Archive for 2011

Critical reviews on selective oxidation of glycerol and recycling homogeneous catalysts using mebrane separation.

Selective catalytic oxidation of glycerol – perspectives for high value chemicals. The increasing worldwide production of biodiesel has led to an excess supply of crude glycerol, prompting researchers to investigate its valorisation.  Thanks to its three hydroxyl groups, glycerol is a potential starting material for several high-value fine chemicals.  Various metals can catalyse glycerol oxidation.  However, the selectively of these reactions is dependent on the active phase, metal particle size, pore size of the support and pH of the reaction medium.  In this review, Dumeignil and co-workers look at the recent developments in new catalysts and spotlight the role of reaction conditions. (Green Chem., 2011, DOI: 10.1039/c1gc15320j)

Recent advances in recycling of homogeneous catalysts using membrane separation. Membrane filtration is now an attractive approach for the recycling of soluble catalysts.  Nanofiltration has shown great potential as a method for process intensification in organo-, anzyme, and homogeneous catalysis.  Vogt and co-workers discuss selected, recent advances in catalyst recovery by membrane filtration in this review and look at implications for future development.  (Green Chem., 2011, DOI: 10.1039/c1gc15264e)
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New Impact Factor for Green Chemistry

Green Chemistry received a 5-year impact factor* of 6.056 in the 2010 Journal Citation Reports released by Thomson ISI this week.  This reveals steady growth in the impact of Green Chemistry over the last 5 years, reinforcing the importance and maturity of the Journal. 

Five years ago Green Chemistry had an impact factor of 3.255 and its 2010 impact factor of 5.472 demonstrates the Journal’s increasing quality, putting it in the top 20 of all multidisciplinary chemistry journals.

We would like to thank our Editorial and Advisory Board members and all of our authors and referees for their contributions; this support is vital to the continuing success of Green Chemistry.

The release of the 2010 impact factors also brought good news for RSC Publishing with a rise in the average impact factor across all journals and some great individual performances… read more here.

*A 5-year impact factor is the average number of times articles from a journal published in the past five years have been cited in the JCR year.  It is calculated by taking the number of citations in the JCR year to articles published in the preceding 5 years and dividing by the number of articles published in the previous 5 years.

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Controlled lactide polymerisation in supercritical carbon dioxide with organo-catalyst

Researchers from Australia and the UK have developed a truly ‘green’ process for the synthesis of polylactic acid in the absence of toxic solvents and catalysts.

The team led by Idriss Blakely (The University of Queensland, Australia) and Steven Howdle (University of Nottingham, UK) have developed an approach where polylactide can be synthesised in a controlled manner in supercritical CO2 using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organo-catalyst.  This new method, unlike others before it, does not require the use of organic solvents or metal catalysts, and is conducted at much lower temperatures than for bulk polymerisation of lactic acid.

To read more, click the link below! FREE until 27 July.

Controlled polymerisation of lactide using an organo-catalyst in supercritical carbon dioxide, Idriss Blakey, Anguang Yu, Steven M. Howdle, Andrew K. Whittaker and Kristofer J. Thurecht, Green Chem., 2011, DOI: 10.1039/C1GC15344G

If you liked this, you may also be interested in this article too!

Direct conversion of polyamides to ω-hydroxyalkanoic acid derivatives by using supercritical MeOH, Akio Kamimura, Kouji Kaiso, Shuzo Suzuki, Yusuke Oishi, Yuki Ohara, Tsunemi Sugimoto, Kohichi Kashiwagi and Makoto Yoshimoto, Green Chem., 2011, DOI: 10.1039/C1GC15172J

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A free environmental assessment tool for liquid chromatography methods

Scientists from Sweden, Egypt, Denmark and India have collaborated to develop a computational tool to assess the greenness of high performance liquid chromatography (HPLC) methods.

This environmental assessment tool (EAT) takes into account the safety, environmental and health issues for all solvents involved or used in the chromatographic method.  A total score is then calculated that can be used to compare the greenness of various HPLC methods.  Although other tools have been developed to try and evaluate the green aspect of these methods, they often do not provide a sufficiently quantitative result for comparison between various methods and are not always user-friendly or widely accessible.

The HPLC-EAT software can be downloaded free of charge at http://www.biotek.lu.se/hplc-eat/ and can also be combined with another free software eco-solvent tool to perform life cycle assessments of waste disposal options (such as distillation or incineration).

Click the link below to find out more! Read the full text for free until 22 July

Energy & environment: Free environmental assessment for liquid chromatography solvents, Y Gaber, U Tornvall, M A Kumar, M A Amin and R Hatti-Kaul, Green Chem., 2011, DOI: 10.1039/c0gc00667j

You may also be interested in the following article too!

Expanding GSK’s solvent selection guide – embedding sustainability into solvent selection starting at medicinal chemistry, Richard K. Henderson, Concepción Jiménez-González, David J. C. Constable, Sarah R. Alston, Graham G. A. Inglis, Gail Fisher, James Sherwood, Steve P. Binks and Alan D. Curzons, Green Chem., 2011, 13, 854-862 DOI: 10.1039/C0GC00918K

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Recycling polyamides to give valuable chemicals

 Polyamides have been decomposed to ω-hydroxyalkanoic acid derivatives – important intermediates in the chemical industry – using supercritical methanol.  This is one of the first methods for economical upgrading of polymers through the depolymerisation process.

Akio Kamimura and colleagues from Yamaguchi University and UIbe Industries Ltd., Japan, have developed a method to convert polyamides to valuable chemicals.  Currently, recycling of plastics commonly involves converting the polymers back to their monomers. However, these methods are not always economically viable because they are often more expensive than other ways of treating waste plastics.  By converting polymers to valuable chemicals, this would make polymer recycling a more attractive route and solve some of the economic problems. 

In this study, by using supercritical methanol, Kamimura converted nylon-6 selectively to two valuable compounds – methyl 6-hydroxycapronate and methyl 5-hexenoate. Given that the average price for these ω-hydroxyalkanoic acid derivatives is about 6-7 times higher (per kg, based on 2008 figures) than the monomer (caprolactam), Kamimura believes that this method will open up new avenues in the development of plastics recycling.

To read more, please click the link below!  Full text Free until 20th July.

Direct conversion of polyamides to ω-hydroxyalkanoic acid derivatives by using supercritical MeOH, Akio Kamimura, Kouji Kaiso, Shuzo Suzuki, Yusuke Oishi, Yuki Ohara, Tsunemi Sugimoto, Kohichi Kashiwagi and Makoto Yoshimoto, Green Chem., 2011, DOI: 10.1039/C1GC15172J

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2011 Presidential Green Chemistry Challenge Awards

For the 16th year, the U.S. Environmental Protection Agency is recognizing pioneering chemical technologies developed by leading researchers and industrial innovators who are making significant contributions to pollution prevention in the United States. These prestigious awards recognise and promote research and development of less-hazardous alternatives to existing technologies that reduce or eliminate waste, particularly hazardous waste, in industrial production.

The Presidential Green Chemistry Challenge Awards are bestowed in five categories. Green Chemistry would like to congratulate the 2011 award winners:

  • Academic: Bruce H. Lipshutz, PhD, University of California, Santa Barbara
  • Small business: BioAmber, Inc., Plymouth, Minn.
  • Greener synthetic pathways: Genomatica, San Diego, Calif.
  • Greener reaction conditions: Kraton Performance Polymers, Inc., Houston, Texas
  • Designing greener chemicals: The Sherwin-Williams Company, Cleveland, Ohio

The awards were made on Monday night, June 20th at the Green Chemistry Challenge Awards ceremony in Washington D.C. as an opener to the 15th Annual Green Chemistry & Engineering Conference which is being held in concert with the 5th International Conference on Green & Sustainable Chemistry.

Green Chemistry Editor Sarah Ruthven is in Washington D.C. attending the Conferences; if you would like to meet her there please contact the Editorial Office.

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Domino reaction to make heterocyclic spiro compounds

A new method has been developed to synthesis spiro-substituted benzo[b]furo[3,4-e][1,4]diazepene derivatives in one step, forming two spiro rings and five σ bonds in the process.

This chemo- and regioselective [4+2+1] domino cyclization reaction was discovered by scientists from Xuzhou Normal University, China and Texas Tech University, USA.  The synthesis of  heterocyclic compounds with quaternary carbon centres is important as these compounds are useful intermediates in organic synthesis and are often biologically active. 

The procedure developed here is performed in water with microwave irradiation and uses easily available and cheap starting materials.  This one-pot reaction can be performed in 10-18 minutes with reduced waste production and without the use of any strong acids or metal promoters.  In addition, recrystallization and chromatography purification procedures can be avoided as the pure products can be obtained by simply washing the crude product with 95% ethanol.

The authors feel this will serve as a nice addition to Group-Assistant Purification chemistry.

Click the link below to read more! Full text free until 18th July.

[4+2+1] Domino cyclization in water for chemo- and regioselective synthesis of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives, Chuang Cheng, Bo Jiang, Shu-Jiang Tu and Guigen Li, Green Chem., 2011, DOI: 10.1039/C1GC15183E

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“In tube” NMR procedure for analysis of Chiral alcohols and amines

An efficient method for the NMR analysis of chiral alcohols and amines has been developed with an improved detection limit. Valentine Ananikov and Nikolay Orlov, Zelinsky Institute of Organic Chemistry, Russia, prepared samples for analysis directly in the NMR tubes; this has big advantages over existing methods to analyse these compounds. 

NMR analysis of chiral compounds normally involves derivatisation with a suitable chiral agent to allow you to tell apart diastereoisomers in NMR spectra. The major limitation of this has been the fact that the derivatisation has to be done as a seperate reaction. This adds further work-up and purification procedures (generating waste), is time-consuming and means a relatively large sample is required for analysis.

However, Ananikov derivatised samples within the NMR tube, avoiding waste generation and providing samples for analysis in less than 5 min (including preparation time).  All analysis could be performed on a routine NMR instrument, and could give accurate measurements for samples less than 0.01 mg. This underlines the environmentally benign and superior nature of the procedure developed by this group.

To read more, please see:

NMR analysis of chiral alcohols and amines: development of an environmentally benign “in tube” procedure with high efficiency and improved detection limit, Nikolay V. Orlov and Valentine P. Ananikov, Green Chem., 2011, DOI: 10.1039/C1GC15191F

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Green Solvents for Synthesis Conference Report

Conference report by Ewa Gebauer-Henke and Mark Muldoon 

The latest issue of Green Chemistry features papers from the “Green Solvents for Synthesis” conference that was held in October 2010. The bi-annual DECHEMA conference on green solvents has a reputation for attracting world leaders in the field of green chemistry and also for being held in beautiful locations in Germany. In 2008, the meeting was held in Friedrichshafen on Lake Constance, while this recent meeting was in the stunning town of Berchtesgaden in the German Bavarian Alps. 

Berchtesgaden

Berchtesgaden

Common themes throughout the conference were the use of ionic liquids, water, supercritical fluids (CO2 and water), CO2 expanded solvent systems and solvents from renewable sources. The meeting attracted a mix of industrialists, academics and graduate students from across the globe. Addressing the challenges in this area requires an interdisciplinary approach and attendees had a wide range of scientific and engineering backgrounds. The varied nature of the research presented at this meeting is clear from the contributions to this special issue. For those interested, the full conference programme can still be viewed online

One of the things that seemed clear from the discussions and debates among participants was that this field is continuing to mature and strive for higher standards. Many of the discussions related to improving the overall greenness of processes and topics such as “life cycle analysis” and “energy” were often raised. The claim that a solvent is intrinsically green in itself is not something that holds up to scrutiny and therefore researchers are having to demonstrate how solvents can be used to improve a process overall; for example by allowing catalyst separation and recycling or delivering improved reaction rates and product selectivity. 

The first lecture of the conference by Philip Jessop highlighted many of these issues and set the tone for the meeting. He outlined what he felt were the four “grand challenges” in the field of green solvents. Additionally, he had polled some of the leading academic researchers in the field of solvents prior to the conference, asking them what solvents they felt would have the biggest impact in the coming years. He then discussed the interesting results of this survey during his talk. The details of his lecture can be seen in his paper “Searching for green Solvents”. 

Ionic liquids have gathered a great deal of interest in the last decade or so and a number of talks highlighted how these solvents can be used to improve the greenness of a process. For example, Peter Wasserscheid delivered a very well received talk on the topic of ionic liquids in the field of heterogeneous catalysis. He discussed both SILP (“Supported Ionic Liquid Phase”) technology and SCILLs (Solid Catalysts with Ionic Iiquid Layers’).  For a number of years, researchers have been investigating the use of SILPs; which involves utilising a thin ionic liquid layer on a solid support to immobilise homogeneous transition metal catalysts. However, more recently, the SCILL approach has emerged, and this involves coating a “traditional” heterogeneous type catalyst with a layer of ionic liquid. The layer of ionic liquid can result in modification of the properties and performance of the heterogeneous catalyst. Peter’s talk illustrated well how ionic liquids could improve catalyst performance, therefore leading to a greener process.   

The conference chairman Prof Walter Leitner

The conference chairman Prof Walter Leitner

Continuous flow is often the best way to improve the efficiency of a process and “alternative solvent systems” can enable flow processes to be developed in ways not possible with conventional organic solvents. For example, Pedro Lozano described his group’s work on continuous flow enzymatic synthesis of biodiesel in mono- and multiphase systems using a combination of ionic liquids and supercritical CO2. While Lasse Greiner discussed the application of continuous flow systems for the synthesis of ionic liquids. He stressed how the transition from batch to continuous is only possible, when kinetic and thermodynamic studies have been carried out and showed how inline ATR-IR and calorimetry were powerful tools for such studies.  He demonstrated that the synthesis of ionic liquids can be realized with consistent product specifications; necessary in large scale production. 

The importance of in-situ techniques was also highlighted in Jan-Dierk Grunwald’s talk “Heterogeneous catalysis in dense carbon dioxide: opportunities, limitations and mechanistic understanding”.  He presented work on both catalytic hydrogenations and oxidations in dense and supercritical CO2. As part of these studies, ATR-IR was used to determine phase behaviour and X-ray adsorption spectroscopy to study the catalyst under high pressure reaction conditions. Developing an in-depth understanding of reactions in such solvents is important if they are to be fully exploited in an industrial setting. 

Ultimately, the aim of green chemistry is to have an impact in the real world and there are an increasing number of industrial processes that now utilise “alternative solvent” technologies. Several examples were highlighted during this conference including those that exploited supercritical water. This was particularly nice to see as this is a solvent system that is often labelled as an academic curiosity. More details of industrial scale processes for scH2O are described in the paper by Adschiri and co-workers. 

Solvents play a crucial role to vast number of processes and they are therefore key in developing more sustainable chemical processes. We would highly recommend that researchers interested in the important area of green chemistry attend a future DECHEMA green solvents conference. The next one is scheduled for early October 2012 (and starts just as Oktoberfest in finishing in Munich). As mentioned, these meetings bring together leaders from academia and industry from across a range of disciplines. In fact many of these leading figures not only discuss their research but also entertain the participants! At this past it closed with a traditional Bavarian banquet dinner where some very well known academics entertained the attendees singing that Leitner and Howdle classic “Always Use Green Chemistry Tools”; something, previously highlighted by Kathleen Too in this blog (October 15th entry). 

Ewa Gebauer-Henke
CAT Catalytic Center Postdoctoral Fellow
ITMC, RWTH Aachen University 

Mark Muldoon
School of Chemistry and Chemical Engineering
Queen’s University Belfast

Pictures, courtesy of Prof Kenneth Seddon (QUILL, Queen’s University of Belfast)

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Green Chemistry Themed Issue on Green Solvents Marks the International Year of Chemistry

Graphical abstract: The echoes of green chemistryTo mark the International Year of Chemistry in 2011, Green Chemistry has published a themed issue on green solvents for synthesis.  This themed issue is online now and contains articles by world-leading chemists detailing the recent advances and challenges faced in this area. It has been approved as an official IYC Activity.

The issue showcases the innovative research towards the substitution of volatile organic solvents in solution phase synthesis. The series of articles presented in this themed issue are based on the keynote presentations at an international conference organised by Dechema, held in October 2010 in Berchtesgaden, Germany. 

You can read Guest Editor Walter Leitner’s editorial online here and the full issue online here.

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