Archive for the ‘Hot Article’ Category

Methyl vinyl glycolate: a renewable platform compound with industrial potential

MVG reaction pathways

The metathesis and Claisen chemistry of methyl vinyl glycolate

Danish scientists have highlighted the diverse chemistry methyl vinyl glycolate (MVG) – a byproduct of the stannosilicate-catalysed formation of methyl lactate from monosaccharides and disaccharides – can offer as a powerful green platform molecule.

Robert Madsen and colleagues at the Technical University of Denmark used Grubbs-type catalysts to dimerise MVG by homo metathesis to yield (E)-2,5-dihydroxyhex-3-enedioate, a diastereomeric diester with potential for use as a monomer in the synthesis of functionalised polyesters. Cross metathesis of MVG with long chain terminal olefins gave unsaturated fatty acid methyl esters, which may be hydrogenated into customisable surfactants.

Performing Claisen-type rearrangements, the team also obtained industrially important unsaturated derivatives of adipic acid – a starting material for synthetic fibres. Palladium-catalysed transposition of MVG’s allylic alcohol derivative also resulted in a 1,4-dioxygenated motif which could be used as a precursor to 1,4-butanediol or γ-butyrolactone.

Want to know more? Read this article online, which is free to access until 30 September 2016:

Methyl vinyl glycolate as a diverse platform molecule” by A. Sølvhøj et al., Green Chem., 2016, DOI: 10.1039/C6GC01556E

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Tunable hemicellulose product streams

Japanese scientists have discovered a method to convert tree hemicellulose (xylan) in a tunable fashion to either one of three chemical product streams, depending on the combination of catalysts and solvent phases employed. Hemicellulose is 20-30% of the structural lignocellulose component of biomass, with cellulose (40-50%) and lignin (20-30%) accounting for the remainder. As part of a biorefinery, it is important to be able to advantageously develop all of the feedstock into products in order to reduce waste and value the economic and material investment made during biomass production.

First, rhenium was introduced into an iridium impregnated silica. The resulting catalyst was capable of producing xylitol from xylan (79% yield) if used in combination with sulphuric acid in an aqueous reaction. Some success in achieving a partial reduction to pentanol was then observed when an organic solvent was introduced to the reaction. Finally, full hydrogenolysis to give pentane (in 70% yield) was accomplished by adding a HZSM-5 zeolite to the biphasic reaction.

The heterogeneous catalyst is recoverable and can be reactivated to continue providing a good yield of pentane. Thus a new flexibility to woody biomass processing has been demonstrated, complementing the more prevalent studies on cellulose and lignin.

This work is included in a online collection showcasing work presented at the 3rd International Symposium on Green Chemistry held in La Rochelle, France on 3rd-7th May 2015. Access the full collection of articles here.

Selective transformation of hemicellulose (xylan) into n-pentane, pentanols or xylitol over a rhenium-modified iridium catalyst combined with acids
Sibao Liu, Yasuyo Okuyama, Masazumi Tamura, Yoshinao Nakagawa, Akio Imai and Keiichi Tomishige
Green Chem., 2016, Advance Article. DOI: 10.1039/C5GC02183A

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Recent HOT articles in Green Chemistry

The following HOT articles have been highlighted by the reviewers of the articles as being particularly interesting or significant pieces of research. These are all free to access until 30/11/2015. The order they appear in the list has no meaning or ranking.

Zinc(II)-catalyzed reactions of carbon dioxide and propargylic alcohols to carbonates at room temperature
Jiayin Hu, Jun Ma, Qinggong Zhu, Qingli Qian, Hongling Han, Qingqing Mei and Buxing Han
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01870F, Communication


Synthesis of a polyisobutylene-tagged fac-Ir(ppy)3 complex and its application as recyclable visible-light photocatalyst in a continuous flow process
Daniel Rackl, Peter Kreitmeier and Oliver Reiser
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01792K, Paper


Precise oxygen scission of lignin derived aryl ethers to quantitatively produce aromatic hydrocarbons in water
Zhicheng Luo, Yimeng Wang, Mingyuan He and Chen Zhao
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01790D, Paper


Selective hydrogenation of levulinic acid to 1,4-pentanediol in water using a hydroxyapatite-supported Pt–Mo bimetallic catalyst
T. Mizugaki, Y. Nagatsu, K. Togo, Z. Maeno, T. Mitsudome, K. Jitsukawa and K. Kaneda
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01878A, Communication


Oxidative desulfurization of DBT with H2O2 catalysed by TiO2/porous glass
C. Shen, Y. J. Wang, J. H. Xu and G. S. Luo
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01653C, Paper


Cooperative catalysis of Pt/C and acid resin for the production of 2,5-dimethyltetrahydrofuran from biomass derived 2,5-hexanedione under mild conditions
Huacong Zhou, Jinliang Song, Qinglei Meng, Zhenhong He, Zhiwei Jiang, Baowen Zhou, Huizhen Liu and Buxing Han
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01741F, Paper


Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
Zhengang Ke, Yan Zhang, Xinjiang Cui and Feng Shi
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01992C, Paper


Efficient pyrido[1,2-a]benzimidazole formation from 2-aminopyridines and cyclohexanones under metal-free conditions
Yanjun Xie, Jun Wu, Xingzong Che, Ya Chen, Huawen Huang and Guo-Jun Deng
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01978H, Communication


Antimony recovery from the halophosphate fraction in lamp phosphor waste: a zero-waste approach
David Dupont and Koen Binnemans
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01746G, Paper


An efficient and recyclable tetraoxo-coordinated zinc catalyst for the cycloaddition of epoxides with carbon dioxide at atmospheric pressure
Ran Ma, Liang-Nian He and Yue-Biao Zhou
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01826A, Paper


Production of solubilized carbohydrate from cellulose using non-catalytic, supercritical depolymerization in polar aprotic solvents
Arpa Ghosh, Robert C. Brown and Xianglan Bai
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC02071A, Paper


Attractive aerobic access to the α,β-unsaturated acyl azolium intermediate: oxidative NHC catalysis via multistep electron transfer
L. Ta, A. Axelsson and H. Sundén
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01965F, Communication


Catalyst-free dehydrative SN1-type reaction of indolyl alcohols with diverse nucleophiles “on water”
Jian Xiao, Hao Wen, Liang Wang, Lubin Xu, Zhihui Hao, Chang-Lun Shao and Chang-Yun Wang
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01838B, Paper


Towards sustainable fuels and chemicals through the electrochemical reduction of CO2: lessons from water electrolysis
Antonio J. Martín, Gastón O. Larrazábal and Javier Pérez-Ramírez
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01893E, Perspective


Light driven styrene epoxidation and hydrogen generation using H2O as an oxygen source in a photoelectrosynthesis cell
P. Farràs, C. Di Giovanni, J. N. Clifford, P. Garrido-Barros, E. Palomares and A. Llobet
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01589H, Paper


Synthesis of Ni-based co-catalyst functionalized W:BiVO4 nanofibers for solar water oxidation
Ki Ro Yoon, Jong Wan Ko, Doo-Young Youn, Chan Beum Park and Il-Doo Kim
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC01588J, Communication


Biomass-derived binderless fibrous carbon electrodes for ultrafast energy storage
R. Berenguer, F. J. García-Mateos, R. Ruiz-Rosas, D. Cazorla-Amorós, E. Morallón, J. Rodríguez-Mirasol and T. Cordero
Journal Article
Green Chem., 2015, Advance Article
DOI: 10.1039/C5GC02409A, Paper

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Addressing the ‘hidden’ pollution behind water purification membranes

Membrane technology is a major contributor to present day desalination and other water purification processes. Ironically, the benefits to water quality that membranes provide are counteracted by the actual membrane fabrication procedure, which collectively emits billions of litres of wastewater, contaminated with reprotoxic organic solvents, every year. Only 31% of membrane manufacturing companies surveyed treat the waste water, either themselves or using a waste management company. The rest dispose of this contaminated water down the sink.

This study, carried out by researchers at the University of Manchester, UK, sought to identify reusable absorbents for the purpose of purifying the aqueous wastestreams from membrane production. Several absorbents were found to be suitable for extracting DMF and NMP from wastewater. These include imprinted polymers, zeolites, and graphene based materials, all of which can be regenerated and reused. The purified waste water could also be reused in the membrane fabrication process, vastly reducing water use. Membrane waste water treatment

This article is open access and available to everyone to read for free:

Sustainable wastewater treatment and recycling in membrane manufacturing

Razali et al., Green Chem., 2015, advanced article. DOI: 10.1039/c5gc01937k

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LCA study expresses caution over assuming bio-based is green

A new study comparing life cycle assessments has shown that changing from a fossil derived feedstock to biomass is not necessarily beneficial to the environment. A reliance on food crops and inefficient conversion into chemical products will cause impact the environmental and result in an expensive product, also limiting its commercial opportunities.

Taking the example of hexamethylenediamine, the precursor to nylon-66, scientists based at Solvay in China have shown that the benefit of adopting a renewable feedstock (starch, in this instance) is counteracted by eutrophication concerns and greenhouse gas emissions. The issue largely stems from the cultivation of the biomass and the energy required to process the starch into chemical intermediates. The renewable route requires several high energy transformations to remove the original functionality of the biomass and obtain the conventional nylon monomer.

One lesson to be taken from this study is to give greater consideration to novel bio-based polymers that can be produced advantageously from bio-based feedstocks. Ideally, these would include wastes and agricultural by-products, thus making use of the reactive chemical groups inherent to the biomass rather than removing them.

Hexamethylenediamine (HMDA) from Fossil vs. Bio-based Routes: An Economic and Life Cycle Assessment Comparative Study

A. B. Dros et al., Green Chem., 2015, advanced article. DOI: 10.1039/C5GC01549A

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Recent HOT articles in Green Chemistry

The following HOT articles have been highlighted by the reviewers of the articles as being particularly interesting or significant pieces of research. These are all free to access until 30/09/2015. The order they appear in the list has no meaning or ranking.


Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(III) chloride and hydrochloric acid solution
T. Dallas Swift, Hannah Nguyen, Andrzej Anderko, Vladimiros Nikolakis and Dionisios G. Vlachos
Journal Article
DOI: 10.1039/C5GC01257K, Paper

C5GC01257K GA


Expanding the scope of biogenic substrates for the selective production of formic acid from water-insoluble and wet waste biomass
Jakob Albert and Peter Wasserscheid
Journal Article
DOI: 10.1039/C5GC01474C, Paper

C5GC01474C GA


Hybrid bipolar membrane electrodialysis/ultrafiltration technology assisted by a pulsed electric field for casein production
Sergey Mikhaylin, Victor Nikonenko, Gérald Pourcelly and Laurent Bazinet
Journal Article
DOI: 10.1039/C5GC00970G, Paper

C5GC00970G GA


Solvent free depolymerization of Kraft lignin to alkyl-phenolics using supported NiMo and CoMo catalysts
Chowdari Ramesh Kumar, Narani Anand, Arjan Kloekhorst, Catia Cannilla, Giuseppe Bonura, Francesco Frusteri, Katalin Barta and Hero Jan Heeres
Journal Article
DOI: 10.1039/C5GC01641J, Paper
From themed collection Lignin chemistry and valorisation

C5GC01641J GA


An interchangeable homogeneous ⇔ heterogeneous catalyst system for furfural upgrading
Lu Wang and Eugene Y.-X. Chen
Journal Article
DOI: 10.1039/C5GC01648G, Communication

C5GC01648G GA


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Re-routing aromatic degradation to give pyridine dicarboxylic acids

Biocatalytic conversion of lignin to aromatic dicarboxylic acids in Rhodococcus jostii RHA1 by re-routing aromatic degradation pathwaysBritish scientists, lead by Professor Tim Bugg at the University of Warwick, have reported a new method of converting lignin into useful monomers for the chemical industry. Processing difficulties mean that lignin remains an underutilised resource for the production of renewable chemicals. Only with the development of efficient depolymerisation methods will the potential of these waste products be realised. In this latest advance, the metabolic pathways in the bacterium Rhodococcus jostii RHA1 for the degradation of  lignin have been re-routed to generate aromatic dicarboxylic acids. Insertion of recombinant genes into R. jostii RHA1, followed by ammonia cyclisation generates pyridine-2,4-dicarboxylic acid or pyridine-2,5-dicarboxylic acid in yields of up to 125 mg L−1 from a wheat straw lignocellulose feed. The products have been identified as the building blocks of new bio-based polymers, and could help contribute to biomass resource efficiency and growth in the bio-polymer market.

This article is free to access untill 31st August 2015:

Biocatalytic conversion of lignin to aromatic dicarboxylic acids in Rhodococcus jostii RHA1 by re-routing aromatic degradation pathways, Z. Mycroft, M. Gomis, P. Mines, P. Law and T. D. H. Bugg, Green Chem., 2015, Advance Article. DOI: 10.1039/C5GC01347J

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From chip fat to biofuel

Chips in deep fat fryer

© Shutterstock

Researchers from Singapore and China have developed a cheap and green catalytic system for turning fatty acids into fuel that doesn’t require hydrogen or a solvent.

Hydrocarbon biofuels made from waste fats and oils, such as leftover cooking oil could help reduce our dependence on fossil fuels. Traditionally, these biofuels are synthesised by transesterifying lipids under harsh alkaline conditions; in addition to generating waste solvent, this technique does not remove enough oxygen, so the products are incompatible with diesel engines. The process also doesn’t work with fatty acids as they become soapy and deactivate the catalyst. Read the full article in Chemistry World»


Read the original journal article in Green Chemistry – it’s free to access until 17th August:
Effective deoxygenation of fatty acids over Ni(OAc)2 in the absence of H2 and solvent
Wenjing Li, Yongjun Gao, Siyu Yao, Ding Ma and Ning Yan
DOI: 10.1039/C5GC01147G, Paper

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Bread leavening proves useful for energy storage

Freshly baked bread

© Shutterstock

 Just like bread, hierarchically porous carbons (HPCs), are judged on their texture; so researchers in China have called on their baking know-how to cook up a sustainable method for producing these supercapacitor components

 HPCs could prove useful in energy storage because of their high surface area and short ion transport pathway. But existing synthetic methods for producing HPCs, including nanocasting and soft-templating, are unfeasible for industrial application as they require complex, expensive processes. Read the full article in Chemistry World» 


Read the original journal article in Green Chemistry – it’s free to access until 3rd August:
Inspired by bread leavening: one-pot synthesis of hierarchically porous carbon for supercapacitors
Jiang Deng, Tianyi Xiong, Fan Xu, Mingming Li, Chuanlong Han, Yutong Gong, Haiyan Wang and Yong Wang
DOI: 10.1039/C5GC00523J, Pape

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Plant waste solar panels

 A low cost, low energy route to solar grade silicon from rice hull ash (RHA), a sustainable source High purity silicon is essential for manufacturing solar panels. Unfortunately this prerequisite conversion of silica to elemental silicon requires a lot of energy, and the associated greenhouse gas emissions are significant. It has now been demonstrated that the ashes from burning biomass (rice hulls in this case) can provide a rich source of silica than can be reduced to give solar grade silicon.

For the preparation of the silica from rice hull ash only dilute acid and hot water are required. The energy requirement to then produce 99.9999% pure silicon is an order of magnitude less than the conventional process and is actually lower than the energy created by burning the rice hulls in the first place. As the carbon dioxide generated by burning biomass is originally fixed from the atmosphere by plants, the carbon footprint for the production of this sustainable silicon is very low.

Read the advanced article in Green Chemistry online now:

A low cost, low energy route to solar grade silicon from rice hull ash (RHA), a sustainable source

Julien C. Marchal, David J. Krug III, Patrick McDonnell, Kai Sun and Richard M. Laine

Green Chem., 2015, Advance Article. DOI: 10.1039/C5GC00622H

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