Recent Progress in Biocatalysis with Enzymes Immobilized on Mesoporous Hosts

Enzymes are highly desirable in green and sustainable chemistry. One of the major issues in biocatalysis is enzyme stabilization under in vitro process conditions and catalyst recycling. In recent years, mesoporous materials have been extensively explored as supports for immobilization of enzymes. This review describes the recent developments in enzyme immobilization in mesoporous materials and their potential applications as biocatalysts in the chemical and pharmaceutical industry.     

Carrier-Free Enzyme Immobilizates for Flow Chemistry

For the development of efficient and green industrial processes, the combination of biocatalysis and flow chemistry holds great promises. Flow chemical utilization of biocatalysts, essentially made possible by the immobilization (or retention) of enzymes in flow reactors, has attracted increased academic attention during recent years. In the present review we present an overview of immobilization strategies suitable for flow chemistry, particularly focusing on recently developed carrier-free immobilization methods, highlighting advances in the field and presenting future trends.     

Intermolecular Diels-Alder Cycloadditions of Furfural-Based Chemicals from Renewable Resources: A Focus on the Regio- and Diastereoselectivity in the Reaction with Alkenes

A recent strong trend toward green and sustainable chemistry has promoted the intensive use of renewable carbon sources for the production of polymers, biofuels, chemicals, monomers and other valuable products. The Diels-Alder reaction is of great importance in the chemistry of renewable resources and provides an atom-economic pathway for fine chemical synthesis and for the production of materials. The biobased furans furfural and 5-(hydroxymethyl)furfural, which can be easily obtained from the carbohydrate part of plant biomass, were recognized as “platform chemicals” that will help to replace the existing oil-based refining to biorefining. Diels-Alder cycloaddition of furanic dienes with various dienophiles represents the ideal example of a “green” process characterized by a 100% atom economy and a reasonable E-factor. In this review, we first summarize the literature data on the regio- and diastereoselectivity of intermolecular Diels-Alder reactions of furfural derivatives with alkenes with the aim of establishing the current progress in the efficient production of practically important low-molecular-weight products. The information provided here will be useful and relevant to scientists in many fields, including medical and pharmaceutical research, polymer development and materials science.     

绿色化学技术在制药工业中的应用

绿色化学是当今国际化学研究的前沿，是21世纪的科学，并将成为各化学基础学科和应用技术研究的热点。本文综述了几种绿色化学技术在制药工业中的应用及进展．并指出了绿色化学是我国制药工业可持续发展的必由之路。     

New Trends and Future Opportunities in the Enzymatic Formation of C−C,C−N,and C−O bonds

Organic chemistry provides society with fundamental products we use daily. Concerns about the impact that the chemical industry has over the environment is propelling major changes in the way we manufacture chemicals. Biocatalysis offers an alternative to other synthetic approaches as it employs enzymes, Nature's catalysts, to carry out chemical transformations. Enzymes are biodegradable, come from renewable sources, operate under mild reaction conditions, and display high selectivities in the processes they catalyse. As a highly multidisciplinary field, biocatalysis benefits from advances in different areas, and developments in the fields of molecular biology, bioinformatics, and chemical engineering have accelerated the extension of the range of available transformations (E. L. Bell et al., Nat. Rev. Meth. Prim. 2021 , 1, 1–21). Recently, we surveyed advances in the expansion of the scope of biocatalysis via enzyme discovery and protein engineering (J. R. Marshall et al., Tetrahedron 2021 , 82, 131926). Herein, we focus on novel enzymes currently available to the broad synthetic community for the construction of new C−C, C−N and C−O bonds, with the purpose of providing the non-specialist with new and alternative tools for chiral and sustainable chemical synthesis.     

Real-time electrochemical monitoring: toward green analytical chemistry

This Account presents a survey of recent advances in electrochemical sensing technology relevant to green analytical chemistry and examines the potential advantages, limitations, and applications of these monitoring devices. Stricter environmental control and effective process monitoring have created considerable demands for innovative analytical methodologies. New devices and protocols, with negligible waste generation or no hazardous substances, and in situ real-time monitoring capability are particularly needed for addressing the challenges of green analytical chemistry. The coupling of modern electrochemical detection principles with recent advances in molecular recognition, microelectronics, and microfabrication has led to powerful, compact, and "user-friendly" analytical devices. The unique features of such electrochemical monitoring systems make them particularly attractive for addressing environmental and industrial problems and the challenges of green chemistry. These developments allow the instrument to be taken to the sample (rather than the traditional way of bringing the sample to the laboratory) and hence to ensure effective process or pollution control.     

酶催化工艺用于制药工业的研究进展

介绍了近年来酶催化工艺在医药领域中,如酶法合成半合成抗生素、手性药物及中间体等生产中的一些应用及酶催化剂的一些特点和新发展,并对酶催化工艺用于制药工业的研究和发展进一步作了评述。     

Process considerations for the scale-up and implementation of biocatalysis

With increasing emphasis on renewable feed-stocks and green chemistry, biocatalytic processes will have an important role in the next generation of industrial processes for chemical production. However, in comparison with conventional industrial chemistry, the use of bioprocesses in general and biocatalysis in particular is a rather young technology. Although significant progress has been made in the implementation of new processes (especially in the pharmaceutical industry) no fixed methods for process design have been established to date. In this paper we present some of the considerations required to scale-up a biocatalytic process and some of the recently developed engineering tools available to assist in this procedure. The tools will have a decisive role in helping to identify bottlenecks in the biocatalytic development process and to justify where to put effort and resources.     

The transaldolase family: new synthetic opportunities from an ancient enzyme scaffold

Aldol reactions constitute a powerful methodology for carbon-carbon bond formation in synthetic organic chemistry. Biocatalytic carboligation by aldolases offers a green, uniquely regio- and stereoselective tool with which to perform these transformations. Recent advances in the field, fueled by both discovery and protein engineering, have greatly improved the synthetic opportunities for the atom-economic asymmetric synthesis of chiral molecules with potential pharmaceutical relevance. New aldolases derived from the transaldolase scaffold (based on transaldolase B and fructose-6-phosphate aldolase from Escherichia coli) have been shown to be unusually flexible in their substrate scope; this makes them particularly valuable for addressing an expanded molecular range of complex polyfunctional targets. Extensive knowledge arising from structural and molecular biochemical studies makes it possible to address the remaining limitations of the methodology by engineering tailored biocatalysts.     

绿色合成分子筛的研究进展

分子筛由于具有规则的孔道结构、适宜的酸性、良好的热和水热稳定性等特点,广泛应用于吸附、分离、离子交换及催化等领域。传统水热法制备分子筛因需要使用大量溶剂和有机模板剂,存在合成效率低、生产成本高、污染环境等一系列问题。近年来,随着"绿色化学"理念的深入人心,开发绿色、可持续的分子筛制备路线备受关注,逐渐成为该领域的研究热点。本文主要从水热法、离子热法、干胶法以及无溶剂法等几个方面,对国内外分子筛绿色合成的最新研究进展进行综述,并归纳比较上述合成方法的优缺点。最后,提出目前绿色合成分子筛过程中存在的问题,展望其未来发展前景。     

生物催化与生物转化的研究进展

生物催化与生物转化是生物学、化学、过程工程科学的交叉领域,其核心目标是大规模采用微生物或酶为催化剂生产化学品、医药、能源、材料等。本文指出生物催化与生物转化研究重新崛起,并已成为发达国家的重要科技与产业发展战略,概述了生物催化与生物转化技术的发展现状与趋势,介绍了我国重大基础研究项目生物催化与生物转化的研究动态,该项目的关键问题及主要研究方向是：(1)生物催化多样性理论及其实现方法;(2)催化剂改造的方法学;(3)生物系统催化的理论和方法;(4)生物催化剂适应性原理和方法问题;(5)重要生物催化体系的催化机理。     

Trehalose Analogues: Latest Insights in Properties and Biocatalytic Production

Trehalose (α-d-glucopyranosyl α-d-glucopyranoside) is a non-reducing sugar with unique stabilizing properties due to its symmetrical, low energy structure consisting of two 1,1-anomerically bound glucose moieties. Many applications of this beneficial sugar have been reported in the novel food (nutricals), medical, pharmaceutical and cosmetic industries. Trehalose analogues, like lactotrehalose (α-d-glucopyranosyl α-d-galactopyranoside) or galactotrehalose (α-d-galactopyranosyl α-d-galactopyranoside), offer similar benefits as trehalose, but show additional features such as prebiotic or low-calorie sweetener due to their resistance against hydrolysis during digestion. Unfortunately, large-scale chemical production processes for trehalose analogues are not readily available at the moment due to the lack of efficient synthesis methods. Most of the procedures reported in literature suffer from low yields, elevated costs and are far from environmentally friendly. “Greener” alternatives found in the biocatalysis field, including galactosidases, trehalose phosphorylases and TreT-type trehalose synthases are suggested as primary candidates for trehalose analogue production instead. Significant progress has been made in the last decade to turn these into highly efficient biocatalysts and to broaden the variety of useful donor and acceptor sugars. In this review, we aim to provide an overview of the latest insights and future perspectives in trehalose analogue chemistry, applications and production pathways with emphasis on biocatalysis.     

CO_2直接合成碳酸二甲酯催化剂的研究进展

碳酸二甲酯(DMC)是一种重要的绿色化工原料,在工业、农业、医药行业等领域得到广泛的应用。碳酸二甲酯的合成方法有多种,其中光气甲醇法、酯交换法、氧化羰基化法已经工业化,但由于各自的缺点,限制了其规模化。近年来,研究较多的也是公认最绿色环保的合成方法是用二氧化碳与甲醇直接合成碳酸二甲酯。介绍了这种方法所应用的催化剂及其催化机理研究的进展状况,并对诸多催化剂存在的问题提出建议。     

Uranyl Photocleavage of Phosphopeptides Yields Truncated C‐Terminally Amidated Peptide Products

The uranyl ion (UO₂²⁺) binds phosphopeptides with high affinity, and when irradiated with UV‐light, it can cleave the peptide backbone. In this study, high‐accuracy tandem mass spectrometry and enzymatic assays were used to characterise the photocleavage products resulting from the uranyl photocleavage reaction of a tetraphosphorylated β‐casein model peptide. We show that the primary photocleavage products of the uranyl‐catalysed reaction are C‐terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top challenges in green pharmaceutical chemistry.     

乳液膜技术及其在酶化工的应用

本文评述了乳液膜技术在酶反应中的应用情况，着重从增强液膜稳定性，改进传质效果以及减少酶活损失３个方面进行了分析，并对其应用前景作了讨论。     

Glycerol in subcritical and supercritical solvents

Glycerol conversion to added value chemicals is a research avenue that has attracted significant interest in recent years. The utilization of critical solvents such as water and organic solvents in critical conditions as well as subcritical conditions (or hot compressed solvent) and supercritical conditions can offer several advantages to batch processes and in continuous flow systems in view of their potential implementation in industry. This review has been aimed to highlight most recent key processes for glycerol valorization to valuable products using different types of catalysts and processes. © 2016 Society of Chemical Industry     

Photo-biocatalytic Cascades: Combining Chemical and Enzymatic Transformations Fueled by Light

In the field of green chemistry, light – an attractive natural agent – has received particular attention for driving biocatalytic reactions. Moreover, the implementation of light to drive (chemo)enzymatic cascade reactions opens up a golden window of opportunities. However, there are limitations to many current examples, mostly associated with incompatibility between the enzyme and the photocatalyst. Additionally, the formation of reactive radicals upon illumination and the loss of catalytic activities in the presence of required additives are common observations. As outlined in this review, the main question is how to overcome current challenges to the exploitation of light to drive (chemo)enzymatic transformations. First, we highlight general concepts in photo-biocatalysis, then give various examples of photo-chemoenzymatic (PCE) cascades, further summarize current synthetic examples of PCE cascades and discuss strategies to address the limitations.     

Interfacing biocatalysis and organic synthesis

The path to new chemical entities often shows the limitations of existing tools both in biocatalysis and organic chemistry. Organic synthetic procedures to prepare a compound in a target‐oriented synthesis can damage other functional parts of the molecule. Protection–deprotection schemes can lead to a dead end, when a certain protecting group cannot be cleaved off. In biocatalysis, on the other hand, the required biocatalytic toolbox and methodology might not be readily available, therefore limiting a biocatalytic approach. New toolboxes, ingredients, and methodologies at the interface of classical organic synthesis and biocatalytic reactions bridge the gap between these two areas. Since product isolation and purification involves a substantial amount of time in the preparation of chemicals, methodologies to simplify these tasks are necessary to get the pure product into the bottle with less work‐up time. Efficient and safe new pharmaceuticals, intermediates and analytical reagents need to be prepared under certain safety, health, environmental and economical boundary conditions. Biocatalytic reactions have been shown to overcome these limitations successfully and are becoming increasingly important in industrial manufacturing. Building bridges between biocatalysis and organic synthesis will therefore create roads to new synthetic strategies and technological frontiers of both fundamental and practical interest. Copyright © 2007 Society of Chemical Industry     

可见光催化构建碳氮键的研究进展

可见光是一种清洁的可再生能源,利用可见光代替传统的热能进行化学转化具有绿色、高效的优点.碳氮键是广泛存在于多种生物活性分子和药物分子中的重要化学键,光催化构筑碳氮键在有机和药物化学领域中具有重要研究意义.近年来光催化形成碳氮键研究得到了快速发展,许多新颖的合成方法不断涌现.综述了可见光催化构建C(sp2)—N键和C(s...     

半导体合成生物学的研究进展

半导体合成生物学是研究半导体技术与合成生物学之间协同作用的一门交叉学科。其涉及的活细胞-半导体材料杂合体系具有独特的能量和信号转导机制,不仅维持活细胞的代谢能力,而且保留半导体材料的光电学物理特性,在化工、通讯、计算、能源及医疗等领域具有广阔的应用前景。综述了半导体合成生物学在生物催化、智能生物传感以及新型DNA数据存储领域的最新研究进展,讨论了目前研究面临的技术难题及解决方案,旨在为合成生物学和半导体技术这两个影响化工发展的领域提供有价值的参考。