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Special Issue "Chemicals from Biomass"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (20 December 2016)

Special Issue Editors

Guest Editor
Prof. James H. Clark

Green Chemistry Center of Excellence, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
Website | E-Mail
Interests: renewable materials; clean synthesis and platform molecules; natural solvents; microwave chemistry
Guest Editor
Dr. Thomas J. Farmer

Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
Website | E-Mail
Interests: clean synthesis; heterogeneous catalysis; sustainable chemicals; bio-content analysis; microwave chemistry; polymer chemistry; alternative solvents; mixed-metal catalysis; valorisation of waste

Special Issue Information

Dear Colleagues,

Despite the recent slump in global crude oil prices interest in the burgeoning bio-based economy has continued to grow, this is especially so for the bio-based chemicals and materials sector. Evidently researchers, industry and consumers alike see the pressing need to move away from non-renewable petrochemicals and to replace this with sustainably derived bio-based chemicals. Significant developments have been achieved in the field of biomass-derived chemicals and materials over the last 20 years, and this movement has coincided with the proliferation of the concepts of Green and Sustainable Chemistry. Clearly both the use of sustainable non-depleting resources and the application of more environmentally benign synthetic methods make an ideal union for the 21st Century Chemical Industry. However, the switch from crude oil to biomass is not as simple as it first appears. Biomass as a feedstock is considerably more complex than fossil resources, with a chemical composition that varies by species, by season and by location. Biomass also contains substantially more heteroatoms and so the chemicals produced from biomass, so called Platform Molecules, also contain greater functionality. This functionality can be a benefit or a burden, with new catalysts and processes needed to deal with this increased functionality. There are also many possible routes from which chemicals can be derived from biomass, starting from extracting of biochemicals, through to chemical, biological or thermal deconstruction. This Special Issue, Chemicals from Biomass, particularly welcomes research articles and reviews that demonstrate how:

  • Biomass can be used as a feedstock for the production of chemicals and materials, including but not exclusive to pharmaceuticals, solvents, polymers and catalysts
  • Developments have been made in the pre-treatment of biomass, facilitating down-stream processes in biorefineries
  • Recent advances in greener chemical methods have been applied to processing of biomass right through to the manufacture of bio-derived products
  • Biotechnology can also support the conversion of biomass to chemicals
  • Carrying out chemistry on bio-derived chemicals and materials can differ from the current methods established for petrochemicals
  • Assessments of the sustainability/greenness are being used to inform producers of bio-based chemicals as to best routes for the production of chemicals and materials
  • Integration of processes and products can make biorefineries more economically viable
  • The history of bio-based chemicals over the last 20 years has evolved
  • Chemicals from biomass fit into the concept of a “Circular Economy”

Prof. James H Clark
Dr. Thomas J Farmer
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • platform molecules
  • green chemistry
  • biorefinery
  • bio-based chemicals
  • biomass to chemicals
  • sustainable chemicals
  • clean synthesis
  • circular economy
  • biomass pre-treatment

Published Papers (7 papers)

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Research

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Open AccessArticle High-Yield Production of Levulinic Acid from Pretreated Cow Dung in Dilute Acid Aqueous Solution
Molecules 2017, 22(2), 285; doi:10.3390/molecules22020285
Received: 10 January 2017 / Revised: 8 February 2017 / Accepted: 9 February 2017 / Published: 14 February 2017
PDF Full-text (3709 KB) | HTML Full-text | XML Full-text
Abstract
Agricultural waste cow dung was used as feedstock for the production of a high value–added chemical levulinic acid (LA) in dilute acid aqueous solutions. A high LA yield of 338.9 g/kg was obtained from the pretreated cow dung, which was much higher than
[...] Read more.
Agricultural waste cow dung was used as feedstock for the production of a high value–added chemical levulinic acid (LA) in dilute acid aqueous solutions. A high LA yield of 338.9 g/kg was obtained from the pretreated cow dung, which was much higher than that obtained from the crude cow dung (135 g/kg), mainly attributed to the breakage of the lignin fraction in the lignocellulose structure of the cow dung by potassium hydroxide (KOH) pretreatment, and thus enhanced the accessibility of cow dung to the acid sites in the catalytic reaction. Meanwhile, another value-added chemical formic acid could be obtained with a yield of ca. 160 g/kg in the process, implying a total production of ca. 500 g/kg yield for LA and formic acid from the pretreated cow dung with the proposed process. The developed process was shown to be tolerant to high initial substrate loading with a satisfied LA yield. This work provides a promising strategy for the value-increment utilization of liglocellulosic agricultural residues. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Open AccessArticle Adsorption Properties of Nano-MnO2–Biochar Composites for Copper in Aqueous Solution
Molecules 2017, 22(1), 173; doi:10.3390/molecules22010173
Received: 13 December 2016 / Revised: 9 January 2017 / Accepted: 13 January 2017 / Published: 20 January 2017
Cited by 5 | PDF Full-text (4198 KB) | HTML Full-text | XML Full-text
Abstract
There is a continuing need to develop effective materials for the environmental remediation of copper-contaminated sites. Nano-MnO2–biochar composites (NMBCs) were successfully synthesized through the reduction of potassium permanganate by ethanol in a biochar suspension. The physicochemical properties and morphology of NMBCs
[...] Read more.
There is a continuing need to develop effective materials for the environmental remediation of copper-contaminated sites. Nano-MnO2–biochar composites (NMBCs) were successfully synthesized through the reduction of potassium permanganate by ethanol in a biochar suspension. The physicochemical properties and morphology of NMBCs were examined, and the Cu(II) adsorption properties of this material were determined using various adsorption isotherms and kinetic models. The adsorption capacity of NMBCs for Cu(II), which was enhanced by increasing the pH from 3 to 6, was much larger than that of biochar or nano-MnO2. The maximum adsorption capacity of NMBCs for Cu(II) was 142.02 mg/g, which was considerably greater than the maximum adsorption capacities of biochar (26.88 mg/g) and nano-MnO2 (93.91 mg/g). The sorption process for Cu(II) on NMBCs fitted very well to a pseudo-second-order model (R2 > 0.99). Moreover, this process was endothermic, spontaneous, and hardly influenced by ionic strength. The mechanism of Cu(II) adsorption on NMBCs mainly involves the formation of complexes between Cu(II) and O-containing groups (e.g., COO–Cu and Mn–O–Cu). Thus, NMBCs may serve as effective adsorbents for various environmental applications, such as wastewater treatment or the remediation of copper-contaminated soils. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Open AccessArticle Recirculation: A New Concept to Drive Innovation in Sustainable Product Design for Bio-Based Products
Molecules 2017, 22(1), 48; doi:10.3390/molecules22010048
Received: 1 December 2016 / Revised: 1 December 2016 / Accepted: 22 December 2016 / Published: 29 December 2016
Cited by 1 | PDF Full-text (1737 KB) | HTML Full-text | XML Full-text
Abstract
Bio-based products are made from renewable materials, offering a promising basis for the production of sustainable chemicals, materials, and more complex articles. However, biomass is not a limitless resource or one without environmental and social impacts. Therefore, while it is important to use
[...] Read more.
Bio-based products are made from renewable materials, offering a promising basis for the production of sustainable chemicals, materials, and more complex articles. However, biomass is not a limitless resource or one without environmental and social impacts. Therefore, while it is important to use biomass and grow a bio-based economy, displacing the unsustainable petroleum basis of energy and chemical production, any resource must be used effectively to reduce waste. Standards have been developed to support the bio-based product market in order to achieve this aim. However, the design of bio-based products has not received the same level of attention. Reported here are the first steps towards the development of a framework of understanding which connects product design to resource efficiency. Research and development scientists and engineers are encouraged to think beyond simple functionality and associate value to the potential of materials in their primary use and beyond. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Open AccessArticle Simultaneous Saccharification and Fermentation of Sugar Beet Pulp with Mixed Bacterial Cultures for Lactic Acid and Propylene Glycol Production
Molecules 2016, 21(10), 1380; doi:10.3390/molecules21101380
Received: 31 August 2016 / Revised: 7 October 2016 / Accepted: 12 October 2016 / Published: 17 October 2016
Cited by 3 | PDF Full-text (1997 KB) | HTML Full-text | XML Full-text
Abstract
Research into fermentative production of lactic acid from agricultural by-products has recently concentrated on the direct conversion of biomass, whereby pure sugars are replaced with inexpensive feedstock in the process of lactic acid production. In our studies, for the first time, the source
[...] Read more.
Research into fermentative production of lactic acid from agricultural by-products has recently concentrated on the direct conversion of biomass, whereby pure sugars are replaced with inexpensive feedstock in the process of lactic acid production. In our studies, for the first time, the source of carbon used is sugar beet pulp, generated as a by-product of industrial sugar production. In this paper, we focus on the simultaneous saccharification of lignocellulosic biomass and fermentation of lactic acid, using mixed cultures with complementary assimilation profiles. Lactic acid is one of the primary platform chemicals, and can be used to synthesize a wide variety of useful products, including green propylene glycol. A series of controlled batch fermentations was conducted under various conditions, including pretreatment with enzymatic hydrolysis. Inoculation was performed in two sequential stages, to avoid carbon catabolite repression. Biologically-synthesized lactic acid was catalytically reduced to propylene glycol over 5% Ru/C. The highest lactic acid yield was obtained with mixed cultures. The yield of propylene glycol from the biological lactic acid was similar to that obtained with a water solution of pure lactic acid. Our results show that simultaneous saccharification and fermentation enables generation of lactic acid, suitable for further chemical transformations, from agricultural residues. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Open AccessArticle On the Effect of Microwave Energy on Lipase-Catalyzed Polycondensation Reactions
Molecules 2016, 21(9), 1245; doi:10.3390/molecules21091245
Received: 27 July 2016 / Revised: 7 September 2016 / Accepted: 13 September 2016 / Published: 19 September 2016
Cited by 2 | PDF Full-text (1228 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Microwave energy (MWe) is, nowadays, widely used as a clean synthesis tool to improve several chemical reactions, such as drug molecule synthesis, carbohydrate conversion and biomass pyrolysis. On the other hand, its exploitation in enzymatic reactions has only been fleetingly investigated and, hence,
[...] Read more.
Microwave energy (MWe) is, nowadays, widely used as a clean synthesis tool to improve several chemical reactions, such as drug molecule synthesis, carbohydrate conversion and biomass pyrolysis. On the other hand, its exploitation in enzymatic reactions has only been fleetingly investigated and, hence, further study of MWe is required to reach a precise understanding of its potential in this field. Starting from the authors’ experience in clean synthesis and biocatalyzed reactions, this study sheds light on the possibility of using MWe for enhancing enzyme-catalyzed polycondensation reactions and pre-polymer formation. Several systems and set ups were investigated involving bulk and organic media (solution phase) reactions, different enzymatic preparations and various starting bio-based monomers. Results show that MWe enables the biocatalyzed synthesis of polyesters and pre-polymers in a similar way to that reported using conventional heating with an oil bath, but in a few cases, notably bulk phase polycondensations under intense microwave irradiation, MWe leads to a rapid enzyme deactivation. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Open AccessArticle Characterization of French Coriander Oil as Source of Petroselinic Acid
Molecules 2016, 21(9), 1202; doi:10.3390/molecules21091202
Received: 4 August 2016 / Revised: 31 August 2016 / Accepted: 6 September 2016 / Published: 8 September 2016
Cited by 6 | PDF Full-text (387 KB) | HTML Full-text | XML Full-text
Abstract
Coriander vegetable oil was extracted from fruits of French origin in a 23% yield. The oil was of good quality, with a low amount of free fatty acids (1.8%) and a concurrently high amount of triacylglycerols (98%). It is a rich source of
[...] Read more.
Coriander vegetable oil was extracted from fruits of French origin in a 23% yield. The oil was of good quality, with a low amount of free fatty acids (1.8%) and a concurrently high amount of triacylglycerols (98%). It is a rich source of petroselinic acid (C18:1n-12), an important renewable building block, making up 73% of all fatty acids, with also significant amounts of linoleic acid (14%), oleic acid (6%), and palmitic acid (3%). The oil was characterized by a high unsaponifiable fraction, comprising a substantial amount of phytosterols (6.70 g/kg). The main sterol markers were β-sitosterol (35% of total sterols), stigmasterol (24%), and Δ7-stigmastenol (18%). Squalene was detected at an amount of 0.2 g/kg. A considerable amount of tocols were identified (500 mg/kg) and consisted mainly of tocotrienols, with γ-tocotrienol as the major compound. The phospholipid content was low at 0.3%, of which the main phospholipid classes were phosphatidic acid (33%), phosphatidylcholine (25%), phosphatidylinositol (17%), and phosphatidylethanolamine (17%). About 50% of all phospholipids were non-hydratable. The β-carotene content was low at 10 mg/kg, while a significant amount of chlorophyll was detected at about 11 mg/kg. An iron content of 1.4 mg/kg was determined through element analysis of the vegetable oil. The influence of fruit origin on the vegetable oil composition was shown to be very important, particularly in terms of the phospholipids, sterols, and tocols composition. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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Review

Jump to: Research

Open AccessReview Bio-Based Aromatic Epoxy Monomers for Thermoset Materials
Molecules 2017, 22(1), 149; doi:10.3390/molecules22010149
Received: 24 November 2016 / Revised: 26 December 2016 / Accepted: 10 January 2017 / Published: 18 January 2017
Cited by 5 | PDF Full-text (14966 KB) | HTML Full-text | XML Full-text
Abstract
The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance,
[...] Read more.
The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA), a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups. Full article
(This article belongs to the Special Issue Chemicals from Biomass)
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