Paper of the month: Structure/property relationships in copolymers comprising renewable isosorbide, glucarodilactone, and 2,5-bis(hydroxymethyl)furan subunits

Lillie et al. report the synthesis of linear carbohydrate derived polyesters and their effect on mechanical properties.

Polyesters obtained from bio-derived monomers are often used as building blocks with the ultimate aim of meeting consumer demands for high-performance and sustainable materials. To this end, Reineke, Tolman, and Lillie sought to establish how changing the ratio of the sustainable D-glucaro-1,4:6,3-dilactone containing α, ω-diene (GDLU) and isosorbide undecanoate (IU) may influence the thermal, chemical and mechanical properties of the acyclic diene metathesis (ADMET)-derived polymers. The authors synthesized a series of random copolymers consisting of a range of GDLU and IU compositions and fully characterized them by uniaxial tensile testing, small-amplitude oscillatory shear rheology, X-ray scattering, and hydrolytic degradation testing.

 

It was found that small compositional changes have a detrimental impact on their mechanical performance and degradability. In addition, the authors investigated which carbohydrate-based building block was most important in promoting the elasticity and shape-memory abilities of this class of materials. To address this issue, GDL or isosorbide were replaced with a different sustainable diol, 2,5-bis(hydroxymethyl) furan. Studies of the resulting copolymers indicated that GDLU is responsible for imparting both elasticity and shape memory properties. Further, more economical and environmentally-friendly routes for the synthesis of GDLU and IU feedstocks were also explored.

 

Tips/comments directly from the authors:

  1. Acetonitrile appears to be the essential solvent for the scandium triflate-catalyzed esterification of GDL with 10-undecenoic acid anhydride.
  2. 10-Undecenoic acid anhydride can rapidly degrade on wet silica gel. To prevent this, oven dry (120 °C) the silica gel prior to its use and minimize the excess 10-undecenoic acid anhydride used in the reaction.
  3. Due to the hydrolytic instability of GDL and GDL-containing polymers, they should be stored in a vacuum desiccator to protected from moisture to prevent degradation between uses.

 

Read this exciting research for free until 13/08/2017 through a registered RSC account.

 

Structure/property relationships in copolymers comprising renewable isosorbide, glucarodilactone, and 2,5-bis(hydroxymethyl)furan subunits
Polym. Chem., 2017, 8, 3746-3754, DOI: 10.1039/c7py00575j

 

 

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About the webwriterAthina Anastasaki

Dr. Athina Anastasaki is a web writer for Polymer Chemistry. She is currently a Global Marie Curie Fellow working alongside Professor Craig Hawker at the University of California, Santa Barbara (UCSB). Please visit this website for more

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European Polymer Federation – Australian European Workshop

At this year’s European Polymer Federation Congress, Polymer Chemistry is pleased to sponsor the Australian-European Polymer Symposium, which will take place on Tuesday 4 July. The workshop will include 12 lectures (six from Australia, six from Europe) to illustrate connections, interactions and collaborations between European and Australian polymer researchers and will also include the presentation of Polymer Chemistry and Soft Matter poster prizes.

Invited speakers include:

Emmanuel P. Giannelis (Cornell University, USA)
Gaetano Guerra
(Università degli Studi di Salerno, Italy)
Dave Haddleton
(University of Warwick)
Tanja Junkers
(Universiteit Hasselt, Belgium)
Simon Harrisson
(Université de Toulouse III Paul Sabatier, France)
Felix Schacher
(Friedrich Schiller University Jena, Germany)
Hans Heuts
(Technische Universiteit Eindhoven, Netherlands)
Leonie Barner
(Queensland University of Technology, Australia)
Holger Schönherr 
(Universität Siegen, Germany)
Neil Cameron
(Monash University, Australia)
Markus Muellner
(University of Sydney, Australia)
Greg Qiao
(University of Melbourne, Australia)

EPF 2017 will be held from 2-7 July at the Lyon Convention Center and will focus on the latest trends in the polymer science and technology industry, including macromolecular chemistry; physics of polymers and polymer materials; modelling and simulation and polymer characterisation.

To register now, click here or visit the EPF website for more details on the speaker list and other workshops.

 

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Paper of the month: Block copolymer synthesis in one shot: concurrent metal-free ATRP and ROP processes under sunlight

Aydogan et al. report the.facile synthesis of block copolymers consisting of different monomer familes via successfully combining ATRP and ROP strategies.

Block copolymers are of a great interest to the polymer chemistry community as they provide intermediate physicochemical properties when compared to the respective homopolymers. Sequential monomer addition, mechanistic transformation and coupling of different segments are three of the most popular approaches to obtain block copolymers. However, all these approaches suffer from several drawbacks such as being limited to monomers that can be polymerized only under the same polymerization mechanism or requiring extreme experimental precautions and elongated purification steps.



In order to address the latter challenge, Yagci, Yilmaz and co-workers developed the first metal free example of block copolymer formation in which they concurrently polymerize structurally different monomers from a junction point serving as two functional groups for each polymerization. Since atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP) are not expected to interfere with each other and as such could be the ideal candidates for such a system. In order to test this hypothesis, a specifically designed initiator was synthesized possessing a tertiary bromine at one end (capable of initiating an ATRP reaction) and a hydroxyl functionality at the other end (capable for initiating a ROP reaction). Under carefully optimized conditions and in the presence of both the ATRP and ROP catalysts both methyl methacrylate (MMA) and ε- caprolactone could be simultaneously polymerized yielding a diblock copolymer with good agreement between theoretical and experimental value sand low dispersity values. Interestingly, the reaction took place on the roof of the chemistry department at Istanbul technical university utilizing natural sunlight as the light source. The applicability of this technique was further demonstrated by the simultaneous polymerization of different sets of monomers including n butyl acrylate- ε- caprolactone and methyl methacrylate-lactide combinations. As such, the successful combination of ATRP with ROP in the same reaction media allows for the facile one pot synthesis of block copolymers which can find use in further applications where excess of metals or inorganic residues would be undesirable.

Tips/comments directly from the authors:

1. All chemicals should be added into the reaction tube under nitrogen atmosphere in dark (perhaps by covering the outside of the tube with an aluminium foil) to avoid any premature light induced polymerization.
2. ROP polymerization can take place even in dark. Therefore, the ROP catalyst should be added last, and afterwards, the reaction tube should be exposed to sunlight as soon as possible. This way, one can provide the optimum conditions for the polymerizations to be realized simultaneously.
3. The method is best applicable in sunny days. Sunlight was deliberately selected as the most natural and simple way of light exposure. However, various other irradiation sources that emit in the wavelength regions matching with the absorption of appropriate sensitizers can also be used.

Read this exciting research for free until 17/07/2017 through a registered RSC account.

 

Block copolymer synthesis in one shot: concurrent metal-free ATRP and ROP processes under sunlight
Polym. Chem., 2017, 8, 2899-2903, DOI: 10.1039/c7py00069c

 

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About the webwriterAthina Anastasaki

Dr. Athina Anastasaki is a web writer for Polymer Chemistry. She is currently a Global Marie Curie Fellow working alongside Professor Craig Hawker at the University of California, Santa Barbara (UCSB). Please visit this website for more

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Focus on: Naturally Occurring Polymers

This month we focus on 3 articles published in Polymer Chemistry which report the use of naturally occurring polymers. As opposed to synthetic polymers, naturally occurring polymers are produced by living organisms in nature. Classes of naturally occurring polymers include proteins, polynucleotides, polyisoprenes, lignin and polysaccharides. These polymers can be extracted and utilised in various applications. In particular, polysaccharides such as cellulose and chitosan are cheap and abundant, biodegradable and are being used increasingly due to growing environmental concerns. Here, chitosan and/or celluose are utilised for the preparation of hydrogels, cellulose modification, and with thermo-conductive carbon nanotubes, exemplifying the broad versatility of these naturally occurring polymers.

1. Highly cost-effective and high-strength hydrogels as dye adsorbents from natural polymers: chitosan and cellulose
Hu Tu, Yi Yu, Jiajia Chen, Xiaowen Shi, Jialin Zhou, Hongbing Deng, Yumin Du
Polym. Chem., 2017, 8, 2913-2921; DOI: 10.1039/C7PY00223H

The authors decribe the preparation of composite hydrogels comprising chitosan, cellulose and rectorite for use as adsorbents for waste water treatment. The hydrogels had good elasticity and strength with the ability to restore their shape after compression. The adsorption efficiency was demonstrated with a dye molecule, which was adsorbed from solution. In addition these materials show promise as adsorbents for heavy metals.

2. Tandem modification of amphiphilic cellulose ethers for amorphous solid dispersion via olefin cross-metathesis and thiol-Michael addition
Yifan Dong, Laura I. Mosquera-Giraldo, Lynne S. Taylor, Kevin J. Edgar
Polym. Chem., 2017, 8, 3129-3139; DOI: 10.1039/C7PY00228A

The combination of olefin cross-metathesis and thiol-Michael addition chemistries have been used to functionalise cellulose derivatives. This methodology allowed for the design of certain cellulose-based polymers for potential use in amorphous solid dispersion, which can enhance the bioavailability of a poorly soluble drug. Mild reaction conditions and functional group tolerance make this strategy appealing for use with other polysaccharides.

3. Thermo conductive carbon nanotube-framed membranes for skin heat signal-responsive transdermal drug delivery
Ji-Hye Kang, Han-Sem Kim, Ueon Sang Shin
Polym. Chem., 2017, 8, 3154-3163; DOI: 10.1039/C7PY00570A

Smart carbon nanotube (CNT)-framed membranes were prepared from CNTs, chitosan and a thermoresponsive polymer, with an LCST around body temperature. The chitosan was used as a biocompatible adhesive to give cohesion to the CNTs. The loading and release of bovine serum albumin (BSA) was investigated and a high loading capacity was found, with temperature-dependent release of the BSA. The hybrid memberanes show potential as patch type transdermal drug delivery devices.

Read these articles for free until July 17th


About the webwriterFiona Hatton

Dr. Fiona Hatton is a web writer for Polymer Chemistry. She is currently a postdoctoral researcher in the Armes group at the University of Sheffield, UK. Find her on Twitter: @fi_hat

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Polymer Chemistry Lectureship Award Julien Nicolas at APME 2017

Dr. Julien Nicolas (Université Paris Sud, France) was presented the 2017 Polymer Chemistry Lectureship at APME 17 – Advanced Polymers via Macromolecular Engineering in Ghent

Dr Julien Nicolas (Université Paris Sud, France) was presented the 2017 Polymer Chemistry Lectureship award at APME 17 – Advanced Polymers via Macromolecular Engineering in Ghent. The prize was awarded by Polymer Chemistry Associate Editor Prof. Dr. Christopher Barner-Kowollik from Queensland University of Technology and Karlsruhe Institute of Technology.

 
APME 2017 (Advanced Polymers via Macromolecular Engineering) took place in Ghent, Belgium on May 21-25, 2017.  The focus of the APME2017 meeting was on macromolecular engineering for the design of advanced polymeric structures, in connection to their characterisation and recent applications.

 

Dr. Julien Nicolas (left) holding the Polymer Chemistry prize awarded by Prof. Dr. Christopher Barner-Kowollik (right)

 

 

Congratulations to Julien on his award!

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International Symposium on Ionic Polymerization – IP 2017

The 12th International Symposium on Ionic Polymerization (IP 2017) will be held at Durham University, UK from 17 – 22 September, organised and hosted by the Durham Centre for Soft Matter. 

The focus of IP 2017 will be on academic and industrial research in the areas of anionic, cationic and ring-opening polymerization mechanisms. Contributions related to other methods of living/controlled polymerization (catalytic, controlled free-radical, and step-growth polymerizations) will also be covered.

IP 2017 will feature also feature number of international leading invited speakers, as well as oral presentations, short talks for younger researchers and a poster session, supported by Polymer Chemistry, which will provide participants the opportunity to highlight their recent work. Submission deadlines for all abstracts is 31 May.

If you would like to attend, please register before 1 August in order to claim the early-bird rate. You can also read more about the symposium on the IP 2017 website.

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Paper of the month: Mild and efficient synthesis of ω,ω-heterodifunctionalized polymers and polymer bioconjugates

Figg et al. report the efficient synthesis of ω,ω-heterodifunctionalized polymers and polymer bioconjugates under mild reaction conditions.

 

The versatile and high yielding modification of polymer end groups is a critical tool for controlling materials properties. However, when multiple different functionalities are needed, pre-installation of two different functional groups at the polymer end groups is typically a tedious requirement. Sumerlin, Castellano and co-workers managed to circumvent this by developing a mild approach that enables the efficient synthesis of ω-ω-heterodifunctionalized polymers and polymer bioconjugates. Key to this strategy is the use of the recently introduced reagent benzotrifuranone (BTF) which allows the introduction of differentially “clickable” functional groups to monomethyl ether poly(ethylene glycol) amine (mPEG amine). In contrast to conventional polymer heterofunctionalization approaches that require high temperatures, significant excess of reagents and numerous synthetic steps, BTF serves as an ideal functionalization handle that operates at ambient temperature using near-stoichiometric amounts of reagents. Importantly, following functionalization of BTF with alkyne and alkene functional groups a fluorescent (coumarin) dye and biotin could be successfully conjugated to the end of mPEG-amine. These polymer bioconjugates were then able to bind avidin while showing an unexpected disruption of avidin tetramer formation. Overall, the compatibility of BTF with a broad scope of amine nucleophiles and thermally sensitive moieties (e.g. proteins) in combination with the highly efficient and mild nature of this reagent holds great promise for more elaborate heterofunctionalization strategies.

 

 

Tips/comments directly from the authors:

 

  1. The reaction time of the first and second addition to BTF should be monitored (typically by thin layer chromatography) to ensure minimal over/under functionalization occurs.
  2. The trisubstitution products are tolerant to many reaction conditions; however, when performing reactions that include radical intermediates, higher than usual reagent equivalents may be needed due to the radical scavenging nature of the phloroglucinol
  3. When one-pot homodifunctionalizations are performed, be sure to add enough nucleophile to consume both electrophilic sites on the polymer end group and the three electrophilic sites on any unreacted BTF.
  4. Regarding BTF synthesis: 1) Using fresh polyphosphoric acid and monitoring the reaction temperature is very important for the ring-closing in the last step of the synthesis, and 2) BTF and the mono- and difuranone derivatives are sensitive to silica gel, so avoid letting the compounds reside in a column too long during purification.

 

Read this exciting research for free until 21/06/2017 through a registered RSC account.

 

Mild and efficient synthesis of ω,ω-heterodifunctionalized polymers and polymer bioconjugates
Polym. Chem., 2017,8, 2457-2461, DOI: 10.1039/C7PY00225D

 

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About the webwriterAthina Anastasaki

Dr. Athina Anastasaki is a web writer for Polymer Chemistry. She is currently a Global Marie Curie Fellow working alongside Professor Craig Hawker at the University of California, Santa Barbara (UCSB). Please visit this website for more

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Focus on: Polymer Self-Assembly

Self-assembly of block copolymers is well-known to form polymeric particles with various morphologies, for example, spherical, cylindrical and vesicular morphologies. This month we focus on three research articles published in Polymer Chemistry involving polymer self-assembly.

Polymer self-assembly is driven by the respective solubilities of the blocks of the copolymer in the solvent media present. For example, when water is the desired media the polymer is designed so that one block is water soluble and one block is water insoluble. Either post-polymerisation self-assembly, or in situ polymerisation-induced self-assembly can be employed to form a range of particle morphologies. Post-polymerisation self-assembly typically relies on a solvent switch technique whereby the block copolymer is dissolved in a good solvent for the whole polymer, and is subsequently added to another miscible solvent which is a good solvent for one block and a non-solvent for another. On the other hand, polymerisation-induced self-assembly involves the chain extension of a soluble stabiliser block with a monomer, which when polymerised is insoluble, therefore the polymerisation of the monomer drives the self-assembly process.

The first two articles here utilise polymerisation-induced self-assembly, whilst the third employs post-polymerisation self-assembly. Interestingly, all of the articles highlighted here have employed reversible addition-fragmentation chain-transfer (RAFT) polymerisation as the polymerisation technique of choice to prepared the polymers studied.

 

 

1. In situ synthesis of a self-assembled AB/B blend of poly(ethylene glycol)-b-polystyrene/polystyrene by dispersion RAFT polymerization
Bing Yuan, Xin He, Yaqing Qu, Chengqiang Gao, Erika Eiser, Wangqing Zhang
Polym. Chem., 2017,8, 2173-2181; DOI: 10.1039/C7PY00339K

In this article, the authors present the self-assembly of diblock copolymers and homopolymers through a dispersion RAFT polymerisation. The use of a poly(ethylene glycol) macromolecular chain-transfer agent (macro-CTA) and a small molecule CTA led to the formation of various self-assembled morphologies that were considerably different from the pre-synthesised equivalent blends. Morphologies obtained include: vesicles, compartmentalized vesicles and porous nanospheres.

2. RAFT/MADIX emulsion copolymerization of vinyl acetate and N-vinylcaprolactam: towards waterborne physically crosslinked thermoresponsive particles
Laura Etchenausia, Abdel Khoukh, Elise Deniau Lejeune, Maud Save
Polym. Chem., 2017, 8, 2244-2256; DOI: 10.1039/C7PY00221A

Here, the RAFT/MADIX batch emulsion copolymerisation of vinyl acetate (VAc) and N-vinyl caprolactam (VCL) was performed using a poly(ethylene glycol) macro-CTA. The resulting particles were physically crosslinked and thermoresponsive, and particles with a core composition of VAc and VCL of 47:53 exhibited a reversible swelling-to-collapse transition with heating. The hydrolysis of VAc units to vinyl alcohol gave thermoresponsive biocompatible statistical copolymers.

3. CO2-Triggered UCST transition of amphiphilic triblock copolymers and their self-assemblies
Shaojian Lin, Jiaojiao Shang, Patrick Theato
Polym. Chem., 2017, 8, 2619-2629; DOI: 10.1039/C7PY00186J

RAFT polymerisation was used to prepare triblock copolymers consisting of poly[(ethylene glycol)methyl ether]-b-poly(acrylamide-co-acrylonitrile)-b-poly(diethylamino ethyl methacrylate), which self-assembled in water to form vesicles. As this triblock copolymer contains a temperature responsive segment and a COresponsive block, a morphological transition from vesicles to micelles could be achieved with a COpurge, and then to unimers with an increase in temperature.

Read these articles for free until June 21th


About the webwriterFiona Hatton

Dr. Fiona Hatton is a web writer for Polymer Chemistry. She is currently a postdoctoral researcher in the Armes group at the University of Sheffield, UK. Find her on Twitter: @fi_hat

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2017 Polymer Chemistry Lectureship awarded to Julien Nicolas

It is with great pleasure that we announce Dr Julien Nicolas (Université Paris Sud, France) as the recipient of the 2017 Polymer Chemistry Lectureship.

This award, now in its third 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.

Read on to find out more about Julien…

Dr Julien Nicolas

Julien Nicolas obtained his Doctor of Philosophy in Chemistry and Physical Chemistry of Polymers in 2005 from the Laboratory of Polymer Chemistry, at the Université Pierre and Marie Curie, in Paris, France, under the supervision of Prof. Bernadette Charleux. He then joined Prof. David Haddleton’s group at the University of Warwick as a postdoctoral fellow in 2006. In 2007, he became a CNRS researcher at Institut Galien, Paris Sud, and became a Director of Research in the same institute in 2016. He has published more than 80 refereed scientific articles (h-index 36), filled 5 patents and is currently Associate Editor for Chemistry of Materials (ACS).

Julien’s current research interests are multidisciplinary and span from organic chemistry and polymer synthesis to nanoparticulate systems and biomedical applications. The current interests of his group are focused on multifunctional biodegradable nanoparticles, well-defined molecular/polymer prodrug nanoparticles and controlled polymerization techniques from both fundamental and applied standpoints, with an emphasis on their application for the synthesis of biodegradable vinyl polymers and innovative biomaterials. Awards and honours he has received to date include the French Polymer Society (GFP) / French Chemical Society (SCF) award in 2016, and the 2017 Polymer Chemistry Lectureship award.

 

 

To learn more about Julien’s research, have a look at some of his publications in Polymer Chemistry:

Structure–cytotoxicity relationship of drug-initiated polymer prodrug nanoparticles
Yinyin Bao and Julien Nicolas
Polym. Chem., 2017, DOI: 10.1039/C7PY00536A

Efficient synthesis of 2-methylene-4-phenyl-1,3-dioxolane, a cyclic ketene acetal for controlling the NMP of methyl methacrylate and conferring tunable degradability
Johanna Tran,Elise Guégain, Nada Ibrahim, Simon Harrisson and Julien Nicolas
Polym. Chem., 2016, 7, 4427-4435

On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation
Elise Guégain, Vianney Delplace, Thomas Trimaille, Didier Gigmes, Didier Siri, Sylvain R. A. Marque, Yohann Guillaneuf and Julien Nicolas
Polym. Chem., 2015,6, 5693-5704

Recent trends in the design of anticancer polymer prodrug nanocarriers
Vianney Delplace, Patrick Couvreur and Julien Nicolas
Polym. Chem., 2014, 5, 1529-1544

We would like to thank everybody who nominated a candidate for the Lectureship; we received many excellent nominations, and the Editorial Board had a difficult task in choosing between some outstanding candidates.

Please join us in congratulating Julien on his award!

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3rd Functional Polymeric Materials Conference

The third FPM series will bring together leaders in polymers and polymeric materials from around the world to describe their most recent and cutting edge discoveries.

The aim of the conference, which takes place in Rome, Italy from 7-10 July, is to capture the multidisciplinary nature of polymer chemistry with topics spanning “basic synthesis and methodology” to “nanoscale and bioinspired materials”.

This conference will appeal to academics, students, postdoctoral research associates, industrial scientists and leaders, governmental researchers and those currently involved in the development of polymeric material applications to address the most critical needs in areas such as medicine, energy and sustainability.

Talk submission ends 1 Mayregsiter here

Poster submission ends 10 Maysubmit here

For more information and to see the full list of invited speakers, visit the conference website.

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