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Faraday Discussions

Hana Dureckova, Tom K Woo, Konstantin A Udachin, John A Ripmeester, Saman Alavi
Clathrate hydrate phases of Cl2 and Br2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds...
July 19, 2017: Faraday Discussions
Alison J Edwards, Campbell F Mackenzie, Peter R Spackman, Dylan Jayatilaka, Mark A Spackman
Structure-property relationships are the key to modern crystal engineering, and for molecular crystals this requires both a thorough understanding of intermolecular interactions, and the subsequent use of this to create solids with desired properties. There has been a rapid increase in publications aimed at furthering this understanding, especially the importance of non-canonical interactions such as halogen, chalcogen, pnicogen, and tetrel bonds. Here we show how all of these interactions - and hydrogen bonds - can be readily understood through their common origin in the redistribution of electron density that results from chemical bonding...
July 19, 2017: Faraday Discussions
Lisa Weigand, Shahrokh Mostame, Agnieszka Brandt-Talbot, Tom Welton, Jason P Hallett
The ionoSolv pretreatment is a new technique employing protic low-cost ionic liquids and has previously been applied to successfully fractionate switchgrass and the grass Miscanthus giganteus. This study investigates the effect of using the protic ionic liquid solution [N2220][HSO4]80% with two different acid/base ratios (1.02 and 0.98) at 120, 150 and 170 °C on the pretreatment outcome of the hardwood willow. The ionic liquid solution was able to fractionate willow, and a pulp and lignin fraction were recovered after treatment...
July 18, 2017: Faraday Discussions
Yun-Yan Wang, Yi-Ru Chen, Simo Sarkanen
Lignins upgrade the lignocellulosic cell-wall domains in all vascular plants; they embody 20-30% of terrestrial organic carbon. For 50 years, mistaken assumptions about the configuration of lignin have hindered the development of useful polymeric materials with a lignin content above 40 wt%. Now, polymeric materials composed only of methylated softwood lignin derivatives can exhibit better tensile behavior than polystyrene. Marked improvements may be achieved with small quantities (5-10 wt%) of miscible blend components as simple as poly(ethylene glycol)...
July 12, 2017: Faraday Discussions
Jos Lelieveld
In atmospheric chemistry, interactions between air pollution, the biosphere and human health, often through reaction mixtures from both natural and anthropogenic sources, are of growing interest. Massive pollution emissions in the Anthropocene have transformed atmospheric composition to the extent that biogeochemical cycles, air quality and climate have changed globally and partly profoundly. It is estimated that mortality attributable to outdoor air pollution amounts to 4.33 million individuals per year, associated with 123 million years of life lost...
July 12, 2017: Faraday Discussions
Barbara J Finlayson-Pitts
The term "Anthropocene" was coined by Professor Paul Crutzen in 2000 to describe an unprecedented era in which anthropogenic activities are impacting planet Earth on a global scale. Greatly increased emissions into the atmosphere, reflecting the advent of the Industrial Revolution, have caused significant changes in both the lower and upper atmosphere. Atmospheric reactions of the anthropogenic emissions and of those with biogenic compounds have significant impacts on human health, visibility, climate and weather...
July 7, 2017: Faraday Discussions
Ian P Wood, Enriqueta Garcia-Gutierrez, Nikolaus Wellner, Keith W Waldron
Plant cell wall materials derived from a range of waste biomass sources have great potential as a source of sustainable alternatives to petrochemicals. Perhaps the most straightforward way of realising this potential would be to hydrolyse the most efficiently fermentable polymers into their constituent sugars and use yeast to ferment these into useful chemicals. However, it also makes sense to pre-extract components which have a greater value in polymeric form. This is particularly true for non-cellulosic polymers, which are rich in poorly-fermentable pentose sugars...
July 6, 2017: Faraday Discussions
J G Santaclara, A I Olivos-Suarez, I du Fossé, A Houtepen, J Hunger, F Kapteijn, J Gascon, M A van der Veen
The highly porous titanium based metal-organic framework NH2-MIL-125(Ti) has recently attracted significant attention in the field of photocatalysis as a promising material for H(+) reduction. This work reveals charge transfer upon visible light illumination from this MOF to two different charge acceptors, as an alternative to sacrificial electron donors. Charge transfer is demonstrated through a combined spectroscopic study between this MOF and: (1) 2-(1H-pyrazol-3-yl)phenol, a molecule that functionally mimics the tyrosine-histidine pair, responsible for shuttling the holes to the oxygen evolving centre in natural photosynthesis, and (2) TEMPO, a well known and stable radical...
July 5, 2017: Faraday Discussions
Jiayue He, Kefeng Huang, Kevin J Barnett, Siddarth H Krishna, David M Alonso, Zachary J Brentzel, Samuel P Burt, Theodore Walker, Williams F Banholzer, Christos T Maravelias, Ive Hermans, James A Dumesic, George W Huber
Catalytic strategies for the synthesis of 1,5-pentanediol (PDO) with 69% yield from hemicellulose and the synthesis of 1,6-hexanediol (HDO) with 28% yield from cellulose are presented. Fractionation of lignocellulosic biomass (white birch wood chips) in gamma-valerolactone (GVL)/H2O generates a pure cellulose solid and a liquid stream containing hemicellulose and lignin, which is further dehydrated to furfural with 85% yield. Furfural is converted to PDO with sequential dehydration, hydration, ring-opening tautomerization, and hydrogenation reactions...
July 5, 2017: Faraday Discussions
Marco Balabajew, Nina Balke, Martin Bazant, Roland Bennewitz, Nikolay Brilliantov, Astrid S de Wijn, Ranabir Dey, Carlos Drummond, Robert Dryfe, Hubert Girault, Kelsey Hatzell, Robert Hillman, Konstantin Kornev, Alexei A Kornyshev, Irena Kratochvilova, Tom Krupenkin, Alpha Lee, Andy Mount, Frieder Mugele, Hyacinthe Randriamahazaka, Oliver Robotham, George Schatz, David Schiffrin, Elisabeth Smela, Andriy Yaroshchuk
No abstract text is available yet for this article.
July 4, 2017: Faraday Discussions
Martin Bazant, Roland Bennewitz, Lydéric Bocquet, Nikolay Brilliantov, Ranabir Dey, Carlos Drummond, Robert Dryfe, Hubert Girault, Kelsey Hatzell, Konstantin Kornev, Alexei A Kornyshev, Irena Kratochvilova, Anthony Kucernak, Mohit Kulkarni, Sunny Kumar, Alpha Lee, Serge Lemay, Himani Medhi, Andrew Mount, Frieder Mugele, Susan Perkin, Mark Rutland, George Schatz, David Schiffrin, Elisabeth Smela, Evgeny Smirnov, Michael Urbakh, Andriy Yaroshchuk
No abstract text is available yet for this article.
July 4, 2017: Faraday Discussions
David Andersson, Martin Bazant, Roland Bennewitz, Lyderic Bocquet, Fernando Bresme, Nikolay Brilliantov, Astrid S de Wijn, Carlos Drummond, Robert Dryfe, Robert Hillman, Alexei A Kornyshev, Günther Krämer, Mohit Kulkarni, Alpha Lee, Hua Li, Frieder Mugele, Carla Perez Martinez, Susan Perkin, Mircea Rastei, Oliver Robotham, George Schatz, David Schiffrin, Ran Tivony, Michael Urbakh, Andriy Yaroshchuk
No abstract text is available yet for this article.
July 4, 2017: Faraday Discussions
Martin Bazant, Roland Bennewitz, Samuel Booth, Robert Dryfe, Hubert Girault, Robert Hillman, Alexei A Kornyshev, Alpha Lee, Serge Lemay, Andy Mount, Frieder Mugele, Oliver Robotham, George Schatz, David Schiffrin, Debabrata Sikdar, Evgeny Smirnov, Ran Tivony, Michael Urbakh
No abstract text is available yet for this article.
July 4, 2017: Faraday Discussions
José-Vitor Bomtempo, Flavia Chaves Alves, Fabio de Almeida Oroski
This paper proposes a framework with six dimensions that can be useful for evaluating the potential and the current stage of a bio-based platform chemical. The framework considers the technological and strategic challenges to be fulfilled by a company that intends to lead a platform based on a bio-based chemical. A platform chemical should be an intermediate molecule, with a structure able to generate a number of derivatives, that is produced at a competitive cost, capable of allowing exploitation of the scale and scope economies, and inserted within a complete innovation ecosystem that is able to create value with governance mechanisms that are capable of allowing coordination of the innovation process and facilitation of the value capture by the focal company leading the platform, in our case the producer of the platform molecule...
July 3, 2017: Faraday Discussions
Maxim V Galkin, Davide Di Francesco, Ulrica Edlund, Joseph S M Samec
This review discusses the challenges within the research area of modern biomass fractionation and valorization. The current pulping industry focuses on pulp production and the resulting cellulose fiber. Hemicellulose and lignin are handled as low value streams for process heat and the regeneration of process chemicals. The paper and pulp industry have therefore developed analytical techniques to evaluate the cellulose fiber, while the other fractions are given a low priority. In a strive to also use the hemicellulose and lignin fractions of lignocellulosic biomass, moving towards a biorefining concept, there are severe shortcomings with the current pulping techniques and also in the analysis of the biomass...
July 3, 2017: Faraday Discussions
A A Lapkin, P K Heer, P-M Jacob, M Hutchby, W Cunningham, S D Bull, M G Davidson
Data-mining of Reaxys and network analysis of the combined literature and in-house reactions set were used to generate multiple possible reaction routes to convert a bio-waste feedstock, limonene, into a pharmaceutical API, paracetamol. The network analysis of data provides a rich knowledge-base for generation of the initial reaction screening and development programme. Based on the literature and the in-house data, an overall flowsheet for the conversion of limonene to paracetamol was proposed. Each individual reaction-separation step in the sequence was simulated as a combination of the continuous flow and batch steps...
July 3, 2017: Faraday Discussions
Marcel Lorenz, Stefan Sattler, Mehedi Reza, Alexander Bismarck, Eero Kontturi
Cellulose nanocrystals (CNCs) are topical in materials science but their full potential is yet to be fulfilled because of bottlenecks in the production: the process consumes huge amounts of water, recycling the strong acid catalyst is difficult, and purification steps are cumbersome, particularly with lengthy dialysis. Production of CNCs with HCl vapour overcomes many of these difficulties but the dispersion of CNCs from the already hydrolysed fibre matrix is a formidable challenge. This study is a fundamental effort to explore very basic means to facilitate CNC dispersion from cotton linter fibres (filter paper), hydrolysed to levelling off degree of polymerization by HCl vapour...
July 3, 2017: Faraday Discussions
Sacha Pérocheau Arnaud, Linglin Wu, Maria-Angelica Wong Chang, James W Comerford, Thomas J Farmer, Maximilian Schmid, Fei Chang, Zheng Li, Mark Mascal
A family of monomers, including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA), terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives, all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (Tg) than those prepared from their primary diol equivalents...
July 3, 2017: Faraday Discussions
Long Zhou, Fabio Santomauro, Jiajun Fan, Duncan Macquarrie, James Clark, Christopher J Chuck, Vitaliy Budarin
Generally, biorefineries convert lignocellulosic biomass into a range of biofuels and further value added chemicals. However, conventional biorefinery processes focus mainly on the cellulose and hemicellulose fractions and therefore produce only low quality lignin, which is commonly burnt to provide process heat. To make full use of the biomass, more attention needs to be focused on novel separation techniques, where high quality lignin can be isolated that is suitable for further valorisation into aromatic chemicals and fuel components...
June 30, 2017: Faraday Discussions
Max Cárdenas-Fernández, Maria Bawn, Charlotte Hamley-Bennett, Penumathsa K V Bharat, Fabiana Subrizi, Nurashikin Suhaili, David P Ward, Sarah Bourdin, Paul A Dalby, Helen C Hailes, Peter Hewitson, Svetlana Ignatova, Cleo Kontoravdi, David J Leak, Nilay Shah, Tom D Sheppard, John M Ward, Gary J Lye
Over 8 million tonnes of sugar beet are grown annually in the UK. Sugar beet pulp (SBP) is the main by-product of sugar beet processing which is currently dried and sold as a low value animal feed. SBP is a rich source of carbohydrates, mainly in the form of cellulose and pectin, including d-glucose (Glu), l-arabinose (Ara) and d-galacturonic acid (GalAc). This work describes the technical feasibility of an integrated biorefinery concept for the fractionation of SBP and conversion of these monosaccharides into value-added products...
June 30, 2017: Faraday Discussions
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