Author Archive

Green Solvents 2012 – Submission deadline extended to the 30th April 2012!

The latest event in the biennial ‘Green Solvents for Synthesis‘ conference series is being held on the 7th-10th October 2012 in Boppard, Germany – Advanced Concepts for Solution Phase Chemistry and Processes.

The submission deadline for abstracts for oral and poster presentations has now been extended to the 30th April 2012!  To submit your abstract or for more details, please click here.

This year’s scientific focus lies on energy-efficient processes, selectivity control for waste prevention, alternative and efficient use of raw materials, activation and capture of CO2 and integrated reaction and separation processes.

The scientific programme features the traditional Sunday evening lecture, keynote lectures by renowned experts in the field and submitted oral presentations.  An additional highlight is the poster session which will give you the opportunity for gripping discussions on cutting-edge research results.

More information can be found at the conference website: http://events.dechema.de/events/en/gsfs2012.html.  Registration for the event will open by the end of June.

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Perspective: Process intensification strategies and membrane engineering

In this perspective, Enrico Drioli and colleagues evaluate how membrane systems can help achieve ‘green process engineering’.

The principles of a process intensification strategy can lead to the development and redesign of new processes which are more compact and efficient than their traditional counterparts.  These new processes can allow for better exploitation of raw materials, lower energy consumption and a reduced plant volume.  Membrane technologies can be seen as contributing to these principles and over the last few years, the scope for membrane operations has become widely recognised.

In this perspective article, the authors provide an overview of membrane applications and their perspectives in the fields of hydrogen production and distillation will be analysied through case studies.  The aim of this review is to show how redesigning traditional operations as membrane systems might contribute to the realization of the goals of process intensification. 

This article is free to access until the 16th May 2012! Click on the link below to find out more…

Process intensification strategies and membrane engineering, Enrico Drioli, Adele Brunetti, Gianluca Di Profio and Giuseppe Barbieri, Green Chem., 2012, DOI: 10.1039/C2GC16668B

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RSC US Roadshows 2012 – Week 1: California

As week 1 of the RSC US Raodshows 2012 begins, look out for Green Chemistry Editor Sarah Ruthven who will be visiting universities in California this week.

Starting on the 16th April, RSC Publishing will be touring the United States of America to share more than 170 years experience of publishing in the chemical sciences. Sixteen universities across the country will be hosting these one-day events, which are open to all members of the hosting institute.

Week 1 sees RSC Publishing visit four universities in California:

  • 16th AprilUniversity of California Irvine
  • 17th AprilUniversity of California Los Angeles
  • 18th AprilUniversity of California Santa Barbara
  • 20th AprilUniversity of California Berkeley

Click here to find out more…

Keep up to date with the RSC US roadshow by following the Royal Society of Chemistry on Facebook, or look out for #RSC2012 on Twitter!

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The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?

A continuous flow Barbier reaction was employed for the production of a key pharmaceutical intermediate (1) in the synthesis of edivoxetine·HCl (a highly selective norepinephrine re-uptake inhibitor).

US scientists from Eli Lilly and Company and D&M Continuous Solutions, led by Michael Kopach, report the development of a continuous Barbier reaction which preserves chirality and the product obtained in >99% ee.  The team ran the process in a series of continuous stirred tank reactors, where residence time, solvent composition, stoichiometry and operations temperature were optimised to produce 12 g per hour of the ketone precursor to 1 with 98% ee and 88% in situ yield for 47 hours total flow time.  Continuous salt formation and isolation of 1 could then be achieved from the ketone solution with >99% purity.

This process offers up several significant advantages over a traditional Grignard batch process.  This continuous flow method gave greater than 30% reduced process mass intensity and magnesium usage relative to the batch method.  Equally, the flow process resulted in >100 x less excess magnesium to quench and >100 x less diisobutylaluminum hydride to initiate giving significant safety benefits.  The authors expect that the maximum long-term scale of the process is 50 L which would replace 4000-6000 L batch reactors.

This article is free to access until the 11th May 2012! Click on the link below to find out more…

The continuous flow Barbier reaction: an improved environmental alternative to the Grignard reaction?, Michael E. Kopach, Dilwyn J. Roberts, Martin D. Johnson, Jennifer McClary Groh, Jonathan J. Adler, John P. Schafer, Michael E. Kobierski and William G. Trankle, Green Chem., 2012, DOI: 10.1039/C2GC35050E

You may also be interested in the following article as well – free to access for 2 weeks!

Development of safe and scalable continuous-flow methods for palladium-catalyzed aerobic oxidation reactions, Xuan Ye, Martin D. Johnson, Tianning Diao, Matthew H. Yates and Shannon S. Stahl, Green Chem., 2010, 12, 1180-1186

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Meet our Authors: Franck Dumeignil

© CNRS Photothèque / Cyril FRESILLON

Franck Dumeignil is a Professor in the Unit of Catalysis and Solid State Chemistry at the University of Lille, France.  His research is focused on upgrading alcohols from biomass to obtain fuel, solvents and building blocks for the chemical industry, and enhancing bio-oil for energy needs.  Franck took a few moments to talk to Green Chemistry

Who or what initially inspired you to become a chemist? 

I always liked science in general – mathematics, physics and chemistry. I must confess that I was a lazy student at that time, but I could obtain nice results in chemistry without working a lot, while for mathematics I had to work a lot harder to achieve good results! That was when I decided to select chemistry as a speciality. At University we had an impressive teacher, Prof. Ginette Leclercq, who was responsible for the catalysis lectures. Thanks to her I fell in love with catalysis and became a specialist in the subject! Ironically, after my PhD thesis in France and having spent almost 7 years in Japan, I came back to France, and obtained a full professor position due to an opening available because of the retirement of none other than Prof. Leclercq! I feel this is an amazing thing in my life – I could never have expected this when I was a student following the top-quality lectures of Prof. Leclercq, while being so impressed… 

What has been the motivation behind your recent research? 

My recent research concerns catalysis for biorefineries. This is an exciting subject with so many perspectives, so many new things to discover and new processes to develop and implement! 

What do you see as the main challenges facing research in this area? 

There are multiple challenges. The molecules issued from biomass are more reactive than those issued from fossil resources. This can be seen as a decisive advantage, but when using heterogeneous catalysis, the catalysts then tend to coke much more rapidly. Furthermore, the feeds contain water, and the reactions generate water in most of the cases: what happens to the catalytic sites in these conditions? Another challenge is that the biomass-derived molecules usually contain a few different moieties, and selective attack is also an issue. 

Where do you see the field of Green Chemistry being in 5 or 10 years time? 

Green chemistry will develop and reach maturity as green metrics will be refined and become more and more reliable. What people usually need is ‘numbers’, which are much more concrete than concepts. Reliably and systematically quantifying green chemistry for any process/reaction will be a decisive advance in this field. 

And finally… 

If you could not be a scientist, but could be anything else, what would you be? 

A pianist, or a composer (not too late!), or a F1 driver, or even a squash player! My hobbies are of course in line with this!

Take a look a couple of Franck’s recent articles in Green Chemistryfree to access until the 4th May 2012:

Selective catalytic oxidation of glycerol: perspectives for high value chemicals, Benjamin Katryniok, Hiroshi Kimura, Elżbieta Skrzyńska, Jean-Sébastien Girardon, Pascal Fongarland, Mickaël Capron, Rémy Ducoulombier, Naoki Mimura, Sébastien Paul and Franck Dumeignil, Green Chem., 2011, 13, 1960-1979

Glycerol dehydration to acrolein in the context of new uses of glycerol, Benjamin Katryniok, Sébastien Paul, Virginie Bellière-Baca, Patrick Rey and Franck Dumeignil, Green Chem., 2010, 12, 2079-2098

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The fate of bio-carbon in FCC co-processing products

French scientists have investigated the mechanisms involved in producing mixed bio/fossil fuels and the fate of the bio-carbon during the process.

In order to meet the regulation constraints for transportation fuels set by the European Commission, a promising solution is to produce mixed bio/fossil fuels by co-processing biomass pyrolysis oil with crude oil fractions (obtained from distillation in a standard oil refinery).  In previous work, Yves Schuurman and colleagues from the University of Lyon, France, showed that gasoline could be produced by co-processing hydrodeoxygenated pyrolysis oil with conventional vacuum gas oil in a lab-scale fluid catalytic cracking (FCC) unit.  However, up till now, accurate determination of the proportion of renewable molecules in the target product to be commercialised, i.e. gasoline, has not be preformed, but is very important for technical and marketing reasons. 

In this work, the Carbon-14 (14C) method was used to determine bio-carbon content in FCC products.  While fossil fuel is virtually 14C-free, biofuels contain the present-day ‘natural’ levels of 14C.  The results from this study have given valuable information on the co-processing mechanism, and the authors show that co-processing bio-oil with fossil fuel resources leads to bio-carbon impoverished gasoline but bio-carbon enriched liquefied petroleum gas.

This article is free to access until 3rd May 2012!  Click on the link below to find out more…

The fate of bio-carbon in FCC co-processing products, Gabriella Fogassy, Nicolas Thegarid, Yves Schuurman and Claude Mirodatos, Green Chem., 2012, DOI: 10.1039/C2GC35152H

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Molecular interactions between polybenzimidazole and [EMIM]OAc, and derived ultrafiltration membranes for protein separation

Scientists from Singapore have employed an ionic liquid to fabricate polybenzimidazole (PBI) membranes for protein separation and water reuse.

PBI has been extensively investigated in the field of membrane separation technologies due to its high glass transition temperature, stable thermal properties and excellent chemical resistance in harsh environments.   One major drawback of PBI though is its low solubility.  Only a few highly polar and aprotic organic solvents are able to dissolve PMI (such as DMSO, DMF and N,N-dimethylacetamide), but these are relatively toxic and volatile.

Here, the team from the National University of Singapore led by Tai-Shung Chung found that 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) was able to dissolve PBI under much lower temperatures and pressures compared to traditional solvents.  The acetate anion of the ionic liquid could form hydrogen bonds with the PBI chains, effectively breaking the interchain bonding in PBI. Ultrafiltration membranes could then be made from the PBI-[EMIM]OAc solution by a non-solvent induced phase separation method, with the resulting membranes achieving a high separation factor. 

This article is free to access until the 27th April 2012!  Click on the link below to find out more…

Molecular interactions between polybenzimidazole and [EMIM]OAc, and derived ultrafiltration membranes for protein separation, Ding Yu Xing ,  Sui Yung Chan and Tai-Shung Chung, Green Chem., 2012, DOI: 10.1039/C2GC35134J  

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Green Chemistry issue 4 now online!

The latest issue of Green Chemistry is now available online!

The front cover highlights work by Milton Hearn and colleagues from Monash University, Australia, who investigated the oxidative N-demethylation of tropane alkaloids to their nortropane derivatives using hydrogen peroxide (H2O2) and an iron (III) tetraamido macrocycle catalyst.  The tertiary N-methylamine group is commonly found in a range of naturally occurring alkaloids, and modification of this tertiary amine group on tropane alkaloids alters their pharmacological properties. Previous methods for removing this methyl group tend to involve the use of large molar excess of expensive and/or toxic reagents.  The method reported by Hearn and his team uses a relatively benign oxidising reagent that can be easily decomposed to innocuous products once the reaction is complete.

One-pot oxidative N-demethylation of tropane alkaloids with hydrogen peroxide and a FeIII-TAML catalyst, Duy D. Do Pham, Geoffrey F. Kelso, Yuanzhong Yang and Milton T. W. Hearn, Green Chem., 2012, 14, 1189-1195

The inside front cover features work by Ana Rodríguez and co-workers from the University of Santiago de Compostela and the University of Vigo, Spain, who report on the duel role of surfactants in microalga cell lysis for the extraction of antioxidants.  The integrated process proposed uses non-ionic surfactants as cell disruptors and organic extractants of intracellular antioxidants.  The viability of the process was checked using real samples which yielded higher antioxidant activity than that provided by a traditional ultrasound-based method. 

On the double role of surfactants as microalga cell lysis agents and antioxidants extractants, G. Ulloa, C. Coutens, M. Sánchez, J. Sineiro, J. Fábregas, F. J. Deive, A. Rodríguez and M. J. Núñez, Green Chem., 2012, 14, 1044-1051

These articles will be free to access for 6 weeks!

Stay up-to-date with the latest content in Green Chemistry by registering for our free table of contents alerts.

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An efficient recyclable peroxometalate-based polymer-immobilised ionic liquid phase (PIILP) catalyst for hydrogen peroxide-mediated oxidation

Scientists have developed an efficient peroxophosphotungstate-based polymer-immobilised ionic liquid phase catalyst for the epoxidation of allylic alcohols and alkenes.

Polyoxometalates (POMs) have been shown to be efficient Bronsted acid catalysts and selective oxidation catalysts in various important transformations.  Research in recent years has been focused on surface immobilisation of POMs in order to develop continuous flow process and improve the robustness and recyclability of the catalysts and to avoid or reduce catalyst leaching.

In this work, scientists from Newcastle University and Queen’s University, Belfast led by Simon Doherty, Julian Knight and Christopher Hardacre prepared a linear cation-decorated polymeric support with tuneable surface properties and microstructure by ring-opening metathesis polymerisation of a norbornene-based monomer with cyclooctene.  The resulting peroxophosphotungstate-based polymer-supported ionic liquid phase catalyst presented an efficient system for the epoxiadation of allylic alcohols and alkenes.  Importantly, the catalysts could be easily recovered and reused with only a slight reduction in performance. 

This article is free to access until the 19th April 2012!  Click on the link below to find out more…

An efficient recyclable peroxometalate-based polymer-immobilised ionic liquid phase (PIILP) catalyst for hydrogen peroxide-mediated oxidation, Simon Doherty, Julian G. Knight, Jack R. Ellison, David Weekes, Ross W. Harrington, Christopher Hardacre and Haresh Manyar, Green Chem., 2012, DOI: 10.1039/C2GC16679H

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Salt modified starch: sustainable, recyclable plastics

Utilization of starch as a recyclable plastic has been achieved giving a flexible plastic with mechanical properties similar to oil derived plastics.

Currently, the search for biodegradable polymers from sustainable resources has mainly focused on polylactic acid (PLA).  However, compared to petroleum based plastics, the cost of PLA is still high.  Starch as a highly abundant and sustainable material is an attractive alternative to PLA, but extensive hydrogen bonding between chains makes the plasticisation of starch difficult. 

In this work, Andrew Abbott and colleagues from the University of Leicester, UK, show that incorporation of a simple quaternary ammonium salt can overcome this problem and lead to a flexible plastic with mechanical properties similar to oil-derived plastics.  A transparent material can be produced by compression moulding which has a mechanical strength similar to polyolefin plastics.  These samples were also shown to be recyclable, losing little of their original properties.

This article is free to access until the 13th April 2012!  Click on the link below to find out more…

Salt modified starch: sustainable, recyclable plastics, Andrew P. Abbott, Andrew D. Ballantyne, Jesus Palenzuela Conde, Karl S. Ryder and William R. Wise, Green Chem., 2012, DOI: 10.1039/C2GC16568F

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