Co-reporter:Yiping Luo;Jiajun Fan;Vitaliy L. Budarin;Changwei Hu
Green Chemistry (1999-Present) 2017 vol. 19(Issue 20) pp:4889-4899
Publication Date(Web):2017/10/16
DOI:10.1039/C7GC02300F
A green process for the microwave-assisted hydrothermal selective dissolution and utilisation of hemicellulose in Phyllostachys heterocycla cv. Pubescens (shortened to pubescens) was developed. The process facilitated the efficient dissolution of hemicellulose at 200 °C, while obtaining hemicellulose-free residue that could be further used as starting materials within many industrial processes. A variety of analytical techniques (e.g., HPLC, FT-IR, SEM, TG/TGA, Py-GC/MS, TG-IR, 13C liquid NMR, 2D HSQC NMR, and 13C CPMAS NMR analysis) were used for the analysis of the obtained liquid and solid products, which revealed that hemicellulose was completely extracted from pubescens. A solid residue left after this process consists of cellulose and lignin in a pure form and can be used for production of glucose and aromatic compounds. Interestingly, a new route to produce hemicellulose-based films that could potentially be used for food packaging was achieved. The developed approach opens avenue for a low-cost and sustainable bamboo-based biorefinery.
Co-reporter:H. J. Salavagione;J. Sherwood;M. De bruyn;V. L. Budarin;G. J. Ellis;J. H. Clark;P. S. Shuttleworth
Green Chemistry (1999-Present) 2017 vol. 19(Issue 11) pp:2550-2560
Publication Date(Web):2017/06/06
DOI:10.1039/C7GC00112F
Nanomaterials have many advanced applications, from bio-medicine to flexible electronics to energy storage, and the broad interest in graphene-based materials and devices means that high annual tonnages will be required to meet this demand. However, manufacturing at the required scale remains unfeasible until economic and environmental obstacles are resolved. Liquid exfoliation of graphite is the preferred scalable method to prepare large quantities of good quality graphene, but only low concentrations are achieved and the solvents habitually employed are toxic. Furthermore, good dispersions of nanomaterials in organic solvents are crucial for the synthesis of many types of nanocomposites. To address the performance and safety issues of solvent use, a bespoke approach to solvent selection was developed and the renewable solvent Cyrene was identified as having excellent properties. Graphene dispersions in Cyrene were found to be an order of magnitude more concentrated than those achieved in N-methylpyrrolidinone (NMP). Key attributes to this success are optimum solvent polarity, and importantly a high viscosity. We report the role of viscosity as crucial for the creation of larger and less defective graphene flakes. These findings can equally be applied to the dispersion of other layered bi-dimensional materials, where alternative solvent options could be used as drop-in replacements for established processes without disruption or the need to use specialized equipment. Thus, the discovery of a benign yet high performance graphene processing solvent enhances the efficiency, sustainability and commercial potential of this ever-growing field, particularly in the area of bulk material processing for large volume applications.
Co-reporter:James H. Clark
Current Opinion in Green and Sustainable Chemistry 2017 Volume 8(Volume 8) pp:
Publication Date(Web):1 December 2017
DOI:10.1016/j.cogsc.2017.07.008
•What is now called Waste should be treated as a resource.•End-of-life plastics are a rich source of small organic chemical compounds.•Food waste contains many interesting organic chemical compounds but is complex.•Bio-refineries should convert biomass to chemicals, materials and energy.Waste is an extremely valuable resource that we have been accumulating over a long period. Interesting and viable organic “waste-to-resource” opportunities include plastics and food supply chain wastes. Their use as chemical feedstocks will fit well with a circular economy model. Plastics is a major waste opportunity: worldwide we only recycle a few % of the plastic we use, yet plastic manufacturing consumes some 10% of all the oil we consume, and much of it causes serious environmental damage through negligent release. The chemical content of food supply chain wastes are much more complex and varied than in plastic waste but offers a wide range of valuable chemical products. Bio-refineries can be defined as integrated complexes in which a number of renewable-derived feedstocks (bio-waste, biomass) can be converted in a range of useful products including chemicals, materials and fuels similar and sometimes identical to those obtained from petroleum.
Co-reporter:M. De bruyn, J. Fan, V. L. Budarin, D. J. Macquarrie, L. D. Gomez, R. Simister, T. J. Farmer, W. D. Raverty, S. J. McQueen-Mason and J. H. Clark
Energy & Environmental Science 2016 vol. 9(Issue 8) pp:2571-2574
Publication Date(Web):08 Jul 2016
DOI:10.1039/C6EE01352J
An unexpected opportunity is reported to improve the sustainability of biorefineries whereby 8 wt% levoglucosenone (LGE) can be derived from unconverted saccharides in a lignin-rich biorefinery waste stream in a highly selective fashion (>90%). Additionally, in the process a purer lignin is obtained which can be used for further processing or materials applications. LGE is a valuable and versatile product with a plethora of applications.
Co-reporter:James H. Clark, Thomas J. Farmer, Lorenzo Herrero-Davila and James Sherwood
Green Chemistry 2016 vol. 18(Issue 14) pp:3914-3934
Publication Date(Web):25 Apr 2016
DOI:10.1039/C6GC00501B
A circular economy will look to chemistry to provide the basis of innovative products, made from renewable feedstocks and designed to be reused, recycled, or the feedstock renewed through natural processes. The substances that products are made of will increasingly be treated as a resource equal to the raw materials, and not just disposed of. This perspective discusses the role of chemists in a world without waste.
Co-reporter:T. J. Farmer, J. H. Clark, D. J. Macquarrie, J. K. Ogunjobi and R. L. Castle
Polymer Chemistry 2016 vol. 7(Issue 8) pp:1650-1658
Publication Date(Web):22 Jan 2016
DOI:10.1039/C5PY01729G
Post-polymerisation modification of α,β-unsaturated polyesters (UPEs) is useful to deliver polymers with tuneable properties and applications different from their parent backbone. Bio-derivable itaconate unsaturated polyesters, with a range of co-monomers, were modified via a heterogeneously catalysed microwave-assisted Michael addition of pendants, acetylacetone (Hacac) and dimethyl malonate (DMM), to the polymer backbones with very short reaction times. Differential scanning calorimetry analysis showed an increase in the glass-transition temperatures of most of the saturated polyesters considered. Solubility and complexation studies demonstrated metal chelating abilities of the acetylacetone pendant can be retained, even following tethering to a polyester backbone. Additionally, it is demonstrated for the first time that Michael addition with Hacac and DMM can be used to reverse Ordelt saturation, an unwanted side-reaction in the synthesis of UPEs.
Co-reporter:Dr. Gema Durá;Dr. Vitaliy L. Budarin;Dr. José A. Castro-Osma;Dr. Peter S. Shuttleworth;Sophie C. Z. Quek; James H. Clark; Michael North
Angewandte Chemie 2016 Volume 128( Issue 32) pp:9319-9323
Publication Date(Web):
DOI:10.1002/ange.201602226
Abstract
Mesoporous carbonaceous materials (Starbons®) derived from low-value/waste bio-resources separate CO2 from CO2/N2 mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8–32 % versus 73 %) yet adsorb up to 65 % more CO2. The presence of interconnected micropores and mesopores is responsible for the enhanced CO2 adsorption. The Starbons® also showed three–four times higher selectivity for CO2 adsorption rather than N2 adsorption compared to AC.
Co-reporter:Dr. Gema Durá;Dr. Vitaliy L. Budarin;Dr. José A. Castro-Osma;Dr. Peter S. Shuttleworth;Sophie C. Z. Quek; James H. Clark; Michael North
Angewandte Chemie International Edition 2016 Volume 55( Issue 32) pp:9173-9177
Publication Date(Web):
DOI:10.1002/anie.201602226
Abstract
Mesoporous carbonaceous materials (Starbons®) derived from low-value/waste bio-resources separate CO2 from CO2/N2 mixtures. Compared to Norit activated charcoal (AC), Starbons® have much lower microporosities (8–32 % versus 73 %) yet adsorb up to 65 % more CO2. The presence of interconnected micropores and mesopores is responsible for the enhanced CO2 adsorption. The Starbons® also showed three–four times higher selectivity for CO2 adsorption rather than N2 adsorption compared to AC.
Co-reporter:Manmeet Kour, Satya Paul, James H. Clark, Vivek K. Gupta, Rajni Kant
Journal of Molecular Catalysis A: Chemical 2016 Volume 411() pp:299-310
Publication Date(Web):January 2016
DOI:10.1016/j.molcata.2015.11.001
•Design, synthesis and characterization of C/TiO2–SO3M.•4H-Pyrimido[2,1-b]benzothiazoles and benzoxanthenones were synthesised.•Multicomponent synthesis was effectively carried out under solvent-free conditions.•The catalyst showed excellent recyclability with negligible leaching of Lewis acid.A series of novel and highly efficient Lewis acids covalently grafted over sulfonic acid functionalized carbon@titania composites were successfully synthesized via sulfonation of carbon@titania composites followed by treatment with different Lewis acids like AlCl3, FeCl3, SbCl3, SnCl2, Cu(OAc)2 and Bi(NO3)3. The utility of the developed catalysts was explored for the synthesis of a diverse range of 4H-pyrimido[2,1-b]benzothiazoles and benzoxanthenones, and among various catalysts, C/TiO2–SO3–SbCl2 was found to be the most active. We report here the synthesis of five novel compounds and the structure of one of the compounds has also been confirmed by single-crystal X-ray diffraction. All the five prepared composites were characterized by FTIR and ICP-AES analysis, whereas the most active one, C/TiO2–SO3–SbCl2 was further characterized by XRD, EDX, CHNS, SEM, TEM, HRTEM and TGA. The catalyst can be recovered and reused for atleast five runs without any significant impact on catalytic activity and selectivity. The high catalytic activity, thermal stability, simple recovery and reusability, and eco-friendly nature of the catalyst makes the present method to be particularly attractive from the view point of green chemistry.A series of Lewis acid covalently grafted over sulfonated carbon@titania composites have been designed and investigated as sustainable recyclable catalytic system for multicomponent synthesis.
Co-reporter:C. Robert McElroy, Andri Constantinou, Leonie C. Jones, Louise Summerton and James H. Clark
Green Chemistry 2015 vol. 17(Issue 5) pp:3111-3121
Publication Date(Web):27 Mar 2015
DOI:10.1039/C5GC00340G
A unified metrics toolkit has been developed to evaluate sustainability of reactions, encompassing a comprehensive and holistic range of criteria for measuring how green a reaction is, covering quantitative and qualitative criteria both upstream and downstream of the reaction itself. In addition, three new metrics are proposed, optimum efficiency (OE), renewable percentage (RP) and waste percentage (WP). The structure of the toolkit is tailored to give a level of detail and complexity commensurate with the stage of research, with an initial ‘light-touch’ appraisal at a few mg scale through to very in-depth analyses incorporating lifecycle considerations at large (multi-kg) scale. The toolkit additionally allows benchmarking of reactions against state-of-the-art in terms of their ‘green credentials’. By promoting critical thinking in the user it also lends itself to being an educational tool, and its widespread adoption will support the training of a new generation of chemists to whom the use of greener and more sustainable techniques becomes second nature.
Co-reporter:Aleksra Borisova;Mario De Bruyn;Vitaliy L. Budarin;Peter S. Shuttleworth;Jennifer R. Dodson;Mateus L. Segatto
Macromolecular Rapid Communications 2015 Volume 36( Issue 8) pp:774-779
Publication Date(Web):
DOI:10.1002/marc.201400680
Co-reporter:P. S. Shuttleworth, M. De bruyn, H. L. Parker, A. J. Hunt, V. L. Budarin, A. S. Matharu and J. H. Clark
Green Chemistry 2014 vol. 16(Issue 2) pp:573-584
Publication Date(Web):28 Nov 2013
DOI:10.1039/C3GC41555D
Biorefineries are facilities that process biomass into fuels, power and value-added chemicals and with the increasing population and depleting petroleum reserves they are fast becoming more important to society. The technology required to process a wide variety of biomass types can be highly complex due to potentially unknown, varying or difficult to breakdown chemical structures within them. One of the prospective routes to a successful biorefinery, that can treat a wide range of biomass and produce products with good selectivity, is the use of nanoparticles as heterogeneous catalysts. The potential of nanoparticles to catalyse and modify chemical processes, thereby influencing both the nature of the products and their distribution is seen as highly promising. In this publication, we aim to give an overview of the use of a range of nano-catalysts and nano-enzymatic supports for greener biorefinery processing. Finally, future prospects of greener routes to nanoparticle production and their integration into biomass are discussed.
Co-reporter:Giulia Paggiola, Andrew J. Hunt, Con R. McElroy, James Sherwood and James H. Clark
Green Chemistry 2014 vol. 16(Issue 4) pp:2107-2110
Publication Date(Web):20 Jan 2014
DOI:10.1039/C3GC42526F
An improved multi-parameter approach to the correlation of enzymatic activity and solvent properties is proposed. The development of the correlation facilitated the introduction of renewable solvents in a CALB catalysed synthesis of fatty esters.
Co-reporter:James Sherwood, Mario De bruyn, Andri Constantinou, Laurianne Moity, C. Rob McElroy, Thomas J. Farmer, Tony Duncan, Warwick Raverty, Andrew J. Hunt and James H. Clark
Chemical Communications 2014 vol. 50(Issue 68) pp:9650-9652
Publication Date(Web):01 Jul 2014
DOI:10.1039/C4CC04133J
Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent. The dipolarity of dihydrolevoglucosenone is similar to NMP, DMF and sulpholane. Dihydrolevoglucosenone demonstrates similar performance to NMP in a fluorination reaction and the Menschutkin reaction.
Co-reporter:Andrew S. Marriott, Ed Bergström, Andrew J. Hunt, Jane Thomas-Oates and James H. Clark
RSC Advances 2014 vol. 4(Issue 1) pp:222-228
Publication Date(Web):05 Nov 2013
DOI:10.1039/C3RA44428G
This study reports the development of calcium alginate-based highly mesoporous carbon spheres (AMCS). These materials exhibit significant potential in chromatographic applications and demonstrated similar efficiency to commercially available porous graphitic carbon (PGC) and are superior to Starbon® materials in separation of polar carbohydrate analytes. The AMCS exhibit a narrow particle size distribution, are highly spherical and exhibit extensive mesoporous networks (up to ca. 90% mesoporosity). It is shown how calcium content can significantly influence the textural properties of the resulting AMCS materials. The AMCS production process requires no additional templating agents and temperatures of only 800 °C. In contrast, PGC are manufactured through an energy-intensive manufacture process, which requires a hard-templated mesoporous carbon intermediate to be pyrolysed to over 2000 °C under argon. Thus AMCS demonstrate promise as a green alternative to PGC in chromatographic applications.
Co-reporter:Jiajun Fan ; Mario De bruyn ; Vitaliy L. Budarin ; Mark J. Gronnow ; Peter S. Shuttleworth ; Simon Breeden ; Duncan J. Macquarrie
Journal of the American Chemical Society 2013 Volume 135(Issue 32) pp:11728-11731
Publication Date(Web):July 29, 2013
DOI:10.1021/ja4056273
A systematic investigation of the interaction of microwave irradiation with microcrystalline cellulose has been carried out, covering a broad temperature range (150 → 270 °C). A variety of analytical techniques (e.g., HPLC, 13C NMR, FTIR, CHN analysis, hydrogen–deuterium exchange) allowed for the analysis of the obtained liquid and solid products. Based on these results a mechanism of cellulose interaction with microwaves is proposed. Thereby the degree of freedom of the cellulose enclosed CH2OH groups was found to be crucial. This mechanism allows for the explanation of the different experimental observations such as high efficiency of microwave treatment; the dependence of the selectivity/yield of glucose on the applied microwave density; the observed high glucose to HMF ratio; and the influence of the degree of cellulose crystallinity on the results of the hydrolysis process. The highest selectivity toward glucose was found to be ∼75% while the highest glucose yield obtained was 21%.
Co-reporter:Lucie A. Pfaltzgraff, Mario De bruyn, Emma C. Cooper, Vitaly Budarin and James H. Clark
Green Chemistry 2013 vol. 15(Issue 2) pp:307-314
Publication Date(Web):02 Jan 2013
DOI:10.1039/C2GC36978H
Our society currently faces the twin challenges of resource depletion and waste accumulation leading to rapidly escalating raw material costs and increasingly expensive and restrictive waste disposal legislation. The variety of food processes used in the food and drink industry globally generate food supply chain waste on a multi tonne scale every year. Such resides include wheat straw surpluses, spent coffee grounds or citrus peels, all of which represent a resource for an integrated, product focused biorefinery. Orange peel is particularly interesting: pectin and D-limonene, two marketable components, can be produced together with several flavonoids under the same conditions at a litre scale using low temperature microwave treatment. The running costs for such a process on large scale (50000 metric tonnes per annum) have been estimated on the basis of the combined production of pectin and D-limonene.
Co-reporter:J. R. Dodson, V. L. Budarin, A. J. Hunt, P. S. Shuttleworth and J. H. Clark
Journal of Materials Chemistry A 2013 vol. 1(Issue 17) pp:5203-5207
Publication Date(Web):15 Mar 2013
DOI:10.1039/C3TA10568G
Reproducible highly mesoporous monolithic materials (0.5–0.7 cm3 g−1, 9–15 nm) are prepared from a variety of fresh shaped abundant macroalgae using a simple green approach without the necessity for supercritical carbon dioxide (scCO2) drying. This opens up the possibility for low cost and sustainable structured materials for chromatography, catalyst supports and drug delivery systems.
Co-reporter: James H. Clark;Dr. Duncan J. Macquarrie ;James Sherwood
Chemistry - A European Journal 2013 Volume 19( Issue 16) pp:5174-5182
Publication Date(Web):
DOI:10.1002/chem.201204396
Abstract
The traditional Biginelli reaction is a three-component condensation between urea, benzaldehyde and an acetoacetate ester to give a dihydropyrimidinone. An investigation into catalytic and solvent effects has returned the conclusion that the diketo–enol tautomerisation equilibrium of the dicarbonyl reactant dictates the yield of the reaction. Whereas the solvent is responsible for the tautomerisation equilibrium position, the catalyst only serves to eliminate kinetic control from the reaction. Generally, to preserve reaction efficiency and improve sustainability, bio-derivable p-cymene was found to be a useful solvent. The metal–enolate intermediate that results from the application of a Lewis acidic catalyst often cited as promoting the reaction appears to hinder the reaction. In this instance, a Brønsted acidic solvent can be used to return greater reactivity to the dicarbonyl reagent.
Co-reporter:James H Clark;Thomas J Farmer;Duncan J Macquarrie
Sustainable Chemical Processes 2013 Volume 1( Issue 1) pp:
Publication Date(Web):2013 December
DOI:10.1186/2043-7129-1-23
Ionic liquids have found uses in many applications, one of which is the joint solvation and catalysis of chemical transformations. Suitable Brønsted acidic ionic liquids can be formed by combining lactams with sulphonic acids. This work weighs up the relative benefits and disadvantages of applying these Brønsted acidic ionic liquid catalysts in esterifications through a series of comparisons using green chemistry metrics.A new bio-based ionic liquid was synthesised from N-methyl pyrrolidinone and p-cymenesulphonic acid, and tested as a catalyst in three Fischer esterifications under different conditions. An evaluation of the performance of this Brønsted acidic ionic liquid was made through the comparison to other ionic liquid catalysts as well as conventional homogeneous Brønsted acids.Extending the argument to feedstock security as well as mass utilisation, ultimately in most instances traditional mineral acids appear to be the most sensible option for Brønsted acid esterification catalysts. Ester yields obtained from Brønsted acidic ionic liquid catalysed procedures were modest. This calls into question the diversity of research exploring esterification catalysis and the role of ionic liquids in esterifications.
Co-reporter:Rafael Luque;James H Clark
Sustainable Chemical Processes 2013 Volume 1( Issue 1) pp:
Publication Date(Web):2013 December
DOI:10.1186/2043-7129-1-10
Waste valorisation practises have attracted a significant amount of attention in recent years with the aim of managing waste in the most sustainable way. Food waste constitutes a largely under-exploited residue from which a variety of valuable chemicals can be derived. This contribution is aimed to set the scene for a further development and promotion of sustainable food waste valorisation practises to different end products using green chemical technologies.
Co-reporter:H.-B. Yue, Y.-D. Cui, P. S. Shuttleworth and James H. Clark
Green Chemistry 2012 vol. 14(Issue 7) pp:2009-2016
Publication Date(Web):14 May 2012
DOI:10.1039/C2GC35509D
Cottonseed protein bioplastics (CPBs) from cottonseed flour were successfully prepared by hot-press molding in the presence of urea, aldehydes and glycerol. The effect of cross-linking treatment on the thermal stability, water absorption resistance and mechanical strength was investigated, and found to improve all properties. Increasing glycerol concentration resulted in a decrease in denaturation and α-relaxation temperature of the cottonseed protein as well as storage modulus of the plasticised CPBs. Interestingly, the colour and odor of the CPBs before and after hot compression changed. The mechanism proposed involved urea induced protein denaturation and Maillard-driven generation of the cross-linked structure, both in thermal and alkaline processed conditions. According to Fickian diffusivity, liquid transport and liquid permeability, chemical interactions and physical transport processes are responsible for the different water transport behaviours in the CPBs and the cross-linked CPBs, respectively. These findings could provide valuable in-depth information for tailoring the properties of the environmentally sustainable CPBs, which are attractive for low-load bearing applications, such as agriculture, packing and garden amenities, etc.
Co-reporter:James H. Clark, Duncan J. Macquarrie and James Sherwood
Green Chemistry 2012 vol. 14(Issue 1) pp:90-93
Publication Date(Web):01 Dec 2011
DOI:10.1039/C1GC16299C
(R)-(+)-Limonene, which is available in large quantities from citrus waste, and its close derivative p-cymene are shown herein to be viable yet sustainable solvents for amidation and esterification reactions.
Co-reporter:Alina Mariana Balu;Dr. Vitaliy Budarin;Dr. Peter S. Shuttleworth;Lucie A. Pfaltzgraff; Keith Waldron;Dr. Rafael Luque; James H. Clark
ChemSusChem 2012 Volume 5( Issue 9) pp:1694-1697
Publication Date(Web):
DOI:10.1002/cssc.201200381
Co-reporter:Vitaliy L. Budarin, Yizhe Zhao, Mark J. Gronnow, Peter S. Shuttleworth, Simon W. Breeden, Duncan J. Macquarrie and James H. Clark
Green Chemistry 2011 vol. 13(Issue 9) pp:2330-2333
Publication Date(Web):07 Jul 2011
DOI:10.1039/C1GC15560A
Macro-algae (seaweed) is an abundant and, for the most part, under-utilised resource. This study has shown that microwave (MW)-mediated pyrolysis of seaweed occurs at extremely low temperatures and produces chemical rich bio-oils which are rich in aromatics, sugars and other high value chemicals.
Co-reporter:Jennifer R. Dodson, Andrew J. Hunt, Vitaly L. Budarin, Avtar S. Matharu and James H. Clark
RSC Advances 2011 vol. 1(Issue 3) pp:523-530
Publication Date(Web):23 Aug 2011
DOI:10.1039/C1RA00271F
Considerable mineralogical changes occur during the combustion of biomass such as wheat straw, which lead to variation in the physical, chemical and textural properties of the ashes formed. Mineralogical and chemical changes occur above combustion temperatures of 500 °C causing reductions in the solubility of potassium, chloride, silica and sulfate. This can be directly correlated to the evaporation of KCl, dissociation of K2SO4, softening of silica and formation of alkali silicates. Calcium extraction increased above combustion temperatures of 700 °C due to the decomposition of CaCO3. We have discovered, for the first time, that the inherent alkali in unleached wheat straw is sufficient to solubilise up to 30% of the silica in the ash at room temperature. This could be used to produce potassium silicate solution as a new valuable by-product of wheat straw combustion. It was also found that incomplete combustion at high temperatures, following leaching of ashes can lead to the formation of porous activated carbons and inorganic materials, demonstrating yet another valuable use for this waste material.
Co-reporter:Jiajun Fan, Mario De bruyn, Zongyuan Zhu, Vitaliy Budarin, Mark Gronnow, Leonardo D. Gomez, Duncan Macquarrie, James Clark
Chemical Engineering and Processing: Process Intensification (September 2013) Volume 71() pp:37-42
Publication Date(Web):1 September 2013
DOI:10.1016/j.cep.2013.01.004
The conversion of cellulose and cellulosic waste to fermentable sugars has been successfully demonstrated. Using a novel microwave intensified hydrothermal depolymerisation of cellulosic materials in liquid hot water, at pressures below 300 psi, conversions of up to 40% of fermentable sugars were obtained with limited by-product formation. A high selectivity for glucose over other sugars has been observed. Temperature is the crucial parameter as limited conversion is observed below 180 °C and optimum conversion is attained around 220 °C.Graphical abstractDownload full-size imageHighlights► Novel microwave system has been successfully designed for waste utilisation. ► Using this intensified system for cellulosic waste 30% of glucose was obtained. ► A high selectivity for glucose over other sugars has been observed. ► The optimum conversion temperature was found around 220 °C. ► The system does not require any additives such as base or acid.
Co-reporter:Peter Shuttleworth, Vitaliy Budarin, Mark Gronnow, James H. Clark, Rafael Luque
Journal of Natural Gas Chemistry (May 2012) Volume 21(Issue 3) pp:270-274
Publication Date(Web):1 May 2012
DOI:10.1016/S1003-9953(11)60364-2
A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues. Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures (120–180°C vs 250–400°C). The gas obtained from microwave-assisted pyrolysis was found to contain CO2, CH4 and CO as major components as well as other related chemicals (e.g. acids, aldehydes, alkanes) which were obtained in different proportions depending on the selected feedstock.
Co-reporter:Sarah Abou-Shehada, James H. Clark, Giulia Paggiola, James Sherwood
Chemical Engineering and Processing: Process Intensification (January 2016) Volume 99() pp:88-96
Publication Date(Web):1 January 2016
DOI:10.1016/j.cep.2015.07.005
•A tunable solvent has variable properties precisely controlled by the user.•Distillation can be avoided with the use of tunable solvents.•Applications of non-volatile solvents increase when tuned with carbon dioxide.Research into the synthesis and application of green solvents is a developing field of interest relevant to a variety of chemical manufacturers. Tunable solvents utilising carbon dioxide lend themselves to a reduction in work-up solvent and can help avoid the need for energy intensive solvent recovery options such as distillation. This perspective examines the potential benefits of tunable solvents to the chemical manufacturing industry and the environment. Freed from the usual reliance on distillation, high boiling solvents with an inherently lessened potential to cause air emissions can be used as part of a tunable solvent system. The application of bio-based solvents as tunable reaction media is highlighted as an area for further development.Download full-size image
Co-reporter:Louise Summerton, Rick J. Taylor, James H. Clark
Sustainable Chemistry and Pharmacy (December 2016) Volume 4() pp:67-76
Publication Date(Web):1 December 2016
DOI:10.1016/j.scp.2016.09.003
•Promoting uptake of green and sustainable methodologies in pharmaceutical synthesis.•Suite of free, shareable and interactive educational resources have been created.•User-friendly tools and guides can be readily integrated into everyday practice.•Bespoke online learning platform provides opportunity to tailor training.•Benefits to medicinal and process chemistry are showcased via novel research.An extensive suite of educational and training resources have been created by the CHEM21 project to promote the uptake and application of green and sustainable methodologies in the synthesis of pharmaceuticals. They include a bespoke online learning platform containing free, shareable and interactive material suitable for distance learning; easy to use tools and guides that can be readily embedded into everyday practice; and a new RSC text book available in both print and electronic format. These initiatives were specifically designed to result in the elaboration of an educational program to train both students and those currently working within the industry. The involvement of EFPIA partners in their development has ensured that the training materials and methods developed have practical applicability within the medicinal and process chemist community. The research originated by the CHEM21 project has also informed the development of the educational and training material and provided case studies to exemplify the benefits of adopting sustainable chemistry in medicinal and process chemistry.
Co-reporter:J. R. Dodson, V. L. Budarin, A. J. Hunt, P. S. Shuttleworth and J. H. Clark
Journal of Materials Chemistry A 2013 - vol. 1(Issue 17) pp:NaN5207-5207
Publication Date(Web):2013/03/15
DOI:10.1039/C3TA10568G
Reproducible highly mesoporous monolithic materials (0.5–0.7 cm3 g−1, 9–15 nm) are prepared from a variety of fresh shaped abundant macroalgae using a simple green approach without the necessity for supercritical carbon dioxide (scCO2) drying. This opens up the possibility for low cost and sustainable structured materials for chromatography, catalyst supports and drug delivery systems.
Co-reporter:James Sherwood, Mario De bruyn, Andri Constantinou, Laurianne Moity, C. Rob McElroy, Thomas J. Farmer, Tony Duncan, Warwick Raverty, Andrew J. Hunt and James H. Clark
Chemical Communications 2014 - vol. 50(Issue 68) pp:NaN9652-9652
Publication Date(Web):2014/07/01
DOI:10.1039/C4CC04133J
Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent. The dipolarity of dihydrolevoglucosenone is similar to NMP, DMF and sulpholane. Dihydrolevoglucosenone demonstrates similar performance to NMP in a fluorination reaction and the Menschutkin reaction.
![Pyridine, 2,3,5,6-tetrafluoro-4-[(trifluoromethyl)thio]-](http://img.cochemist.com/ccimg/99700/99646-85-2.png)
![Pyridine, 2,3,5,6-tetrafluoro-4-[(trifluoromethyl)thio]-](http://img.cochemist.com/ccimg/99700/99646-85-2_b.png)
![Benzene, 4-chloro-2-nitro-1-[(trifluoromethyl)sulfonyl]-](http://img.cochemist.com/ccimg/2000/1948-14-7.png)
![Benzene, 4-chloro-2-nitro-1-[(trifluoromethyl)sulfonyl]-](http://img.cochemist.com/ccimg/2000/1948-14-7_b.png)
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