Search Results (69)

Background/Objectives: As an essential polyunsaturated fatty acid, linoleic acid (LA) plays an important role in maintaining the integrity of cellular membranes, modulating inflammatory responses, and mediating intracellular signaling. This review explores the structure, properties, and nutritional significance of LA and its bioactive derivatives, with particular attention to sustainable production methods and their potential applications. Methods: A comprehensive review of the recent literature was conducted, emphasizing the use of green synthesis techniques, such as enzyme-catalyzed biocatalysis and microbiological transformations, in order to obtain LA-derived nutraceuticals. Analyses were conducted on the key aspects related to food industry applications, regulatory frameworks, and emerging market trends. Results: Through green synthesis strategies, LA derivatives with antioxidant, anti-inflammatory, and antimicrobial properties have been developed. There is potential for these compounds to be incorporated into health-oriented food products. In spite of this, challenges remain regarding their stability and bioavailability. Furthermore, there are inconsistencies in international regulatory standards which prevent these compounds from being widely adopted. Conclusions: The development of functional and sustainable food products based on linoleic acid derivatives obtained using ecological methods offers significant potential. Research is required to optimize production processes, enhance compound stability, and clinically validate health effects. The integration of the market and the safety of consumers will be supported by addressing regulatory harmonization. Full article

Spirocyclic architectures, which feature two rings sharing a single atom, are common in natural products and exhibit beneficial biological and material properties. Due to the significance of these architectures, biocatalytic dearomative spirocyclization has recently emerged as a powerful approach for constructing three-dimensional spirocyclic frameworks under mild, sustainable conditions and with exquisite stereocontrol. This review surveys the latest advances in biocatalyzed spirocyclization of all-carbon arenes (phenols and benzenes), aza-aromatics (indoles and pyrroles), and oxa-aromatics (furans). We highlight cytochrome P450s, flavin-dependent monooxygenases, multicopper oxidases, and novel metalloenzyme platforms that effect regio- and stereoselective oxidative coupling, epoxidation/semi-pinacol rearrangement, and radical-mediated cyclization to produce diverse spirocycles. Mechanistic insights gleaned from structural, computational, and isotope-labeling studies are discussed where necessary to help the readers further understand the reported reactions. Collectively, these examples demonstrate the transformative potential of biocatalysis to streamline access to spirocyclic scaffolds that are challenging to prepare through traditional methods, underscoring biocatalysis as a transformative tool for synthesizing pharmaceutically relevant spiroscaffolds while adhering to green chemistry paradigms to ultimately contribute to a cleaner and more sustainable future. Full article

Natural compounds with significant bioactive properties can be found in abundance within biomasses. Especially prominent for their anti-inflammatory, neuroprotective, antibacterial, and antioxidant activities are cinnamic acid derivatives (CAs). Ferulic acid (FA), a widely studied phenylpropanoid, exhibits a broad range of therapeutic and nutraceutical applications, demonstrating antidiabetic, anticancer, antimicrobial, and hepato- and neuroprotective activities. This research investigates the green enzymatic synthesis of innovative and potentially bifunctional prodrug derivatives of FA, designed to enhance solubility and stability profiles. Selective esterification was employed to conjugate FA with xylitol, a biobased polyol recognized for its bioactive antioxidant properties and safety profile. Furthermore, by exploiting t-amyl alcohol as a green solvent, the enzymatic synthesis of the derivative was optimized for reaction parameters including temperature, reaction time, enzyme concentration, and molar ratio. The synthesized derivative, xylitol monoferulate (XMF), represents a novel contribution to the literature. The comprehensive characterization of this compound was achieved using advanced spectroscopic methods, including ¹H-NMR, ¹³C-NMR, COSY, HSQC, and HMBC. This study represents a significant advancement in the enzymatic synthesis of high-value biobased derivatives, demonstrating increased biological activities and setting the stage for future applications in green chemistry and the sustainable production of bioactive compounds. Full article

Enzyme immobilization plays a critical role in enhancing the efficiency and sustainability of biocatalysis, addressing key challenges such as limited enzyme stability, short shelf life, and difficulties in recovery and recycling, which are pivotal for green chemistry and industrial applications. Classical approaches, including adsorption, entrapment, encapsulation, and covalent bonding, as well as advanced site-specific methods that integrate enzyme engineering and bio-orthogonal chemistry, were discussed. These techniques enable precise control over enzyme orientation and interaction with carriers, optimizing catalytic activity and reusability. Key findings highlight the impact of immobilization on improving enzyme performance under various operational conditions and its role in reducing process costs through enhanced stability and recyclability. The review presents numerous practical applications of immobilized enzymes, including their use in the pharmaceutical industry for drug synthesis, in the food sector for dairy processing, and in environmental biotechnology for wastewater treatment and dye degradation. Despite the significant advantages, challenges such as activity loss due to conformational changes and mass transfer limitations remain, necessitating tailored immobilization protocols for specific applications. The integration of immobilization with modern biotechnological advancements, such as site-directed mutagenesis and recombinant DNA technology, offers a promising pathway for developing robust, efficient, and sustainable biocatalytic systems. This comprehensive guide aims to support researchers and industries in selecting and optimizing immobilization techniques for diverse applications in pharmaceuticals, food processing, and fine chemicals. Full article

Caffeic acid phenethyl ester (CAPE) represents a valuable ester of caffeic acid, which, over time, has demonstrated remarkable pharmacological properties. In general, the ester is obtained in organic solvents, especially by the esterification reaction of caffeic acid (CA) and 2-phenylethanol (PE). In this context, the purpose of this study was the use of the “one pot” system to synthesize CAPE through biocatalysis with various lipases in a choline-chloride-based DES system, employing the “2-in-1” concept, where one of the substrates functions as both reactant and solvent. The synthesis process of CAPE is contingent on the molar ratio between CA and PE; thus, this factor was the primary subject of investigation, with different molar ratios of CA and PE being studied. Furthermore, the impact of temperature, time, the nature of the biocatalyst, and the water loading of the DES system was also examined. This ‘green’ synthesis method, which has demonstrated encouraging reaction yields (%), could secure and maintain the therapeutic potential of CAPE, mainly due to the non-toxic character of the reaction medium. Full article

The value of branched esters comes from the special properties they have in cold environments, which allow them to remain liquid over a wide range of temperatures. These properties make them useful for application in the cosmetic industry or as lubricant additives. This paper presents the studies carried out to ascertain the operational feasibility of the enzymatic esterification of 2-methylpentanoic acid (MPA) with 1,10-decanediol (DD), with the objective of obtaining a novel molecule: decane-1,10-diyl bis(2-methylpentanoate) (DDBMP). The enzymatic reaction is conducted in a thermostated batch reactor, utilizing the commercially available immobilized lipase Lipozyme^® 435 in a solvent-free medium. The reaction conversion is determined by an acid number determination and a gas chromatographic analysis. The most optimal result is achieved at a temperature of 80 °C, a biocatalyst concentration of 2.5% (w/w), and a non-stoichiometric substrate relation. A preliminary economic study and the calculation of Green Metrics has established that the operation with a 30% molar excess of acid is the best option to obtain a product with 92.6% purity at a lower cost than the other options and in accordance with the 12 Principles of Green Chemistry. The synthetized diester has a viscosity index of 210, indicating that this new molecule can be used as a biolubricant at extreme temperatures. Full article

Enzyme catalysis was traditionally used by various human cultures to create value long before its basic concepts were uncovered. This was achieved by transforming the raw materials available from natural resources into useful products. Tremendous scientific and technological progress has been made globally in understanding what constitutes an enzyme; what reactions enzymes can catalyze; and how to search, develop, apply, and improve enzymes to make desired products. The useful properties of enzymes as nature’s preferred catalysts, such as their high selectivity, diversity, and adaptability, enable their optimal function, whether in single or multiple reactions. Excellent opportunities for the resource-efficient manufacturing of compounds are provided by the actions of enzymes working in reaction cascades and pathways within the same reaction space, like molecular robots along a production line. Enzyme catalysis plays an increasingly prominent role in industrial innovation and responsible production in various areas, such as green and sustainable chemistry and industrial or white biotechnology. Sources of inspiration include current manufacturing or supply chain challenges, the treasure of natural enzymes, and opportunities to engineer tailor-made enzymes. Making the best use of the power of enzyme catalysis is essential for changing how current products are manufactured; how renewable biobased resources can replace fossil-based resources; and improving the safety, health, and environmental aspects of manufacturing processes to support cleaner and more sustainable production. Full article

Biocatalysis is a green and sustainable technology based on the use of natural substances to catalyze chemical reactions. Humans have been unconsciously using biocatalysis for thousands of years to produce food and alcoholic beverages, but it is only since the 19th century that we have begun to understand its fundamentals and its enormous potential. In fact, advances in our knowledge of enzymes and metabolic pathways and, in recent decades, the introduction of tools such as bioinformatics, DNA sequencing and protein engineering have made biocatalysis a key strategy in fine chemistry and for the production of active pharmaceutical ingredients. In addition, the discovery of new microorganisms adapted to adverse conditions has also been crucial in advancing this avenue. The present review focuses on the use of unconventional yeasts and their enzymes in the most interesting reactions where biocatalysis is applied. It highlights the advantages of using these microorganisms in industrial chemical processes due to their particular phenotypes, such as their ability to withstand high temperatures and pressures, as well as acidic or alkaline environments, high substrate loads, presence of organic solvents, etc. All this results in a wider range of possible substrates and higher efficiency. Examples of the most important reactions in which their use has been described are included, considering both catalysis by wild-type whole cells or their isolated enzymes and their genetically modified variants. All this information will help to understand the current relevance of unconventional yeasts and their enzymes in biocatalysis. Full article

The use of vegetable oils and their derivatives for polymer synthesis has been a major focus in recent years due to their universal availability, low production costs and biodegradability. In this study, the enzymatic synthesis of oligoesters of ricinoleic acid obtained from castor oil combined with three aromatic natural derivatives (cinnamyl alcohol, sinapic acid, and caffeic acid) was investigated. The formation of the reaction products was demonstrated by FT-IR, MALDI-TOF MS and NMR spectroscopy and for the oligo (ricinoleyl)-caffeate the thermal properties and biodegradability in sweet water were analyzed and a rheological characterization was performed. The successful enzymatic synthesis of oligoesters from ricinoleic acid and aromatic monomers using lipases not only highlights the potential of biocatalysis in green chemistry but also contributes to the development of sustainable and biodegradable methods for synthesizing products with potential applications as cosmetic ingredients. Full article

Deep eutectic solvents (DESs) are a mixture of two or more components, and at a particular composition, they become liquids at room temperature. When the compounds that constitute the DESs are primary metabolites namely, amino acids, organic acids, sugars, or choline derivatives, the DESs are called natural deep eutectic solvents (NADESs). NADESs fully represent green chemistry principles. These solvents are highly welcome, as they are obtained from renewable resources, and gratifyingly are biodegradable and biocompatible. They are an alternative to room-temperature ionic liquids (RTILs). From the pharmaceutical industry’s point of view, they are highly desirable, but they unfortunately have been rarely used despite their enormous potential. In this review, we look at their impact on the asymmetric catalytic synthesis of key target molecules via metal-based catalysis, biocatalysis, and organocatalysis. In many cases, the NADESs that have been used are chiral and can even promote enantioselective reactions; this crucial and very exciting aspect is also discussed and analyzed. Full article

The utilization of chemical reactions is crucial in various industrial processes, including pharmaceutical synthesis and the production of fine chemicals. However, traditional chemical catalysts often lack selectivity, require harsh reaction conditions, and lead to the generation of hazardous waste. In response, biocatalysis has emerged as a promising approach within green chemistry, employing enzymes as catalysts. Among these enzymes, aldolases have gained attention for their efficiency and selectivity in catalyzing C-C bond formation, making them versatile biocatalysts for diverse biotechnological applications. Despite their potential, challenges exist in aldolase-based biocatalysis, such as limited availability of natural aldolases with desired catalytic properties. This review explores strategies to address these challenges, including immobilization techniques, recombinant expression, and protein engineering approaches. By providing valuable insights into the suitability of aldolases as biocatalysts, this review lays the groundwork for future research and the exploration of innovative strategies to fully harness the potential of aldolases in biotechnology. This comprehensive review aims to attract readers by providing a comprehensive overview of aldolase-based biocatalysis, addressing challenges, and proposing avenues for future research and development. Full article

Biocatalysis holds immense potential for pharmaceutical development as it enables synthetic routes to various chiral building blocks with unparalleled selectivity. Therein, solvent and water use account for a large contribution to the environmental impact of the reactions. In the spirit of Green Chemistry, a transition from traditional highly diluted aqueous systems to intensified non-aqueous media to overcome limitations (e.g., water shortages, recalcitrant wastewater treatments, and low substrate loadings) has been observed. Benefiting from the spectacular advances in various enzyme stabilization techniques, a plethora of biotransformations in non-conventional media have been established. Deep eutectic solvents (DESs) emerge as a sort of (potentially) greener non-aqueous medium with increasing use in biocatalysis. This review discusses the state-of-the-art of biotransformations in DESs with a focus on biocatalytic pathways for the synthesis of active pharmaceutical ingredients (APIs). Representative examples of different enzyme classes are discussed, together with a critical vision of the limitations and discussing prospects of using DESs for biocatalysis. Full article

Amino alcohols are important compounds that are widely used in the polymer and pharmaceutical industry, particularly when used as chiral scaffolds in organic synthesis. The hydroxylation of polyamide polymers may allow crosslinking between molecular chains through the esterification reactions of hydroxyl and carboxyl groups. Therefore, this may alter the functional properties of polyamide polymers. 2-hydroxycadaverine (2HyC), as a new type of chiral amino alcohol, has potential applications in the pharmaceutical, chemical, and polymer industries. Currently, 2HyC production has only been realized via pure enzyme catalysis or two-stage whole-cell biocatalysis, which faces great challenges for scale-up production. However, the use of a cell factory is very promising for the production of 2HyC in industrial applications. Here, we designed and constructed a promising artificial pathway in Escherichia coli for producing 2HyC from biomass-derived lysine. This biosynthesis route expands the lysine catabolism pathway and employs two enzymes to sequentially convert lysine into 2HyC. However, the catalytic activity of wild-type pyridoxal phosphate-dependent decarboxylase from Chitinophage pinensis (DC_Cp) toward 3-hydroxylysine is lower, resulting in the lower production of 2HyC. Thus, the higher catalytic activity of DC_Cp is desired for low-cost and expanded industrial applications of 2HyC. To improve the catalytic activity of DC_Cp, a mutant library of DC_Cp was first built using a semi-rational design. The K_cat/K_m of mutant DC_Cp (R53D/V94I) increased by 63%. A titer of 359 mg/L 2HyC was produced in shake flasks, with a 2HyC titer increase of 54% compared to control strain ML101. The results show that the production of 2HyC was effectively increased through a semi-rational design strategy. These findings lay the foundation for the development and utilization of renewable resources to produce 2HyC in microorganisms via an efficient, green, and sustainable biosynthetic strategy for further industrial application. Full article

The bio-based solvent dihydrolevoglucosenone (Cyrene) is a green and sustainable alternative to petroleum-based dipolar aprotic solvents. Cyrene can be prepared from cellulose in a simple two-step process and can be produced in a variety of yields. Cyrene is compatible with a large number of reactions in the chemical industry and can be applied in organic chemistry, biocatalysis, materials chemistry, graphene and lignin processing, etc. It is also green, non-mutagenic and non-toxic, which makes it very promising for applications. In this paper, we have also screened all articles related to Cyrene on the Web of Science and visualised them through Cite Space. Full article

Steroids, the second largest drug category ranked after antibiotics, find widespread use in treatments for reproductive health, endocrine regulation, and inflammation. Advances in steroidal chemistry to date have led to the widespread use of sterols as starting substances in the development of environmentally friendly biotechnologies for steroid production, including biocatalysis, microbial transformations, and biosynthesis using engineered micro-organisms. In this review, we synthesize some of the recent advancements in steroid biocatalysis using the Mycolicibacterium species, including the identification and modification of crucial elements for enhanced production. We also delve into the detailed characterization and reconstruction of metabolic pathways in specific microbial strains, shedding light on their potential for steroid biosynthesis. Additionally, we highlight the development of innovative de novo biosynthesis pathways for steroids within engineered cell factories. These results collectively provide an overview of the current landscape and emerging trends in green steroid manufacturing within the steroidal pharmaceutical industry. Full article