Switchable solvents

Philip Jessop and co-workers report tertiary amine solvents with switchable-hydrophilicity which have been applied to recycling polystyrene foam.

These switchable-hydrophilicity solvents (SHS) have very low miscibility with water and air, but are completely miscible in the presence of a CO2 atmosphere.  Jessop and his team had previously reported using N,N,N’-tributylpentanamidine as a SHS which could easily be removed from organic products.  However, N,N,N’-tributylpentanamidine is very difficult to synthesise and is not commercially available.

Switchable solvents

In this work, Jessop reports the use of several tertiary amines which are either commercially available or easily prepared.  As well as investigating the factors which affect the rate of switching, the group also applied one of the amines studied to the recycling of polystyrene foam.  The polystyrene foam was dissolved in one of the SHSs, and after addition of carbonated water formed dense polystyrene.  In future, this could potentially make the transportation and recycling of polystyrene foam waste less energy intensive and more efficient.

Access this article for free by clicking on the link below:

Tertiary amine solvents having switchable hydrophilicity

Philip G. Jessop, Lisa Kozycz, Zahra Ghoshouni Rahami, Dylan Schoenmakers, Alaina R. Boyd, Dominik Wechsler and Amy M. Holland, Green Chem., 2011, DOI: 10.1039/C0GC00806K

For a related article, please see:

A solvent having switchable hydrophilicity
Philip G. Jessop, Lam Phan, Andrew Carrier, Shona Robinson, Christoph J. Dürr and Jitendra R. Harjani, Green Chem., 2010, 12, 809-814
DOI: 10.1039/B926885E

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Top ten most accessed articles in December

This month sees the following articles in Green Chemistry that are in the top ten most accessed:-

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, DOI: 10.1039/C0GC00307G, Critical Review 

Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts 
Hirokazu Kobayashi, Yukiko Ito, Tasuku Komanoya, Yuto Hosaka, Paresh L. Dhepe, Koji Kasai, Kenji Hara and Atsushi Fukuoka 
Green Chem., 2011, Advance Article, DOI: 10.1039/C0GC00666A, Paper 

Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water 
Thomas S. Hansen, Jerrik Mielby and Anders Riisager 
Green Chem., 2011, 13, 109-114, DOI: 10.1039/C0GC00355G, Paper 

Synthesis of thermoplastic starch mixed esters catalyzed by the in situ generation of imidazolium salts 
André Lehmann, Bert Volkert, Mehdi Hassan-Nejad, Tonino Greco and Hans-Peter Fink 
Green Chem., 2010, 12, 2164-2171, DOI: 10.1039/C0GC00366B, Paper 

ß-cyclodextrin catalysed synthesis of tryptanthrin in water 
Atul Kumar, Vishwa Deepak Tripathi and Promod Kumar 
Green Chem., 2011, 13, 51-54, DOI: 10.1039/C0GC00523A, Communication 

Eco-friendly liquid chromatographic separations based on the use of cyclodextrins as mobile phase additives 
Víctor González-Ruiz, Andrés G. León, Ana I. Olives, M. Antonia Martín and J. Carlos Menéndez 
Green Chem., 2011, 13, 115-126, DOI: 10.1039/C0GC00456A, Paper 

An efficient copper-catalysed aerobic oxybromination of arenes in water 
Jian Wang, Wei Wang and Jing-Hua Li 
Green Chem., 2010, 12, 2124-2126, DOI: 10.1039/C0GC00328J, Communication 

Waste materials – catalytic opportunities: an overview of the application of large scale waste materials as resources for catalytic applications
M. Balakrishnan, V. S. Batra, J. S. J. Hargreaves and I. D. Pulford 
Green Chem., 2011, 13, 16-24, DOI: 10.1039/C0GC00685H, Tutorial Review 

A green protocol for palladium-catalysed Suzuki-Miyaura cross-coupling 
Alexander N. Marziale, Dominik Jantke, Stefan H. Faul, Thomas Reiner, Eberhardt Herdtweck and Jörg Eppinger 
Green Chem., 2011, 13, 169-177, DOI: 10.1039/C0GC00522C, Paper 

Selective hydrogenolysis of biomass-derived xylitol to ethylene glycol and propylene glycol on supported Ru catalysts 
Jiying Sun and Haichao Liu 
Green Chem., 2011, 13, 135-142, DOI: 10.1039/C0GC00571A, Paper 

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Green Chemistry? Then why not submit to us today or alternatively email us your suggestions.

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A reversible CO2 carrier for the carboxylation of ketones at room temperature

Beckman and Munshi reports a reversible CO2 carrier (RCC) for the carboxylation of ketone to β-ketoester under ambient CO2 pressure and temperature.

RCC has been synthesized by immobilizing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) on methylhydrosiloxane support and reacting with CO2 with 100% degree of functionalisation. RCC is found to be recyclable and shows retention of activity in 5 recycles. CO2 absorption under ambient temperature and desorption at 120 °C renders the material suitable for carrying out carboxylation reactions at 25 °C with excellent yields. The yield of the reaction can reach up to 100% with TON 200 in 4 h. The extent of the reaction primarily depends upon enol content of the substrate. β-Ketoacid produced during the reaction can be isolated and converted to its corresponding methyl ester derivative by reacting with methyl iodide.

Access this article for free by clicking on the link below: 

Ambient carboxylation on a supported reversible CO2 carrier: ketone to β-keto ester, Eric J. Beckman and Pradip Munshi, Green Chem., 2011, DOI: 10.1039/C0GC00704H, Advanced Article, Paper

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Top ten most accessed articles in November

This month sees the following articles in Green Chemistry that are in the top ten most accessed:-

Vegetable oil-based polymeric materials: synthesis, properties, and applications 
Ying Xia and Richard C. Larock 
Green Chem., 2010, 12, 1893-1909, DOI: 10.1039/C0GC00264J, Critical Review 

Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions 
Rong Xing, Ayyagari V. Subrahmanyam, Hakan Olcay, Wei Qi, G. Peter van Walsum, Hemant Pendse and George W. Huber 
Green Chem., 2010, 12, 1933-1946, DOI: 10.1039/C0GC00263A, Paper 

Catalytic conversion of biomass to biofuels 
David Martin Alonso, Jesse Q. Bond and James A. Dumesic 
Green Chem., 2010, 12, 1493-1513, DOI: 10.1039/C004654J, Critical Review 

A solid-acid-based process for the conversion of hemicellulose 
Paresh Laxmikant Dhepe and Ramakanta Sahu 
Green Chem., 2010, 12, 2153-2156, DOI: 10.1039/C004128A, Communication 

Fe3O4 nanoparticles: a robust and magnetically recoverable catalyst for three-component coupling of aldehyde, alkyne and amine 
Tieqiang Zeng, Wen-Wen Chen, Ciprian M. Cirtiu, Audrey Moores, Gonghua Song and Chao-Jun Li 
Green Chem., 2010, 12, 570-573, DOI: 10.1039/B920000B, Communication 

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, DOI: 10.1039/C0GC00307G, Critical Review 

A silica gel supported dual acidic ionic liquid: an efficient and recyclable heterogeneous catalyst for the one-pot synthesis of amidoalkyl naphthols 
Qiang Zhang, Jun Luo and Yunyang Wei 
Green Chem., 2010, 12, 2246-2254, DOI: 10.1039/C0GC00472C, Paper 

Microwave-assisted solvent- and ligand-free copper-catalysed cross-coupling between halopyridines and nitrogen nucleophiles 
Zhen-Jiang Liu, Jean-Pierre Vors, Ernst R. F. Gesing and Carsten Bolm 
Green Chem., 2011, 13, 42-45, DOI: 10.1039/C0GC00296H, Communication 

Efficient copper-catalyzed N-arylations of nitrogen-containing heterocycles and aliphatic amines in water 
Xufeng Li, Daoshan Yang, Yuyang Jiang and Hua Fu 
Green Chem., 2010, 12, 1097-1105, DOI: 10.1039/C002172E, Paper 

Highly efficient catalyst for the decarbonylation of lactic acid to acetaldehyde 
Benjamin Katryniok, Sébastien Paul and Franck Dumeignil 
Green Chem., 2010, 12, 1910-1913, DOI: 10.1039/C0GC00203H, Communication 

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Green Chemistry? Then why not submit to us today or alternatively email us your suggestions.
  

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Is cellulose dissolution process with ionic liquids really environmentally friendly?

Righi and co-workers here present the life cycle assessment (LCA) of cellulose dissolution with ionic liquids 1-butyl-3-methylimidazolium chloride (Bmim Cl). The authors compared the “greenness” of the process with the well established environmental friendly N-methyl-morpholine-N-oxide (NMMO)/H2O process. Results from the LCA suggest that both processes are comparable.

Specifically, the process with Bmim Cl generates a higher environmental load on abiotic resource depletion, emissions of volatile organic compounds and ecotoxicity than the NMMO/H2O process. Conversely it has some environmental advantages with regards to human toxicity. In both cellulose dissolution processes, the major contributions to the environmental impacts come from precursor syntheses.

Read more about this article here:

Comparative cradle-to-gate life cycle assessments of cellulose dissolution with 1-butyl-3-methylimidazolium chloride and N-methyl-morpholine-N-oxide

Serena Righi, Andrea Morfino, Paola Galletti, Chiara Samorì, Alessandro Tugnoli and Carlo Stramigioli
Green Chem., 2011, DOI: 10.1039/C0GC00647E, Paper

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New Associate Editor for Green Chemistry

Professor Chao-Jun Li

We are delighted to announce that Professor Chao-Jun Li (McGill University, Canada) is the new Associate Editor for Green Chemistry.

His main area of research is innovative and fundamentally new organic reactions that will defy conventional reactivities and possess high “atom-efficiency”.

Professor Li will handle manuscripts from the Americas and Canada and his editorial office is now open for submissions. We welcome Professor Li to this new role.

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African Green Chemistry congress makes the headlines

The first PACN Green Chemistry Congress took place in Addis Ababa, Ethiopia, on the 15th –17th November 2010. The international event was organised by the RSC Pan Africa Chemistry Network (www.rsc.org/pacn) with support from Green Chemistry. The congress received fantastic media coverage in countries across the African continent and the rest of the world.

The Green Chemistry Congress was opened by the Ethiopian Minister for Water and Energy, H.E. Ato Alemaghu Tegenu. During the event, Tegenu wrote an opinion piece that highlighted the need for science and innovation to improve African people’s lives sustainably, and the important role of the RSC and the Pan Africa Chemistry Network in supporting these scientific developments. This piece was published both in print and online in 13 different newspapers across Africa. To read the piece online, click here.

Green Chemistry Advisory Board member, Yonas Chebude, chaired the local organizing committee. In addition to a number of distinguished scientists from all around the world, both the Chair of the Editorial Board, Martyn Poliakoff, and the Scientific Editor, Walter Leitner, spoke at the Congress, as well as Editorial Board members Buxing Han, Paul Anastas and Tom Welton. The Congress was very well attended with delegates from 22 countries.

One of the main outcomes of the Congress is the writing of a report which will include recommendations. Once the report is finalised we will announce it on the Green Chemistry website.

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Lights, camera, action

Martyn Poliakoff, CBE, FRS, is research professor of chemistry at the University of Nottingham in the UK. His main research interest is the application of supercritical fluids with a focus on green and sustainable chemistry. He is one of the narrators of 'The Periodic Table of Videos', which are popular on YouTube. He is chair of the Green Chemistry editorial board.

Martyn Poliakoff talks to Kathleen Too about the periodic table of videos and passion for green chemistry

Can you tell us a little known fact about yourself? 

I’m an Honorary Professor at Moscow State University, something I share with Fidel Castro and Bill Clinton. 

Which of your academic achievements are you most proud of? 

To me, academic work is rather like journalism – journalists get excited about the story they are working on, but when they move on to the next story, that one is more exciting than the one before. So I think that the only way you can operate as an academic is to be excited about whatever you are doing at a particular time. When I was younger, I did a lot of work on the reactive molecule iron tetracarbonyl, which is completely useless in the green chemistry context because it only exists at room temperature for a millionth of a second or less , but I am still quite proud of my experiments. As a professor, I am proud of the little contributions I can make to the design of an experiment by my research group. Experiments are almost always done by my students or postdocs. Sometimes, as a supervisor, the contributions to the design of the experiments are not as big as one would like. Occasionally, I have a really good idea , which makes the experiments work and that always give me pleasure. 

You’re keen to promote science on YouTube. Could you tell us more? 

I began working with YouTube purely by accident. My university was collaborating with Brady Haran, a very talented video journalist, who wanted to make a periodic table of videos. I didn’t think there was enough to say about some of the more obscure elements but as it turned out, there was plenty to say, at least enough to make short videos. We wanted to show that we enjoy chemistry and how much fun it can be. 

We’re in the process of making videos about different molecules and reactions. There are also other videos that are rather difficult to define, for example, we made a video of gold dissolving in Aqua Regia – a mixture of nitric acid and hydrochloric acid – it’s not exactly a reaction or a molecule but we thought that people may be interested in seeing the gold dissolving. 

Which video was the most fun to make? 

They were all fun, but my favourite is about the element hassium. This is element 108 and I knew nothing about it. In fact, in the precredit sequence – the bit before the main title of the video – I was filmed saying ‘I don’t know anything about hassium, let’s make something up’. 

What is your favourite element? 

I’m very fond of sodium. The chemical symbol for sodium is Na, which was my mother’s nickname when she was a child. Each time I hear the word Na or see it written down, I get a warm feeling. I’m also fond of xenon, because it’s been an important element in my research. 

What excites you about chemistry and what does the future hold for green chemistry? 

Objects we use in everyday life, such as most of the clothes we wear, are made from synthetic chemicals. The jacket I’m wearing is actually leather but the inside is made of polyester – a synthetic material. We couldn’t enjoy any of these without the products of the chemical industry. Chemistry often has a bad image. People generally think about it polluting and destroying the planet but green chemistry allows young people to feel that they are helping both the planet and humanity at the same time. So it’s doubly good! 

With oil running out and the expanding world population leading to a greater demand for chemicals, we have got to do something. One of the greatest challenges is to get green chemistry to work. The future either holds success in delivering what people need or complete failure leading to society collapsing. We have to succeed. I hope that in the end the principles of green chemistry will be applied to most chemistry. You could argue that if green chemistry really succeeds, it will disappear because all chemistry will become green. 

What do you enjoy most about being the chair of Green Chemistry? 

I enjoy interacting with other chemists, inspiring young people and spreading the green chemistry message. I also enjoy promoting the subject in Ethiopia and encouraging people in economically developing countries to take up green chemistry so that they don’t make the same mistakes regarding pollution that we did in the past. 

What advice do you have for young scientists? 

Green chemistry offers terrific opportunities and there are different areas within the subject. It doesn’t matter that some people are using ionic liquids, others using new catalysts, the important message is that green chemistry is not about one area being better than another. We need all those areas and many more to solve our current problems. One of the attractions of green chemistry is that there are huge opportunities for new ideas. 

Which historical scientific figure would you most like to have dinner with and why? 

I have been fortunate to have met many fascinating famous scientists. One of the exciting things is actually finding out what they are like as people and not just learning about what they have discovered. However, historical figures come from a very different age. Possibly, they would strike us as being pompous or very formal compared to nowadays, not because they were famous scientists but because they lived 100 or 200 years ago. From my point of view, there are two quite exciting events that happened in 1869. One was Mendeleev propounding the Periodic Table for the first time. The other was that Thomas Andrews, a physical chemist in Belfast, described the critical point of carbon dioxide for the first time. Supercritical fluids have played a very important part in my research. It’s quite amusing that the two events took place in the same year. I would quite like to have dinner with Thomas Andrews and Mendeleev, though of course, they might not have been able to speak to each other because I am not sure whether Mendeleev could speak English. He definitely spoke German because he published some of his papers in German. It probably would be a rather strange triangular conversation. 

How would your family and friends describe you? 

Always doing chemistry.

When you got your CBE, how was your meeting with the Royal Family? 

A CBE is a British Award, which stands for Commander of the Order of the British Empire. It is presented at Buckingham Palace by a member of the Royal Family. I met with Prince Charles and he was very interested in my work. We had a 45 second discussion about recycling plastics, which was quite unexpected. He really had done his homework! 

You already have a number of fans; you even have a Martyn Poliakoff appreciation society on Facebook. How do you feel about being famous and how do you deal with fame? 

I’m not sure that I’m particularly famous. My brother is a well known playwright in the UK and much better known than me. Ten years ago I was walking through Helsinki with a friend of mine, who is very well known in Finland. I was with him and my postdoc who asked, ‘Have you noticed that everybody is looking at Neil?’ I replied ‘No’, because I am used to people staring at my hair anyway. So I didn’t notice anything different. 

Articles of interests:

Continuous heterogeneous catalytic oxidation of primary and secondary alcohols in scCO2
Adrian O. Chapman, Geoffrey R. Akien, Nicholas J. Arrowsmith, Peter Licence and Martyn Poliakoff, Green Chem., 2010, 12, 310
DOI:10.1039/b913434d

Solubilisation of -chymotrypsin by hydrophobic ion pairing in fluorous systems and supercritical carbon dioxide and demonstration of efficient enzyme recycling
Karima Benaissi, Martyn Poliakoff and Neil R. Thomas, Green Chem., 2010, 12, 54
DOI:10.1039/b904761a

Videos of interests:

Link icon The Periodic Table of Videos – Sodium
The Periodic Table of Videos – Sodium

Link icon The Periodic Table of Videos – Xenon
The Periodic Table of Videos – Xenon

Link icon The Periodic Table of Videos – Hassium
The Periodic Table of Videos – Hassium

Link icon Dissolving gold in aqua regia
Dissolving gold in aqua regia

Link icon Chemistry Christmas Tree
Chemistry Christmas Tree

Link icon Which element for Christmas?
Which element for Christmas?

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Top ten most accessed articles in October

This month sees the following articles in Green Chemistry that are in the top ten most accessed:-

Catalytic conversion of biomass to biofuels 
David Martin Alonso, Jesse Q. Bond and James A. Dumesic 
Green Chem., 2010, 12, 1493-1513, DOI: 10.1039/C004654J, Critical Review  

Vegetable oil-based polymeric materials: synthesis, properties, and applications 
Ying Xia and Richard C. Larock 
Green Chem., 2010, 12, 1893-1909, DOI: 10.1039/C0GC00264J, Critical Review  

Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions 
Rong Xing, Ayyagari V. Subrahmanyam, Hakan Olcay, Wei Qi, G. Peter van Walsum, Hemant Pendse and George W. Huber 
Green Chem., 2010, 12, 1933-1946, DOI: 10.1039/C0GC00263A, Paper  

Sulfonated silica/carbon nanocomposites as novel catalysts for hydrolysis of cellulose to glucose 
Stijn Van de Vyver, Li Peng, Jan Geboers, Hans Schepers, Filip de Clippel, Cedric J. Gommes, Bart Goderis, Pierre A. Jacobs and Bert F. Sels 
Green Chem., 2010, 12, 1560-1563, DOI: 10.1039/C0GC00235F, Communication  

Heterogeneous catalytic synthesis using microreactor technology 
Christopher G. Frost and Lynsey Mutton 
Green Chem., 2010, 12, 1687-1703, DOI: 10.1039/C0GC00133C, Tutorial Review 

Biorenewable polyethylene terephthalate mimics derived from lignin and acetic acid 
Laurent Mialon, Alexander G. Pemba and Stephen A. Miller 
Green Chem., 2010, 12, 1704-1706, DOI: 10.1039/C0GC00150C, Communication 

Fe3O4 nanoparticles: a robust and magnetically recoverable catalyst for three-component coupling of aldehyde, alkyne and amine 
Tieqiang Zeng, Wen-Wen Chen, Ciprian M. Cirtiu, Audrey Moores, Gonghua Song and Chao-Jun Li 
Green Chem., 2010, 12, 570-573, DOI: 10.1039/B920000B, Communication  

Mild water-promoted selective deacetalisatison of acyclic acetals 
D. Bradley G. Williams, Adam Cullen, Alex Fourie, Hendrik Henning, Michelle Lawton, Wayne Mommsen, Portia Nangu, Jonathan Parker and Alicia Renison 
Green Chem., 2010, 12, 1919-1921, DOI: 10.1039/C0GC00280A, Communication  

Sulfated tungstate: a new solid heterogeneous catalyst for amide synthesis 
Pramod S. Chaudhari, Suresh D. Salim, Ravindra V. Sawant and Krishnacharya G. Akamanchi 
Green Chem., 2010, 12, 1707-1710, DOI: 10.1039/C0GC00053A, Communication 

Liquid phase oxidation of p-xylene to terephthalic acid at medium-high temperatures: multiple benefits of CO2-expanded liquids 
Xiaobin Zuo, Fenghui Niu, Kirk Snavely, Bala Subramaniam and Daryle H. Busch 
Green Chem., 2010, 12, 260-267, DOI: 10.1039/B920262E, Paper  

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Green Chemistry? Then why not submit to us today or alternatively email us your suggestions.  

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Eco-friendly chromatography

Spanish scientists have devised a greener form of liquid chromatography by using cyclodextrins as additives in the mobile phase. This results in more water being used in the chromatographic process.

Using cyclodextrins in chromatography could increase the amount of water being used

Cyclodextrins are a natural, renewable compound made from starch and are totally biodegradable. They can be modified and tailor made, and as a result are used in a variety of fields including the pharmaceutical, food and cosmetic industries.

High performance liquid chromatography (HPLC) is a commonly used analytical technique that allows fast separation and quantification of compounds in complex mixtures. Owing to its high resolution and sensitivity, it is widely employed in academic and industrial settings.

Using cyclodextrins in chromatography could increase the amount of water being used
Antonia Martin and colleagues from the Complutense University of Madrid investigated ways of reducing the amount of acetonitrile and developing chromatographic methods that use an increasing amount of water and renewable solvents like ethanol. ‘Due to the toxicity of acetonitrile, these mobile phases have to be treated as chemical waste, so we were interested in using non-toxic solvents, especially alcohols, as an alternative,’ says Martin.

Being greener is only a benefit if the performance of the new system is comparable to current methods. To check this, Martin and her team tested for beta-carbolines, a naturally occurring alkaloid linked to neurological diseases, in human blood serum. The results were as good as non-cyclodextrin modified HPLC in terms of accuracy – in fact the cyclodextrins increased the detection sensitivity.

‘There was a rapid increase in the price of acetonitrile during 2008 so these substitutions will lead to significant cost benefits as well as green chemistry benefits,’ he adds.

Rebecca Brodie

This article is free to access upon a simple registration process:

Eco-friendly liquid chromatographic separations based on the use of cyclodextrins as mobile phase additives
Víctor González-Ruiz, Andrés G. León, Ana I. Olives, M. Antonia Martín and J. Carlos Menéndez, Green Chem., 2011, DOI:10.1039/c0gc00456a

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