appeared earlier in the evolutionary tree than eukarya. Archaea and bacteria evolved probably separately, due to their distinct respective genes coding for G1PDH and G3PDH. We propose that prochiral DHAP is an essential molecule since it provides a convergent link between G1DPH and G3PDH. The synthesis of enantiopure phospholipids from DHAP appeared probably firstly in the presence of chemical catalysts, before being catalysed by enzymes which were the products of later Darwinian selection. The enzymes were probably selected for their efficient catalytic activities during evolution from large libraries of vesicles containing amino acids, carbohydrates, nucleic acids, lipids, and meteorite components that induced symmetry imbalance.

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ZHAO, Yuan, and Ze-Xing CAO. "Global Simulations of Enzymatic Catalysis." Acta Physico-Chimica Sinica 33, no. 4 (2017): 691–708. http://dx.doi.org/10.3866/pku.whxb201612191.

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37

Wilberg, K. Q., T. L. M. Alves, and R. Nobrega. "ENZYMATIC CATALYSIS BY PERMEABILIZED CELLS." Brazilian Journal of Chemical Engineering 14, no. 4 (December 1997): 347–52. http://dx.doi.org/10.1590/s0104-66321997000400008.

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38

Frey, Perry A. "Radical Mechanisms of Enzymatic Catalysis." Annual Review of Biochemistry 70, no. 1 (June 2001): 121–48. http://dx.doi.org/10.1146/annurev.biochem.70.1.121.

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Buckel, Wolfgang. "Highlight: Radicals in Enzymatic Catalysis." Biological Chemistry 386, no. 10 (October 1, 2005): 949–50. http://dx.doi.org/10.1515/bc.2005.110.

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TORAYA, Tetsuo. "Radical Catalysis in Enzymatic Reactions." Kagaku To Seibutsu 33, no. 4 (1995): 224–33. http://dx.doi.org/10.1271/kagakutoseibutsu1962.33.224.

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Young, Douglas D., Jason Nichols, Robert M. Kelly, and Alexander Deiters. "Microwave Activation of Enzymatic Catalysis." Journal of the American Chemical Society 130, no. 31 (August 2008): 10048–49. http://dx.doi.org/10.1021/ja802404g.

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42

Oyama, S. Ted, and Gabor A. Somorjai. "Homogeneous, heterogeneous, and enzymatic catalysis." Journal of Chemical Education 65, no. 9 (September 1988): 765. http://dx.doi.org/10.1021/ed065p765.

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Hansen, David E., and Ronald T. Raines. "Binding energy and enzymatic catalysis." Journal of Chemical Education 67, no. 6 (June 1990): 483. http://dx.doi.org/10.1021/ed067p483.

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Schramm, Vern L. "Introduction: Principles of Enzymatic Catalysis." Chemical Reviews 106, no. 8 (August 2006): 3029–30. http://dx.doi.org/10.1021/cr050246s.

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Zaks, A., and A. M. Klibanov. "Enzymatic catalysis in nonaqueous solvents." Journal of Biological Chemistry 263, no. 7 (March 1988): 3194–201. http://dx.doi.org/10.1016/s0021-9258(18)69054-4.

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Deschl, U., and U. Bach. "Enzymatic catalysis in toxicologic pathology." Applied Catalysis A: General 221, no. 1-2 (November 2001): 159–69. http://dx.doi.org/10.1016/s0926-860x(01)00806-7.

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Kadokawa, Jun-ichi, and Shiro Kobayashi. "Polymer synthesis by enzymatic catalysis." Current Opinion in Chemical Biology 14, no. 2 (April 2010): 145–53. http://dx.doi.org/10.1016/j.cbpa.2009.11.020.

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48

Juais, Danielle, Alliny F. Naves, Chong Li, Richard A. Gross, and Luiz H. Catalani. "Isosorbide Polyesters from Enzymatic Catalysis." Macromolecules 43, no. 24 (December 28, 2010): 10315–19. http://dx.doi.org/10.1021/ma1013176.

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Yuzbasheva, E. Yu, P. M. Gotovtsev, E. B. Mostova, N. I. Perkovskaya, M. A. Lomonosova, V. V. Butylin, S. P. Sineokii, and R. G. Vasilov. "Biodiesel production via enzymatic catalysis." Applied Biochemistry and Microbiology 50, no. 8 (November 4, 2014): 737–49. http://dx.doi.org/10.1134/s0003683814080067.

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Noiva, R. "Enzymatic Catalysis of Disulfide Formation." Protein Expression and Purification 5, no. 1 (February 1994): 1–13. http://dx.doi.org/10.1006/prep.1994.1001.

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Journal articles on the topic 'Enzymatic catalysi'

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