The importance of green chemistry in process research and development

Green Chemistry or Sustainable Chemistry is defined by the Environmental Protection Agency as "the design of chemical products that reduce or eliminate the use of hazardous substances" In recent years there is a greater societal expectation that chemists and chemical engineers should produce greener and more sustainable chemical processes and it is likely that this trend will continue to grow over the next few decades. This tutorial review gives information on solvents and solvent selection, basic environmental metrics collection and three industrial case histories. All three case histories involve enzymatic chemistry. Pregabalin (Lyrica?) is produced using a lipase based resolution and is extremely unusual in that all four manufacturing steps to make pregabalin are performed in water. Sitagliptin (Januvia?) uses a transaminase in the final chemical step. Finally a rosuvastatin (Crestor?) intermediate is produced using a deoxy ribose aldolase (DERA) enzyme in which two carbon-carbon bonds and two chiral centres are formed in the same process step.     

Early Industrial Roots of Green Chemistry and the history of the BHC Ibuprofen process invention and its Quality connection

Conventional wisdom and many published histories of “Green Chemistry” describe its start as being a result of governmental and/or regulatory actions at the US Environmental Protection Agency (“EPA”) during the early 1990’s. But there were many Real World industrial examples of environmentally friendly commercial processes in the oil and commodity chemicals industries for decades prior to the 1990s. Some early examples of commercial “Green Chemistry” are briefly described in this article. The Boots/Hoechst Celanese (“BHC”) Ibuprofen process was one of the earliest multiple-award-winning examples of industrial “Green Chemistry” in the fine chemical/pharmaceutical industry. The author, who conceived the BHC Ibuprofen synthetic strategy in 1984, reveals and documents that the BHC Ibuprofen process was not primarily a result of governmental or regulatory mandates, or environmentalist or political motivations. The BHC ibuprofen process, and probably many other early industrial “green” inventions, evolved from, and their development and commercialization motivated and guided by, a long prior industrial culture of both scientific and technical evolution. The invention and commercialization of these early industrial commercialized processes, and the BHC Ibuprofen process were also guided by both competitive and economic market needs, personal human motivations, and a low waste culture of “Quality” and “Continuous Improvement” that the commodity chemical industry internally promoted in the 1980’s. The author comments on some perceptions of the status of Green Chemistry now, and directions it should consider going in the future. The author recommends that young Green Chemists and/or Green Engineers reconsider “Quality” approaches in order to genuinely lead Society toward a Greener future.     

绿色化学思想在中国的传播——基于“中国期刊网”的文献分析

通过对“中国学术期刊网络出版总库”发表的以“绿色化学”为题的全部文献进行分析,试图从一个侧面勾勒出“绿色化学”概念提出20年来在中国的传播状况、存在的问题和主要发展趋势.     

Green Chemistry: An Innovative Technology

The drive towards clean technology in the chemical industry with an increasing emphasis on the reduction of waste at source requires a level of innovation and new technology that the chemical industry is beginning to adopt. The green chemistry revolution provides an enormous number of opportunities to discover and apply new synthetic approaches using alternative feedstocks; ecofriendly reaction conditions, energy minimizations and the design of less toxic and inherently safer chemicals. In this review exciting opportunities and some successful examples of green chemistry in practice are described. While developments in the 20th century have brought various social and economic benefits to the people but these changes have also caused a range of environmental problems at both local and global levels. Over recent years, sustainable development has been accepted by government, industry and the public as a necessary goal for achieving social, economic and environmental objectives (Uark, 1999). Within this, green chemistry (www.chemsoc.org/gen) plays a key role in maintaining and improving quality of our life and preserving natural environments. The term ‘Green Chemistry’ was first coined by the US Environmental Protection Agency (EPA) in the early 1990s and major interest in green chemistry in the US began in earnest with the passage of the ‘Pollution Prevention Act’ of 1990. Thus Green Chemistry becoming a formal focus of the EPA in 1991.     

UV固化涂料在修复底漆中的应用

综述了UV固化技术和UV固化涂料等相关领域的发展状况,以BASF公司在2005年获得美国总统绿色化学奖的产品为实例,通过与传统产品的对比全面地介绍了绿色环保底漆的组成成分、固化机理和影响因素,最后对UV固化涂料在绿色环保车漆领域的应用展望做一总结。     

The safer chemical design game. Gamification of green chemistry and safer chemical design concepts for high school and undergraduate students

Green chemistry can strongly attract students to chemistry. We, therefore, developed a green chemistry educational game that motivates students at the undergraduate and advanced high school levels to consider green chemistry and sustainability concerns as they design a hypothetical, chemical product. The game is intended for incorporation into any chemistry course for majors and non-majors that teaches sustainability and/or the Principles of Green Chemistry at the undergraduate level. The game is free of charge and encourages students to think like professional chemical designers and to develop a chemical product with respect to function and improved human and environmental health. This computer simulation has been assessed by educators and can be seamlessly integrated into an existing curriculum.     

Exploring Green Chemistry,Sustainable Chemistry and innovative business models such as Chemical Leasing in the context of international policy discussions

This article provides an overview on Green Chemistry and Sustainable Chemistry in the context of the 2030 Agenda for Sustainable Development and different policy frameworks such as the EU Circular Economy Action Plan and SAICM, the Strategic Approach of International Chemicals Management. There is an increasing body of evidence suggesting the practicality and applicability of Green Chemistry and Sustainable Chemistry within industrial development policies and international agreements addressing chemicals and waste concerns. To explore the full potential of Green Chemistry and Sustainable Chemistry, the authors come to the conclusion that innovative business models are required to facilitate the engagement of the different players, including industry. While presenting the United Nations Industrial Development Organization (UNIDO)’s experiences and lessons learnt from ten years of work in UNIDO's Global Chemical Leasing Programme, the article also highlights the role that innovative and circular economy business models could play in achieving inclusive and sustainable economic growth. It therefore explores the potential of integrated Chemical Leasing, Green Chemistry and Sustainable Chemistry initiatives at the global level.     

Analytical Chemistry in the Republic of Ireland training and employment of chemists and technicians

Summary Based on the results of surveys carried out throughout the country the following topics are discussed: employment of chemists in Ireland, employment of chemists and technicians in the field of Analytical Chemistry, training requirements, types of courses and syllabus outlines.Presented at Euroanalysis III conference, Dublin, August 20–25, 1978     

A rechargeable battery based on hydrophilic radical polymer electrode and its green assessment

Abstract

A hydrophilic radical polymer electrode-based rechargeable battery was designed along the concept of green chemistry. A hydrophilic radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl vinylether), was synthesized as an electrode-active material; its battery demonstrated a high charging–discharging rate and long cycle life. The combination of the hydrophilic polymer electrode and an aqueous electrolyte for the battery fabrication was expected to provide safety improvements such as a low ignition risk besides the high battery performance. The green characteristics were studied using the “i-Messe,” an evaluation method proposed by the committee of the Green Sustainable Chemistry Network, Japan. The electrode-active polymer was evaluated for substantial improvements in disaster safety and health safety.     

From pharmacophore to leads: Bioactive compound discovery via computer-aided techniques

Based on the concept of Green Chemistry, a new procedure of finding bioactive compounds and their synthetic routes by computer-aided techniques was proposed. The procedure consists of pharmacophore search against a 3D structural database of natural products for lead discovery and computer-aided synthesis design for avoiding unuseful synthetic experiments. This work demonstrated that computer aided drug design and synthesis design would help us to make the consideration of environmental concerns systematically, rather than having to deal later with the unnecessary waste chemicals. Thus, it is shown that chemical computer-aided design (CAD) is an indispensable part of Green Chemistry.     

Towards a bio-based industry: benign catalytic esterifications of succinic acid in the presence of water

The biorefinery of the future will need to integrate bioconversion and appropriate low environmental impact chemical technologies (Green Chemistry) so as to produce a wide range of products from biomass in an economically effective and environmentally acceptable manner. The challenge for chemists is to develop chemistry that works with fermentation-derived dilute, aqueous mixtures of oxygenated chemicals (platform molecules) rather than the petroleum-derived non-aqueous, non-oxygenated feedstocks we have been working with for 50+ years and to avoid energy intensive and wasteful concentration and purification steps. Here we show that a new family of tuneable mesoporous carbonaceous catalysts derived from starch can be used to accomplish efficient chemistry in aqueous solution. Our new aqueous catalytic chemistry relies on the ability to adjust the surface properties including the hydrophobicity-hydrophilicity balance of mesoporous Starbons by carbonisation at different temperatures (250-750 degrees C). Simple treatment of these materials with sulfuric acid then provides a series of porous solid acids that can function under a range of conditions including dilute aqueous solution. The reactions of succinic acid (platform molecule) in aqueous alcohol demonstrate the outstanding activities of these new catalysts.     

Education and training in Analytical Chemistry

Analytical Chemistry is involved in the undergraduate curriculum in the US in many ways. It is one of four required subjects for accreditation of a college or university by the American Chemical Society. However there is much discussion underway in the US about change in the undergraduate training of analytical chemists to more closely reflect the “problem solving” nature of Analytical Chemistry, and to better address the needs of industry. It is suggested that the curriculum should emphasize the fundamentals but also teach applied Analytical Chemistry, the need for teamwork, and the importance of communication skills.     

绿色路易斯酸三卤化铟在有机合成中的应用

三卤化铟作为温和的路易斯酸可在水、醇等绿色溶剂中实现高化学选择性、高 区域选择性和高立体选择性的化学转化。综述了三卤化铟在羟醛反应和类羟醛-曼 尼希反应、Fiedel-Crafts反应、环氧化合物的重排反应、α-氨基膦酸的合成、喹 啉环系的构建、酯交换反应、Diels-Alder反应和杂Diels-Alder反应,手性呋喃二 醇的合成、水相中的叠氮解反应和二硫缩醛的制备中的应用,同时还总结了本课题 组将三卤化铟应用于Biginelli反应和还原脱氧反应的反应结果。三卤化铟在有机 合成中潜在的优势将推动“绿色化学”的发展。     

Re-casting traditional organic experiments into green guided-inquiry based experiments: student perceptions

ABSTRACT

Green Chemistry principles can be used to re-cast traditional Organic chemistry experiments into more guided-inquiry based experiments. Inquiry questions related to green chemistry principles and metrics have been incorporated into our laboratory for the development of more guided-inquiry based experiments. Re-casting traditional experiments provides time for guided-inquiry by allowing students to evaluate reaction conditions and wastefulness of reactions. This includes evaluating solvent choices, heating methods, use of renewal materials, and contemplating reactants and products impacts on human health and environment. Students examine the changes as it pertains to green chemistry, the success of the reaction and the potential impacts on the mechanism. Involving students in these discoveries rooted in a guiding question made the Organic experiments guided-inquiry. Students were surveyed about their exposure to green chemistry and guided-inquiry based labs. Examples of some of the re-casted experiments, excerpts from student reports, and student impressions of the theme are presented.     

Extraction of humic acid from biological matrix – dry cow dung powder

Abstract

The increased local and global concern, for alarming environmental pollution, offers incentives to explore new green and clean materials and methods for safeguarding the environment. The generation of benign alternate routes for any step in chemical processes, is the need for today and tomorrow. In the present work, humic acid (HA) has been extracted from a green source, “dry cow dung powder”, using simple, cost effective, and eco-friendly methods. HA has been extracted, isolated, and characterized by employing different spectroscopic methods. The process investigated herein imparts a boost to “Green Chemistry”, a promising solution to many global environmental problems.     

Environmental photocatalysis: Perspectives for China

Photocatalysis is based on the double aptitude of the photocatalyst (essentially titania) to simultaneously adsorb reactants and absorb efficient photons. Heterogeneous photocatalysis is able to be efficient in Fine, “Green” and Environmental Chemistry. Photocatalysis induces mild oxidations in the absence of water by generating active neutral atomic O* species. For instance, the oxidation of 4-tert-butyl-toluene is 100% selective in 4-tert-butyl-benzaldehyde. In water treatment, many toxic inorganic ions are oxidized in their harmless upper oxidized state. The elimination of organic pollutants is the main field of water photocatalytic decontamination. Most of aliphatic and aromatic pollutants are totally mineralized into CO₂ and innocuous inorganic anions. More complex molecules, such as pesticides (herbicides, insecticides, fungicides, etc.) or dyes, are totally destroyed. Another example of green chemistry is the total degradation of dyes in water, in particular for the azo-dyes, with 100% selective degradation of -N=N- azo-groups into di-nitrogen. Photocatalysis is also active in the “bio-world” by killing bacteria (E. Coli, streptococcus, etc.) in water without re-growth. Air pollutants can also be destroyed, especially all the VOC’s (volatile organic compounds), providing certain air humidity enabling titania to produce cracking OH^· radicals. For chemical engineering reasons, the photocatalyst has to be fixed on a photo-inert support. In these conditions, UV-irradiated titania-based photocatalysis could be applied to the elimination of air pollutants, VOC’s, solvents, odors, chemicals, etc. Air treatment has to be associated with water and solid waste treatment because of odors. This is conducted by covering water treatment ponds or lagunas by rafts on which large sheets of Ahlstrom paper are deposited, supporting titania associated with activated carbon. Eventually, virus AH5N2, a model virus close to H5N1, responsible for the avian flu could be totally inactivated. Photocatalysis is directly connected with all 12 principles of Green Chemistry defined by Anastas (1998) and possesses open perspectives for China.     

Software tools for green and sustainable chemistry

In this review, we consider green chemistry metrics, related software tools, and the opportunities and challenges for their use in research laboratories. We provide an overview of state-of-the-art software designed both to aid researchers in planning and conducting chemical experiments and to assess sustainability of individual reactions and synthetic routes. The increasing digitalisation of research means that there is great opportunity for more extensive use of computational tools by synthetic chemists and for closer integration of green chemistry principles into the routine work of chemical laboratories. We discuss the scope for using software tools in the laboratory and assisting synthetic chemists in the adoption of green and sustainable chemistry approaches that are suitable for their specific purposes.     

A Showcase of Green Chemistry: Sustainable Synthetic Approach of Zirconium-Based MOF Materials

Zirconium-based metal-organic framework materials (Zr−MOFs) have more practical usage over most conventional benchmark porous materials and even many other MOFs due to the excellent structural stability, rich coordination forms, and various active sites. However, their mass-production and application are restricted by the high-cost raw materials, complex synthesis procedures, harsh reaction conditions, and unexpected environmental impact. Based on the principles of “Green Chemistry”, considerable efforts have been done for breaking through the limitations, and significant progress has been made in the sustainable synthesis of Zr−MOFs over the past decade. In this review, the advancements of green raw materials and green synthesis methods in the synthesis of Zr−MOFs are reviewed, along with the corresponding drawbacks. The challenges and prospects are discussed and outlooked, expecting to provide guidance for the acceleration of the industrialization and commercialization of Zr−MOFs.     

Ecofriendly chromatographic estimation of spasmolytic pharmaceutical mixture along with official toxic impurity, 3,5-dichloroaniline: Complete green profile appraisal

Nowadays, Green Analytical Chemistry is widely applied to provide various analytical methods with eco-friendly procedures employing the least toxic, harmful reagents on humans and the environment without affecting the efficacy of the determination. Accordingly, two eco-friendly, accurate, and reliable high-performance thin-layer chromatography-densitometry and high-performance liquid chromatographic methods were established for the determination and separation of two antispasmodic drugs, namely phloroglucinol and trimethylphloroglucinol in their pure, combined dosage form along with phloroglucinol toxic impurity, 3,5-dichloroaniline. For high-performance thin-layer chromatography-densitometry, efficient separation was developed via utilizing the stationary phase of high-performance thin-layer chromatography silica gel 60 F₂₅₄ plates and developing a system comprising of ethyl acetate-butanol-ammonia in the ratio of 8.0:2.0:0.2, by volume and scanning of the developed bands at 210.0 nm. The subsequent method is isocratic high-performance liquid chromatography with diode array detection in which separation was successively attained using XTerra RP-C₁₈ (250 × 4.6 mm, 5 μm) column as stationary phase and methanol-10.0 mM phosphate buffer, pH 3.7 ± 0.1 as mobile phase in the ratio of 75.0:25.0, v/v at flow rate 1.0 ml/min and scanning at 220.0 nm. The developed liquid chromatography methods were validated according to the International Council for Harmonization guidelines, and all results acknowledged their efficacy. Additionally, the proposed methods worked well for assessing the cited drugs in binary combined commercially available pharmaceutical formulation. The greenness profile of the present methods was assessed and estimated using various assessment tools, namely; Green Analytical Procedure Index, analytical eco-scale method, National Environmental Method Index in addition to Analytical GREEnness tool to evaluate the greenness of the provided methods with a statistical comparison between them to assess the more green ones.