Polymer Chemistry Author of the Month: Suhrit Ghosh

Suhrit Ghosh was born in 1976 in India. After the completion of his undergraduate education (Chemistry major) at the Presidency College (now University), Kolkata, he was admitted to the integrated PhD program (Chemical Science) at the Indian Institute of Science, Bangalore in 1997. He received his MS degree (Chemistry) in 2000 and continued for PhD until 2005 under the supervision of Professor S. Ramakrishnan. Then he moved to the group of Professor S. Thayumanavan at the University of Massachusetts, Amherst, USA, for postdoctoral studies (2005-2007). Subsequently he worked as an Alexander von Humboldt postdoctoral fellow (2007-2008) with Professor Frank Würthner at the University of Würzburg, Germany. In 2008 he joined the Indian Association for the Cultivation of Science (IACS), Kolkata, India, as an Assistant Professor where he currently holds the position of Professor and Chair of the School of Applied and Interdisciplinary Sciences.

Research interests of his group include supramolecular polymerization of donor-acceptor π-systems, H-bonding driven directional assembly of amphiphilic π-systems/macromolecules and biologically relevant stimuli responsive aggregation of amphiphilic polymers (polydisulfides, polyurethanes). He has about 100 publications in peer reviewed journals and ten PhD students have graduated from his group. He is the recipient of the B. M. Birla Science Prize in Chemistry (2014), JSPS Invitation Fellowship (long term) Japan (2014), SwarnaJayanti Fellowship (2015) from the Department of Science and Technology, Government of India, K. Kishore Memorial Award (2016) from the Society of Polymer Science, India and the Bronze medal (2017) from the Chemical Research Society of India. He has been serving as an Associate Editor for the journal RSC Advances since 2015.

What was your inspiration in becoming a polymer chemist?

I was introduced to Polymer Chemistry by two captivating teachers (Professor Manas Chanda and Professor S. Ramakrishnan) during my Master’s Degree course work in the Indian Institute of Science, Bangalore. Subsequently I had an opportunity to carry out a year-long MS project on Polymer Chemistry under the supervision of Professor S. Ramakrishnan when I started learning more about the subject. From group discussions and seminars in the department, I learnt about the emerging topics (of the time) in Polymer Chemistry such as foldamers, molecular imprinting, conjugated polymers, helical polymers, amphiphilic polymers, supramolecular polymers and so on. I was greatly inspired by such diversity in the field and its interdisciplinary nature connecting chemistry with biology and materials science.

What was the motivation behind your most recent Polymer Chemistry article?

Poly(disulfide)s (PDS), although known for long time, lacked structural diversity in the absence of any generally applicable synthetic methodology. Recently we had established a mild step-growth polymerization approach to make linear functional PDS by a facile thiol-disulfide exchange reaction between commercially available 2,2′-dipyridyldisulfide and a di-thiol.  By taking a stoichiometric excess of the first monomer, telechelic PDS could be prepared with the reactive pyridyl-disulfide groups at the chain terminal which could be further functionalized by a functional thiol without disturbing the backbone disulfide groups. This motivated us to extend this approach for the synthesis of hyperbranched PDS, particularly considering the possibility of decorating such hyperbranched polymers with multiple reactive pyridyl-disulfide groups at the periphery for post-polymerization functionalization to produce a range of functional hyperbranched polymers with a fully bio-reducible disulfide backbone. We have exactly demonstrated this in our recent Polymer Chemistry paper and envisage that it might allow the screening of structurally diverse amphiphilic hyperbranched PDS for biological applications such as drug delivery.

Which polymer scientist are you most inspired by?

I am most inspired by Professor E. W. Meijer (Eindhoven University of Technology, The Netherlands), especially because of his pioneering fundamental contribution in the field of supramolecular polymers by connecting supramolecular chemistry and polymer chemistry.

How do you spend your spare time?

I like to cook, spend time with my 10-year-old daughter and socialize with like-minded people.

What profession would you choose if you weren’t a scientist?

Practising literature and creative writing.

Read Suhrit’s full article now for FREE until 8th May!


Hyperbranched polydisulfides

Disulfide containing polymers have been extensively studied as responsive materials for biomedical applications such as drug delivery, gene delivery, bio-sensing and receptor-mediated cellular uptake due to the possibility of cleaving the disulfide linkage with glutathione (GSH), a tri-peptide overexpressed in cancer cells. While linear and branched polymers containing disulfide groups have been already studied and more recently polydisulfides (PDS) have come to the fore, hyperbranched polydisulfides (HBPDS) were not known. This manuscript for the first time reports a generally applicable methodology for the synthesis of HBPDS by an A2 + B3 condensation approach. The B3 monomer contains three pyridyl-disulfide (Py–Ds) groups while a di-thiol compound serves as the A2 monomer. A polycondensation reaction under very mild reaction conditions produces HBPDS (Mw = 14300 g mol−1Đ = 1.9) with a very high degree of branching (DB) value of 0.8 and more than twenty highly reactive Py–Ds groups present at the terminal or linear unit of a polymer on an average. The reactive Py–Ds groups can be completely replaced by post-polymerization functionalization using a hydrophilic thiol resulting in bio-reducible amphiphilic HBPDS. It produces micellar aggregates in water with a hydrodynamic diameter of ∼80 nm, a low critical aggregation concentration (7.0 μM) and a high dye (Nile red) loading content. The exchange dynamics of these micellar aggregates, studied by fluorescence resonance energy transfer (FRET), reveals practically no inter-micellar exchange after 6 h indicating very high non-covalent encapsulation stability. On the other hand, in the presence of glutathione, the PDS backbone can be degraded resulting in an efficient triggered release of the encapsulated dye. Dye release kinetics strongly depends on the GSH concentration and interestingly with a fixed concentration of glutathione the release kinetics appears to be much faster for the hyperbranched PDS micelle compared to its linear analogue. MTT assay with two representative cell lines indicates that the amphiphilic HBPDS is biocompatible up to 500 μg mL−1 which is further supported by hemolysis assay showing merely 6.0% hemolysis up to a polymer concentration of 500 μg mL−1.


About the Webwriter

Simon HarrissonSimon Harrisson is a Chargé de Recherche at the Centre National de la Recherche Scientifique (CNRS), based at the Laboratoire de la Chimie des Polymères Organiques (LCPO) in Bordeaux, France. His research seeks to apply a fundamental understanding of polymerization kinetics and mechanisms to the development of new materials. He is an Advisory Board member for Polymer Chemistry. Follow him on Twitter @polyharrisson

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Outstanding Reviewers for Polymer Chemistry in 2019

We would like to highlight the Outstanding Reviewers for Polymer Chemistry in 2019, as selected by the editorial team, for their significant contribution to the journal. The reviewers have been chosen based on the number, timeliness and quality of the reports completed over the last 12 months.

We would like to say a big thank you to those individuals listed here as well as to all of the reviewers that have supported the journal. Each Outstanding Reviewer will receive a certificate to give recognition for their significant contribution.

Prof. Dagmar D’hooge, Ghent University, ORCID: 0000-0001-9663-9893

Dr Ming Jin, Tongji University, ORCID: 0000-0002-8014-2812

Prof. Dominik Konkolewicz, Miami University, ORCID: 0000-0002-3828-5481

Dr Hua Lu, Peking University, ORCID: 0000-0003-2180-3091

Dr Stefan Naumann, University of Stuttgart, ORCID: 0000-0003-2014-4434

Dr Bernhard Schmidt, University of Glasgow, ORCID: 0000-0002-3580-7053

Dr Yan Xia, Stanford University, ORCID: 0000-0002-5298-748X

Dr Pu Xiao, Australian National University, ORCID: 0000-0001-5393-7225

Prof. Youliang Zhao, Soochow University, ORCID: 0000-0002-4362-6244

Prof. Junpeng Zhao, South China University of Technology, ORCID: 0000-0002-2590-0027

We would also like to thank the Polymer Chemistry board and the polymers community for their continued support of the journal, as authors, reviewers and readers.

 

If you would like to become a reviewer for our journal, just email us with details of your research interests and an up-to-date CV or résumé.  You can find more details in our author and reviewer resource centre.

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Paper of the month: Synthesis of lipase–polymer conjugates by Cu(0)-mediated reversible deactivation radical polymerization: polymerization vs. degradation

Graphic imageZhang and co-workers report aqueous polymerization-induced self-assembly by atom transfer radical polymerization to generate protein-based nanoassemblies.

Polymerization-induced self-assembly (PISA) has opened the way for the in-situ formation of a wide range of nanoparticles with applications ranging from the material to the biomedical field. However, the vast majority of reports focus on utilizing reversible addition-fragmentation chain transfer polymerization as the main methodology while atom transfer radical polymerization (ATRP) is very rarely combined with PISA, mostly due to the limitations of ATRP in water. Zhang and co-workers utilized Cu(0) reversible deactivation radical polymerization by exploiting the disproportionation of CuBr/ligand in aqueous media generating both Cu(0) particles and Cu(II) deactivator. Upon modifying Candida Antarctica lipase B (CALB), it was used as a macroinitiator for both hydrophilic and hydrophobic monomers generating well-defined protein-based nanoassemblies. A range of acrylamide and acrylate based monomers were successfully polymerized under mild reaction conditions (e.g. room temperature) via he “grafting from” strategy. When hydrophilic monomers were selected, water-soluble conjugates could be obtained in a facile manner while by polymerizing more hydrophobic monomers yields spherical nanoparticles, consistent to a traditional PISA formulation. Importantly, it was also found that they hydrolysis of the ester bonds can be very significant in the presence of lipase-based macroinitiators, which will catalyze the hydrolysis of poly(acrylate) to poly(acrylic acid). The versatility of the reported methodology combined with the use of mild reaction conditions may find applications in enzyme immobilization and nanoreactors.

Tips/comments directly from the authors:

  1. It is necessary to purify the commercial CuBr as it could be partially oxidized during storage and routine use.
  2. Typical Cu(0)-RDRP in water is fast enough to reach full conversion in minutes; however, the polymerizations would be slower when grafting from proteins, possibly due to the low concentration of macroinitiators.
  3. Although copper ions were known to be able to denature proteins, CALB still maintained its function after polymerization. The mild reaction conditions such as aqueous system, low reaction temperature (0-25 ℃) and fast polymerization rate (minutes to hours) could be suitable for more sensitive proteins.
  4. The degradation of lipase-poly(acrylate) conjugates was fast and gradual disappearance of precipitates could even be visually observed during the dialysis in water. So it is better to quickly purify the conjugates via centrifugation. From another point of view, such conjugates could be potentially used for drug delivery and controlled release.

Citation to the paper: Synthesis of lipase–polymer conjugates by Cu(0)-mediated reversible deactivation radical polymerization: polymerization vs. degradation, Polym. Chem., 2020, 11, 1386-1392, DOI: 10.1039/c9py01462d

Link to the paper:

https://pubs.rsc.org/en/content/articlelanding/2020/py/c9py01462d#!divAbstract

This paper is free to read until 10th April 2020!

About the Web Writer

Dr. Athina Anastasaki is an Editorial Board Member and a Web Writer for Polymer Chemistry. Since January 2019, she joined the Materials Department of ETH Zurich as an Assistant Professor to establish her independent research group.

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2020 Polymer Chemistry Lectureship awarded to Rachel O’Reilly

It is with great pleasure that we announce Prof Rachel O’Reilly (University of Birmingham) as the recipient of the 2020 Polymer Chemistry Lectureship.

This award, now in its sixth year, honours an early-career researcher who has made significant contribution to the polymer chemistry field. The recipient is selected by the Polymer Chemistry Editorial Board from a list of candidates nominated by the community.

Rachel O'ReillyRead on to find out more about Rachel

Rachel O’Reilly holds a Chair in Chemistry within the College of Engineering and Physical Sciences at the University of Birmingham. From 1st August 2018 she became the Head of the School of Chemistry. She graduated from the University of Cambridge in 1998 with a BA in Natural Sciences, and in 1999 with an MSc in Chemistry and completed her PhD in 2003 from Imperial College London. She has held a number of prestigious fellowships from the ESPRC, Royal Society and Royal Commission for the Exhibition of 1851.

She has published over 175 research papers in scientific journals as well as reviews and book chapters in the fields of polymer synthesis, self-assembly, catalysis and DNA nanotechnology. She has given over 170 invited lectures and was recognised as one of the Royal Society of Chemistry’s 175 faces of Chemistry. She has received major grants and research support from the ERC, BP and EPSRC. She leads a large interdisciplinary team working at the interface of chemistry, materials and biology. Since 2006 she has graduated close to 25 PhD students and mentored over 20 postdoctoral researchers.

Rachel was appointed on the EPSRC strategic advisory network (SAN) in 2009 and served for almost 7 years. During this time she most significantly contributed to white papers on developing more flexible support for early career researchers, managing diversity and delivering impact. She holds a position as a review editor for Science and is an associate editor for Macromolecules.

Rachel leads the Rachel O’Reilly Group. Her group’s work has received numerous national and international awards for her polymer and material efforts, including, uniquely, four from the Royal Society of Chemistry (RSC), and, young researcher medals from the American Chemical Society (ACS) and the International Union of Pure and Applied Chemistry (IUPAC), the world authority on chemical nomenclature and terminology.

To learn more about Rachel’s research have a look at a selection of her publications in Polymer Chemistry:

Self-catalysed folding of single chain nanoparticles (SCNPs) by NHC-mediated intramolecular benzoin condensation
Sofiem Garmendia, Andrew P. Dove, Daniel Taton and Rachel K. O’Reilly

Polym. Chem., 2019,10, 2282-2289

Reversible ionically-crosslinked single chain nanoparticles as bioinspired and recyclable nanoreactors for N-heterocyclic carbene organocatalysis
Sofiem Garmendia, Andrew P. Dove, Daniel Taton and Rachel K. O’Reilly

Polym. Chem., 2018,9, 5286-5294

The application of blocked isocyanate chemistry in the development of tunable thermoresponsive crosslinkers
Marianne S. Rolph, Maria Inam and Rachel K. O’Reilly
Polym. Chem., 2017,8, 7229-7239

Understanding the CDSA of poly(lactide) containing triblock copolymers
Wei Yu, Maria Inam, Joseph R. Jones, Andrew P. Dove and  Rachel K. O’Reilly

Polym. Chem., 2017,8, 5504-5512

We would like to thank everybody who nominated a candidate for the 2020 Polymer Chemistry Lectureship. The Editorial Board had a very difficult task in choosing a winner from the many excellent and worthy candidates.

Please join us in congratulating Rachel on winning this award!

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Polymer Chemistry Author of the Month: Stefan A F Bon

Professor Stefan A. F. Bon

Stefan A. F. Bon is a full professor in the Department of Chemistry at the University of Warwick in the United Kingdom. He studied chemical engineering at the Eindhoven University of Technology (TUe) in the Netherlands (cum laude, 1989-1993), where he also did his Ph.D. (1993-1998) in the polymer chemistry group of prof.dr.ir. Anton L. German. In April 1998 he moved to the UK  where worked as a post-doctoral research assistant in the group of prof. David M. Haddleton at the University of Warwick (1998-2000). He was appointed as Unilever Lecturer in Polymer Chemistry at the University of Warwick in January 2001. During this period of research he focused on the mechanistic aspects of living radical polymerisation in both homogeneous and heterogeneous systems, including the first ever living radical polymerization performed in emulsion. From 2005 Stefan Bon shifted his research interests from living radical polymerization to supracolloidal chemical engineering. Current research focuses on the design of assembled supracolloidal structures and the synthesis of their colloidal and macromolecular building blocks through combination of polymer chemistry, colloid science, soft matter physics, and chemical engineering. Check out www.bonlab.info for more.

What was your inspiration in becoming a polymer chemist?

Eindhoven University of Technology in the 1990s was a fantastic place for polymer science, especially in the fields of emulsion polymerization and polymer physics and processing. We had captivating teachers, such as Alex van Herk, Anton German, and Piet Lemstra.  I was fascinated by it all as an undergrad student and hooked after my international internship at Nippon Paint where I worked on polymer colloids in the summer of 1992. I grabbed the opportunity to do my PhD on nitroxide mediated polymerizations at the end of 1993. What I love about polymer and colloid science is that you can blend chemistry, with physics, mathematics and engineering, fading out boundaries between classical disciplines.

What was the motivation behind your most recent Polymer Chemistry article?

In the mid 2000s we started applying the phenomenon of Pickering stabilization, the concept that particles can adhere to soft deformable interfaces, to mini-emulsion and emulsion polymerization processes. In the last decade we tried to come to a full mechanistic understanding of emulsion polymerization processes in which nanoparticles played the role of molecular surfactants. For the most part we focussed on inorganic nanoparticles, such as clay and silica sols. In 2018/2019 we asked ourselves if Pickering emulsion polymerization would be possible using polymer nanoparticles (10-40 nm), that is nanogels or crosslinked polymer micelles could be used instead. To our delight we found that using nanogels gave us the opportunity to control the morphology of the polymer colloids produced by the Pickering emulsion process. Janus, patchy and armored particles can be made. We wanted to unravel the exact mechanism. The paper in Polymer Chemistry describes a detailed mechanistic study on the effect of inert electrolyte (salt) on the emulsion polymerization process.

Which polymer scientist are you most inspired by?

On passion for emulsion polymerization I would like to mention Bob Gilbert. I know Bob since the mid 1990s, and have great respect for him. I still remember the discussions we had at Santa Margherita Ligure in 1996 on kinetics of radical polymerization and life. I love his mechanistic/kinetic approach to describe scientific concepts and have adopted this as a way of working in my team. On optimism and living larger than life, my former polymer chemistry teacher and friend Alex van Herk, who now works at A*STAR in Singapore. A big thank you to both.

Can you name some up and coming researchers who you think will have a big impact on the field of polymer chemistry?

Restricting myself to people with an academic career path I would like to mention four: Nick Ballard (POLYMAT, Spain), Athina Anastasaki (ETH Zürich, Switzerland), Stuart Thickett (UTAS, Australia), and Zhihong Nie (Fudan University, China). Why? That is simple, all four are fantastic.

How do you spend your spare time?

My husband and I bought a house in Coventry (UK) a bit over a year ago, and since then the garden is undergoing a transformation to see how many different plants we can put into the space. I think soon we will run out of space and there won’t be a single bit of traditional British lawn left. We like to cook (Chinese/Dutch fusion) , travel, and go to the theatre/concerts. We are looking forward to seeing Pink Martini soon in Birmingham. Will pick up playing the guitar again (haha, and if you wonder what style of music: Julio Iglesias of course!).

What profession would you choose if you weren’t a scientist?

That is a hard question. Has to be creative and with people for sure. May be something in the area of people communication/management mediation..

Read Stefan’s full article now for FREE until the 31st March!


Effect of the addition of salt to Pickering emulsion polymerizations using polymeric nanogels as stabilizers

Graphical abstract: Effect of the addition of salt to Pickering emulsion polymerizations using polymeric nanogels as stabilizers

Nanogels made from crosslinked block copolymer micelles are used as stabilizers in the Pickering emulsion polymerization of styrene. The effect of the addition of salt, i.e. NaCl, on the emulsion polymerization is studied. It is shown that an increase in ionic strength of the dispersing medium in these polymerizations led to the formation of latexes of larger diameters. Along with an increase in size, the morphology of these polymer colloids changed from Janus to patchy with an increase in number of nanogels adsorbed on the polymer surface, as a function of the salt concentration in water. In particular, at the highest tested ionic strength, ca. 25 mM, fully armored polymeric particles surrounded by a dense layer of adsorbed stabilizing nanogels were formed. Kinetic studies carried out at varying NaCl concentrations suggested that particle formation in the reaction followed a combination of a coagulative nucleation mechanism, characterized by a clustering process of Janus precursors to form bigger aggregates, and droplet nucleation. Preliminary film formation studies on latexes made with n-butyl acrylate as a comonomer indicated the potential of this technique for the production of coherent polymer films which included a substructure of functional nanogels.


About the Webwriter

Simon HarrissonSimon Harrisson is a Chargé de Recherche at the Centre National de la Recherche Scientifique (CNRS), based at the Laboratoire de la Chimie des Polymères Organiques (LCPO) in Bordeaux, France. His research seeks to apply a fundamental understanding of polymerization kinetics and mechanisms to the development of new materials. He is an Advisory Board member for Polymer Chemistry. Follow him on Twitter @polyharrisson

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Paper of the month: Pulsed-addition ring-opening metathesis polymerization with functional enyne reagents

Dr. Athina Anastasaki is an Editorial Board Member and a Web Writer for Polymer Chemistry. Since January 2019, she joined the Materials Department of ETH Zurich as an Assistant Professor to establish her independent research group.

Zhang and Gutekunst utilize functional enyne molecules in pulsed-addition ring-opening metathesis polymerization to generate multiple functional polymer chains from a single 3rd generation Grubbs initiator.

Ring-opening metathesis polymerization (ROMP) has gained popularity within the polymer chemistry community thanks to the invention of functional group-tolerant ruthenium-based initiators. However, remaining challenges in the area include the use of stoichiometric amounts of metal and the difficulty to satisfactory control the end-group functionality. To address these challenges, Gutekunst and Zhang have elegantly employed functional enyne molecules in pulsed-addition ring-opening metathesis polymerization. This led to the generation of multiple functional polymer chains from a single 3rd generation Grubbs initiator. Importantly, all polymers synthesized displayed monomodal molecular weight distributions and very low dispersity values, as characterized by size exclusion chromatography, thus supporting the high efficiency of enyne chain-transfer. Detailed analysis of the molecular weights obtained from each pulse demonstrate that 50% of the ruthenium initiator remains active even after 10 cycles which corresponds to 4% of catalyst death per cycle. This is improved over previous established protocols where 8.5% of catalyst death per cycle was reported. The materials synthesized were further characterized by mass-spectrometry. In particular, matrix assisted laser desorption ionization showed extremely high end-group fidelity obtained using the enyne chemistry with a single polymer distribution and no observable side reactions. Different monomer structures were tested, the vast majority of which were compatible with the developed protocol. Bifunctional enyne molecules can also be used to give heterotelechelic polymers. Last but not least, the possibility of diblock copolymer formation was also examined yielding well-defined block copolymers with low final dispersity values. It is the author’s belief that their user-friendly and catalyst economical method will yield to the facile synthesis of materials with reduced metal contamination thus paving the way for further biomedical and electronic applications.

Tips/comments directly from the authors:

1. An inert atmosphere is important to this protocol, though a glovebox is not needed. All experiments were performed with a standard Schlenk line, and solutions were degassed by simply bubbling with nitrogen gas.
2. Three equivalents of the enyne CTA are used to ensure complete conversion of the Grubbs 3rd generation initiator, but only 1.2 eq is needed for full transfer after a given polymerization cycle of an exo-norbornene imide monomer. This reflects the differences in reactivity between ruthenium alkylidenes and benzylidenes with the enyne CTAs.
3. The exo-Oxanorbornene imide examined in this protocol was also effective but required 2.4 eq of the enyne CTA to recycle the system. This implies that different monomers may have variable reactivities. 1H NMR is very useful to monitor this process, as each of the ruthenium alkylidene/benzylidene species have diagnostic chemical shifts.
4. Small molecule byproducts are formed in each cycle but are inert under the reaction conditions and do not interfere with the polymerization.
5. If any readers are interested in using this approach, feel free to reach out to willgute@gatech.edu with any questions.

Citation to the paper: Pulsed-addition ring-opening metathesis polymerization with functional enyne reagents, Polym. Chem., 2020, 11, 259-264, DOI: 10.1039/c9py00965e

Link to the paper:
https://pubs.rsc.org/en/content/articlepdf/2020/py/c9py00965e

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Spotlight on Rongrong Hu: 2018 Polymer Chemistry Emerging Investigator

This week’s issue of Polymer Chemistry is our 2020 Emerging Investigators issue, which contains articles from polymer chemistry researchers in the early stages of their independent careers and is accompanied by an Editorial from Editor-in-Chief Professor Christopher Barner-Kowollik. To celebrate this issue we are delighted to feature the profile of Professor Rongrong Hu, who published in our 2018 Emerging Investigators issue. Below, Rongrong talks about her research journey, from student to Professor, and her feelings towards Polymer Chemistry!

“With my organic synthesis training as an undergraduate student at Peking University where I learned the great diversity of organic reactions, and the research experiences on luminescent polymer materials during my PhD study at The Hong Kong University of Science and Technology where I learned the fascinating functionalities that polymers could achieve, I tried to combine organic synthesis and polymer synthesis in my research after I started my career in 2014. We utilize efficient organic reactions for the development of new polymerization methodology and the exploration of new polymer structures and materials. After 5 years of research, I am fully convinced by the huge opportunity that comes with this interdisciplinary study.

Polymer Chemistry, with its topics highly focused on the synthesis, functionalities, and applications of polymers, always provides timely publication and best publishing experiences on exciting progress in the field. It can also sensitively catch new research trend and young polymer chemists. In the 2018 Emerging Investigator issue, we introduced our work about room temperature alkyne and sulfonyl azide-based multicomponent polymerizations, which represent efficient approaches for the convenient construction of polymers with unique structures and functionalities. Encouraged by the broad response of this paper, we further developed several elemental sulfur-based multicomponent polymerizations with practical implication. Most recently, I joined Polymer Chemistry as an Associate Editor, working with the top polymer chemists in the world, to look for most up-to-date innovative and exciting polymer chemistry.”

 

Read Rongrong’s 2018 Emerging Investigators series paper below!

Room temperature multicomponent polymerizations of alkynes, sulfonyl azides, and N-protected isatins toward oxindole-containing poly(N-acylsulfonamide)s
Liguo Xu,   Fan Zhou,   Min Liao,   Rongrong Hu*  and  Ben Zhong Tang*
Polym. Chem., 2018,9, 1674-1683

FREE to read and download until the 1st March 2020.

Biography

Rongrong Hu received her B.S. degree from Peking University and her PhD degree from Hong Kong University of Science and Technology. She is currently a Professor of the State Key Laboratory of Luminescent Materials and Devices at South China University of Technology.

She has published over 110 peer-reviewed articles and reviews. Her research interests include (1) the development of alkyne or isocyanide-based multicomponent polymerization methodology through the combination of organic and polymer synthesis, and (2) luminescent polymers with diverse structures and applications. Her current research focuses on the development of multicomponent polymerizations of elemental sulfur and sulfur-containing functional polymers.

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Spotlight on Antoine Buchard: 2018 Polymer Chemistry Emerging Investigator

This week’s issue of Polymer Chemistry is our 2020 Emerging Investigators issue, which contains articles from polymer chemistry researchers in the early stages of their independent careers and is accompanied by an Editorial from Editor-in-Chief Professor Christopher Barner-Kowollik. To celebrate this issue we are delighted to feature the profile of Dr Antoine Buchard, who published in our 2018 Emerging Investigators issue. Below, Antoine talks about his research journey and his feelings towards Polymer Chemistry!

Dr Antoine Buchard & Dr Ulrich Hintermair from The Centre for Sustainable Chemical Technologies were photogrpahed at a coffee meeting in The Edge for the University of Bath Alumni Relations Impact Report 2018. Shoot ref: 29456 Client: Rachel Skerry – Alumni Relations. Shoot Dates 8th and 9th November 2017

“I started my research career as a student working on new metal complexes for homogeneous catalysis, and only really ventured into polymer chemistry when some of our complexes showed interesting activities in the ring-opening polymerisation of lactide. Since then, I have been really interested in polymer chemistry because it is an incredibly diverse area, which I think offers a lot of creative space for both fundamental and applied work.

Today, using renewable feedstocks to make novel polymers is the underlying theme of my research program. I am particularly interested in using natural sugars as a sustainable, highly diverse and functionalisable resource to build polymers with interesting properties, including potentially less impact on the environment.  Our work addresses all aspects of the development of new polymers, from the synthesis of novel monomers, the design of new polymerisation catalysts and processes (including heterogeneous (ref Polym. Chem., 2019,10, 5894-5904)), detailed mechanistic and structure-properties studies, up to the applications of the polymers themselves. Polymer Chemistry is an ideal publication platform for this research, because of the broad scope of the journal, the diversity and expertise of the editorial team, as well as the breadth of article types possible.

Our group have for example recently discovered a method that replaces phosgene with carbon dioxide for the synthesis of cyclic carbonate monomers. We have successfully applied this protocol to various sugar derivatives, including deoxyribose (ref Polym. Chem., 2018,9, 1577-1582) and thymidine (ref Polym. Chem., 2017,8, 1714-1721) and developed promising tuneable, biocompatible and biodegradable polymers, which were also tested as tissue engineering scaffolds for regenerative medicine.

We took the opportunity of the 2018 Emerging Investigator issue to explore slightly different chemistry than usual and investigate the effect of changing some oxygen atoms with sulfur in the backbones of some of our sugar-based polycarbonate (ref Polym. Chem., 2018,9, 1577-1582). To this day it is still unclear! But along the way, we developed some new methodology for use of CS2 in the cyclothio-carbonation of the trans 1,3-diol motif of ribofuranoses, and isolated the first examples of cyclic xanthate monomers derived from natural sugars. Using controlled ring-opening polymerisation, regular poly(xanthate) and alternating poly(trithio-alt-thiocarbonate) species were obtained, and we showed that the sugar backbone influenced greatly the regioselectivity of monomer opening. These polymers formed a new family of degradable sulfur-containing sustainable polymers that attracted some attention from material scientists, and that we are still investigating today and hoping to report on further soon. Featuring in the 2018 Emerging Investigator issue was a great recognition and reward for the work done in my group over the past few years, and has spurred us to keep working in this area.

I am really looking forward to the 2020 Emerging Investigator issue of Polymer Chemistry. I am always curious to discover newcomers in the field and how they envisage the field. With the biennial Pioneering Investigators issue, these issues really set themselves apart from regular issues. I have found that authors usually want to rise to the challenge and report especially exciting results, so it is often a great read!”

 

Read Antoine’s Polymer Chemistry papers below!

Polymer-supported metal catalysts for the heterogeneous polymerisation of lactones
Ioli C. Howard, Ceri Hammond and Antoine Buchard
Polym. Chem., 2019,10, 5894-5904

Polymers from sugars and CS2: synthesis and ring-opening polymerisation of sulfur-containing monomers derived from 2-deoxy-D-ribose and D-xylose
Eva M. López-Vidal, Georgina L. Gregory, Gabriele Kociok-Köhn and Antoine Buchard
Polym. Chem., 2018,9, 1577-1582 (Emerging Investigator 2018 Issue)

CO2-Driven stereochemical inversion of sugars to create thymidine-based polycarbonates by ring-opening polymerisation
Georgina L. Gregory, Elizabeth M. Hierons, Gabriele Kociok-Köhn, Ram I. Sharma and Antoine Buchard
Polym. Chem., 2017,8, 1714-1721

Polymers from sugars and CO2: ring-opening polymerisation and copolymerisation of cyclic carbonates derived from 2-deoxy-D-ribose
Georgina L. Gregory, Gabriele Kociok-Köhn and Antoine Buchard
Polym. Chem., 2017,8, 2093-2104

 

Biography

Antoine is a Royal Society University Research Fellow and Reader in Chemistry within the Centre for Sustainable and Circular Technologies (CSCT) at the University of Bath (UK). His research interests include novel chemical transformations and use in catalysis of renewable resources for the synthesis of sustainable polymers and their applications. He is also a member of the UK Catalysis Hub.

Antoine studied at the École Polytechnique in France, obtaining the École Polytechnique’s Diploma and a Master’s degree in chemistry in 2006. He also completed his PhD at the Ecole Polytechnique in 2009, under the supervision of Prof Pascal Le Floch. Antoine was then a Postdoctoral Research Assistant at Imperial College with Prof Charlotte Williams. He worked Air Liquide R&D before returning to academia in 2013, as a Whorrod Research Fellow within the CSCT at the University of Bath.

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Polymer Chemistry Author of the Month: Claude St Thomas

Claude St ThomasClaude St Thomas studied chemistry at the École Normale Supérieure, Université d’État d’Haïti, Port au Prince, Haïti. In 2008, he moved to Mexico where he obtained MSc and PhD degrees in polymer chemistry at the Centro de Investigación en Química Aplicada (CIQA) under the guidance of Dr. Ramiro Guerrero Santos. During his PhD studies, he undertook two research stays at the Laboratory of Chemistry and Processes of Polymerization (LCPP), in Lyon, France under the supervision of Prof Bernadette Charleux and Dr. Franck D’Agosto. He designed a novel dual RAFT/NMP chain transfer agent for a tandem polymerization and investigated its use for preparing the self-assembled nanoparticles. This investigation was awarded with the 2015 Rafael Illescas Frisbie prize from the Mexican Chemistry Society as the best PhD thesis. In the same year, he was promoted as a CONACYT research fellow at CIQA.

His research mainly focuses on the preparation of well-defined multiblock copolymers and the development of novel associative polymers featuring stimuli-responsive groups using reversible deactivation radical polymerization (RDRP) techniques. He is also interested in the rheological properties of polymers for applications in coatings, paints, enhanced oil recovery, and water treatment.

What was your inspiration in becoming a polymer chemist?

In my childhood, I was always fascinated by nature. At the beginning, I dreamed about becoming an agronomist. However, my interest for chemistry started in high school by the teachings from chemistry lecturer Sylvain Jean Desir. There, I understood that chemistry is the basis of life. During my MSc and PhD studies I worked with materials of common and daily use and a special interest for polymer chemistry started rising.

What was the motivation behind your most recent Polymer Chemistry article?

In our research group, scientific contributions related to the preparation of water-soluble copolymers have been previously published under the supervision of Dr. Enrique Javier Jiménez Regalado using free radical polymerization. In 2014, the “Consejo Nacional de Ciencía y Tecnología” (CONACYT, México) started a new program for addressing solutions to national problems, where young researchers were engaged and assigned to specific projects. Since, I started in my current position in 2015 and inspired by the versatility of the RAFT polymerization technique, my current research work focuses on the development of novel pathways for preparing well-defined water-soluble associative copolymers.

Inspired by the RDRP techniques and their feasibility for synthesizing polymeric materials with unprecedented properties, our recent contribution describes a new strategy for preparing environmentally-friendly water-soluble associative copolymers using the RAFT technique.

Which polymer scientist are you most inspired by?

A group of scientists have impacted my career. I appreciate the discipline, rigor and professional achievements of both Prof Bernadette Charleux and Dr. Franck D’Agosto. Fascinated by RDRP techniques, I am also inspired by three experts in RDRP: Prof Craig J. Hawker, Prof. San H. Thang and Prof. Krzysztof Matyjaszewski. Their publications describing processes for synthesizing polymers with specific characteristics might allow the use of these materials in different industrial applications.

Can you name some up and coming researchers who you think will have a big impact on the field of polymer chemistry?

Based on application areas of polymeric materials, it would be difficult to mention researchers who will have a big impact on the field. Notwithstanding, I select Dr. Francesco Picchioni (University of Groningen). His research on the development of chemical materials for application in Enhanced Oil Recovery (EOR) displays great interest and could impact the field. For these researches, I am also impressed by the research works of Dr. Michael F. Cunningham (Queens University) and Sébastien Perrier (University of Warwick)

How do you spend your spare time?

Outside of professional activities, I enjoy spending time with my family (wife and four year-old daughter-Nicole) and visiting natural places. My favorite sport is soccer, so I enjoy playing it with friends. I also enjoy playing guitar and reading about new scientific developments and culture.

What profession would you choose if you weren’t a scientist?

Probably an agronomist due to my passion for natural sciences, because it was my first dream.

Read Claude’s full article now for FREE until the 31st January!


Preparation of hydrophobically modified associating multiblock copolymers via a one-pot aqueous RAFT polymerization

Graphical abstract: Preparation of hydrophobically modified associating multiblock copolymers via a one-pot aqueous RAFT polymerization

We describe an efficient strategy for the preparation of hydrophobically associating multiblock copolymers using the RAFT technique. Polymerization reactions were carried out by a one-pot aqueous RAFT polymerization at 70 °C using a symmetrical trithiocarbonate as a chain transfer agent (CTA) in aqueous media. The macroRAFT polyacrylamide (PAM) was synthetized and chain extended by polymerization of N,N′-dihexylacrylamide (DHAM) and acrylamide (AM), respectively. The resultant polymers were intensely characterized by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, diffusion-ordered spectroscopy (DOSY), Fourier transform-infrared (FT-IR) spectroscopy and rheology. The structure and insertion of a hydrophobic block (PDHAM) into the backbone were carefully demonstrated. The rheological measurements confirmed the effect of the hydrophobic block number on the viscosity of polymers at different concentrations and the formation of a reversible physical network of entangled polymers in aqueous media. Moreover, the incorporation of the hydrophobic block (PDHAM) was established by the oscillatory measurement.


About the Webwriter

Simon HarrissonSimon Harrisson is a Chargé de Recherche at the Centre National de la Recherche Scientifique (CNRS), based at the Laboratoire de la Chimie des Polymères Organiques (LCPO) in Bordeaux. His research seeks to apply a fundamental understanding of polymerization kinetics and mechanisms to the development of new materials. He is an Advisory Board member for Polymer Chemistry. Follow him on Twitter @polyharrisson

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Welcome to our new Associate Editor Professor Zhibo Li

We are delighted to announce Professor Zhibo Li (Qingdao University of Science and Technology,) as a new Associate Editor for Polymer Chemistry!

Professor Zhibo LiZhibo Li obtained his B.S. (1998) and Master (2001) degree from the University of Science and Technology of China (USTC). He then completed his Ph.D. working on self-assembly of triblock copolymers in the Chemistry Department, University of Minnesota in 2006. After that, he spent two and half years in UCLA as a postdoctoral scholar. In 2009, he became a professor in the Institute of Chemistry, Chinese Academy of Sciences, and moved to the Qingdao University of Science and Technology in 2015. He was winner of the National Science Fund for Distinguished Young Scholars (2012), and became the Fellow of Royal Society of Chemistry (2018). His research interests include design and synthesis of stimuli-responsive polypeptides, preparation of biodegradable polyesters from biobased monomers, developing organocatalysts and phosphazene  superbase for ring opening (co)polymerization of cyclic esters and epoxides, and studying the self-assembly of copolymers with multi-hydrogen bonding interactions.

 

Read some of his recent articles below for FREE until 17th January!

Self-crosslinking assemblies with tunable nanostructures from photoresponsive polypeptoid-based block copolymers
Jirui Wei,   Jing Sun,   Xu Yang,   Sifan Ji,   Yuhan Wei  and  Zhibo Li
Polym. Chem., 2020, Advance Article (Part of our 2020 Emerging Investigators issue)

Fast, selective and metal-free ring-opening polymerization to synthesize polycarbonate/polyester copolymers with high incorporation of ethylene carbonate using an organocatalytic phosphazene base
Chuanzhi Wei,   Xinhui Kou,   Shaofeng Liu  and  Zhibo Li
Polym. Chem., 2019,10, 5905-5912

Phosphazene superbase catalyzed ring-opening polymerization of cyclotetrasiloxane toward copolysiloxanes with high diphenyl siloxane content
Jinfeng Shi,   Na Zhao,   Shuang Xia,   Shaofeng Liu  and  Zhibo Li
Polym. Chem., 2019,10, 2126-2133

A facile method to prepare high molecular weight bio-renewable poly(γ-butyrolactone) using a strong base/urea binary synergistic catalytic system
Yong Shen,    Zhichao Zhao,   Yunxin Li,   Shaofeng Liu,   Fusheng Liu  and  Zhibo Li
Polym. Chem., 2019,10, 1231-1237

Schiff base and reductive amination reactions of α-amino acids: a facile route toward N-alkylated amino acids and peptoid synthesis
Xiaohui Fu,   Zheng Li,   Jirui Wei,   Jing Sun  and  Zhibo Li
Polym. Chem., 2018,9, 4617-4624

Preparation of biorenewable poly(γ-butyrolactone)-b-poly(l-lactide) diblock copolyesters via one-pot sequential metal-free ring-opening polymerization
Yong Shen,   Jinbo Zhang,   Na Zhao,   Fusheng Liu  and  Zhibo Li
Polym. Chem., 2018,9, 2936-2941


As a Polymer Chemistry Associate Editor, Zhibo will be handling submissions to the journal.

Why not submit your next paper to his Editorial Office?

 

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