Paper of the month: SET-LRP of acrylates catalyzed by a 1 penny copper coin

Aksakal et al. report the Cu(0)-mediated living radical polymerization of acrylates using a British penny coin.

Cu(0)-mediated living radical polymerization, typically referred to as single electron transfer living radical polymerization (SET-LRP), is a versatile tool for the synthesis of advanced materials. The groups of Becer and Resmini have further highlighted this versatility by reporting the SET-LRP of acrylates catalyzed by a penny copper coin. Impressively, a wide range of hydrophobic and hydrophilic monomers were successfully polymerized yielding well-defined polymers with low dispersities, near-quantitative conversions and high end group functionality. The scope of the system was subsequently expanded to include the synthesis of star polymers through the core first approach. Interestingly, the authors used two type of coins, the first one (issued in 1971-1992) consisting of 97% of copper and the second one (issued after 1992) consisting of 6% of copper. Both coins exhibited near identical polymerization results. A series of polymerizations targeting different degrees of polymerization were also conducted, all proceeding with very good control over the molecular weight distributions. In comparison to traditional Cu(0)-wire systems, British penny coins have the additional advantage of prohibiting the induction period, which is typically observed for many SET-LRP reactions. Finally, the scalability of these polymerizations up to 50 gram scale was also successful and thus demonstrating an economic, efficient and easily accessible catalyst for SET-LRP of various acrylic monomers.


Tips/comments directly from the authors:

Comments:

In this study, we provide direct evidence that the traditionally used Cu(0)-wire can be replaced with a copper coin, regardless to its year of issue. To avoid any induction period, this method can be employed for the synthesis of well-defined polymers of acrylates with both linear and star shaped initiators.


Tips:

  1. Since the coins are usually contaminated due to prior circulation, we suggest for reproducibility purposes a quick rinse with a freshly prepared HCl before the polymerization.
  2. As mentioned in the manuscript, both penny coins issued before and after 1992 exhibit near identical polymerization results. However, the coins issued after 1992 consist of 94% steel and are magnetic. Due to this, it should be taken into account that the magnetic stirrer can occasionally spin out of its axis. Therefore, we suggest the use of narrow and long Schlenk tube to avoid any splashing of the polymerization mixture.
  3. Due to the reactivity of the polymerization mixture, samples for both NMR and GPC should be diluted immediately in order to avoid errors during kinetic sampling.
  4. The inhibitor of monomers can be easily removed by passing over a plug of basic aluminium oxide. Due to the high viscosity of the OEGA480 monomer, larger volumes can be diluted in a volatile solvent to decrease viscosity. Evaporation of the solvent will provide the inhibitor-free monomer.

Read this exciting research for free until 25/11/2016 through a registered RSC account:

SET-LRP of acrylates catalyzed by a 1 penny copper coin
R. Aksakal, M. Resmini and C.R. Becer
Polym. Chem.
, 2016, 7, 6564-6569
DOI: 10.1039/C6PY01295G

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About the webwriterAthina Anastasaki

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

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Focus on: Boron Functional Polymers

This month we take a look at three articles published in Polymer Chemistry reporting the use of boron, either as boron-functional polymers or polymerisation catalyst. Boron is an interesting element, essential to life, and has mainly been investigated in the field of polymer chemistry through boronic acid, organoborate and carborane functional polymers. The incorporation of boronic acid into various polymers is of interest due to its responsiveness to pH, and ability to bind 1,2- and 1,3-diols resulting in anionic boronate ester complexes. This has been probably most widely investigated as materials for the detection of glucose which has broad biomedical implications.

The first two articles here focus on the incorporation of boronic acid into polymeric materials, whilst the final article presents the use of a boronate-urea as a co-catalyst for ring opening polymerisation.

ToC figure

1. Bioinspired synthesis of poly(phenylboronic acid) microgels with high glucose selectivity at physiological pH
Qingshi Wu, Xue Du, Aiping Chang, Xiaomei Jiang, Xiaoyun Yan, Xiaoyu Cao, Zahoor H. Farooqi, Weitai Wu
Polym. Chem., 2016, 7, 6500-6512; DOI: 10.1039/C6PY01521B

Here, poly(phenyl boronic acid) microgels were prepared through the free radical polymerisation of 4-vinylphenylboronic acid and a cross-linker in the presence of a surfactant. The microgels swelled in the presence of glucose (0-30 mM) at physiological pH (7.4), with an enhanced swelling ratio when compared to other monosaccharides, and a highly selective glucose-dependant fluorescence emission. These materials showed potential for use as sensors for glucose detecting.

2. Synthesis of novel boronic acid-decorated poly(2-oxazoline)s showing triple-stimuli responsive behavior
Gertjan Vancoillie, William L. A. Brooks, Maarten A. Mees, Brent S. Sumerlin, Richard Hoogenboom
Polym. Chem., 2016, 7, 6725-6734; DOI: 10.1039/C6PY01437B

The authors describe boronic acid functional poly(2-alkyl-2-oxazoline)s through the cationic ring opening copolymerisation of 2-n-propyl-2-oxazoline and a methyl ester oxazoline, followed by subsequent post-polymerisation modification to functionalise the polymer with boronic acid moeities. The subsequent polymers exhibited LCST behaviour, with pH and glucose concentration dependancy for the thermal transitions, highlighting possible applications in drug delivery, for example.

3. Internal Lewis pair enhanced H-bond donor: boronate-urea and tertiary amine co-catalysis in ring-opening polymerization
Songquan Xu, Herui Sun, Jingjing Liu, Jiaxi Xu, Xianfu Pan, He Dong, Yaya Liu, Zhenjiang Li, Kai Guo
Polym. Chem., 2016, 7, 6843-6853; DOI: 10.1039/C6PY01436D

In this article, the use of a boronate-urea (BU)  has been presented as a Lewis pair enhanced H-bond donor for the co-catalysis of the ring opening polymerisation of ʟ-lactide. The polymerisations reached high conversions and the resultant polymers exhibited controlled molecular weights and low dispersites. The BU was shown to be mild, tunable and compatible with several tertiary amines, and more efficient than a common urea.

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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 Global Conference on Polymer and Composite Materials (PCM 2017)

23-25 May 2017, Guangzhou, China

The 2017 Global Conference on Polymer and Composite Materials (PCM 2017) will be held in the beautiful city of Guangzhou, China.

This well-established conference series is dedicated to cover all theoretical and experimental aspects of polymers and composite materials. Building on the hugely successful preceding Conferences (PCM 2014 in Ningbo, PCM 2015 in Beijing, and PCM2016 in Hangzhou), PCM 2017 will provide an ideal academic platform for researchers to present their latest findings, and to facilitate networking and in-depth discussion with peers from Asia, Europe and USA.

The scientific program will focus not only on current advances in the research, but also in the production and use of polymers and composite materials in different fields. The conference setting has a highly focused technical program through plenary, invited, oral and poster presentations.

Keynote speakers

Abstract submission: Click here

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Royal Society of Chemistry and ACS Publications commit to ORCID integration

Yesterday, the Royal Society of Chemistry and the American Chemical Society Publications Division, ACS Publications, both signed the ORCID Open Letter committing to unambiguous identification of all authors that publish in our journals.

The official press release can be found here: http://rsc.li/orcid

In brief, this partnership with ORCID will resolve ambiguity in researcher identification caused by name changes, cultural differences in name presentation, and the inconsistent use of name abbreviations, thereby ensuring their contributions are appropriately recognized and credited.

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11th SPSJ International Polymer Conference (IPC2016)

13 – 16 December 2016, Fukuoka, Japan

13 – 16 December 2016, Fukuoka, Japan

The Society of Polymer Science, Japan (SPSJ) has organized SPSJ International Polymer Conferences (IPC) since 1984 offering an excellent platform to meet and discuss most updated topics in polymer science and technology.
The 11th SPSJ International Polymer Conference (IPC2016) will cover all aspects of polymer chemistry from synthesis to green chemistry, from semiconductor science to bio-related polymers, to make the conference “the cutting edge in polymer science & technology and the next milestone”.


Key oral Sessions:

  • Recent Trends in Polymer Synthesis
  • Recent Trends in Physics for Macro- and Supra-molecules
  • Frontiers in Surface and Interface in Macromolecular Systems
  • Frontiers in Biomedical Polymers and Nanomedicines
  • Optics, Electronics and Energy
  • Polymers in Automobiles and Aircrafts
  • Polymers in Green Chemistry
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RSC Materials Chemistry Division Poster Symposium – final registration deadline

Register by 15 November 2016

RSC Materials Chemistry Division Poster Symposium

This is your last chance to attend RSC Materials Chemistry Division Poster Symposium as the final registration deadline is just a few days away. Be sure to register by 15 November 2016 to secure your place.

For full details of speakers and conference themes, please visit the event web page.

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Focus on: Supramolecular Polymerisation

This month we focus on three articles appearing in Polymer Chemistry which report various types of Supramolecular Polymerisation. Supramolecular polymers are polymers formed through reversible non-covalent bonds, such as hydrogen bonding, π-π interactions, coordination and host-guest interactions. Advantages of supramolecular polymers include self-healing properties, improved processability, degradability and recyclability; these materials have found applications in fields including optoelectronics, tissue engineering, drug delivery, gene transfection, self healing films and networks to name a few. The articles highlighted this month demonstrate supramolecular polymerisation directed by coordination and host-guest interactions.

Graphical abstract

1. Ligand effects on cooperative supramolecular polymerization of platinum(II) acetylide complexes
Zhao Gao, Junlong Zhu, Yifei Han, Xiaoqin Lv, Xiaolong Zhang, Feng Wang
Polym. Chem., 2016, 7, 5763-5767; DOI: 10.1039/C6PY01440B

The authors present the formation of helical nano-fibers and organogels by supramolecular polymerisation of a rod-like platinum(II) acetylide monomer with less bulky ligand substituents. The self-assembly mechanism was found to be through a cooperative nucleation–elongation mechanism, and the more-bulky monomers showed no aggregation. These results highlight the importance of minor monomer variations on the supramolecular polymerisation mechanism.

2. Supramolecular main-chain polycatenanes formed by orthogonal metal ion coordination and pillar[5]arene-based host–guest interaction
Hao Xing and Bingbing Shi
Polym. Chem., 2016, 7, 6159-6163; DOI: 10.1039/C6PY01617K

The combination of catenanes and supramolecular polymers has been reported here, where the authors show the orthogonal use of coordination between zinc ions and terpyridyl groups and pillar[5]arene host-guest interactions. The materials exhibited glue-sol transitions with a change of temperature or hydroxide ion concentration. The mechanical properties were assessed by rheology, which showed improvement compared with a supramolecular polymer without catenane functionality.

3. Pillar[5]arene-based amphiphilic supramolecular brush copolymers: fabrication, controllable self-assembly and application in self-imaging targeted drug delivery
Guocan Yu, Run Zhao, Dan Wu, Fuwu Zhang, Li Shao, Jiong Zhou, Jie Yang, Guping Tang, Xiaoyuan Chen Feihe Huang
Polym. Chem., 2016, 7, 6178-6188; DOI: 10.1039/C6PY01402J

Supramolecular brush copolymers were prepared utilising host-guest interactions between pillar[5]arene and a viologen salt. The supramolecular brush copolymers self-assembled into single chain nanoparticles which were fluorescent due to the aggregation-induced emission effect. Doxorubicin loading was achieved and biotin labelling resulted in targeted drug delivery and imaging capabilities. The single-chain nanoparticles showed excellent anti-tumour efficacy with limited systemic toxicity in vivo.

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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 is now open!

Do you know an early-career researcher who deserves recognition for their contribution to the polymer chemistry field?

Now is your chance to put them forward for the accolade they deserve.

Polymer Chemistry is pleased to announce that nominations are now being accepted for its 2017 Lectureship award. This annual award was established in 2015 to honour an early-stage career scientist who has made a significant contribution to the polymer chemistry field.

Previous winners

2016 – Feihe Huang, Zhejiang University, China

2015 – Richard Hoogenboom, Ghent University, Belgium

Qualification

To be eligible for the Polymer Chemistry Lectureship, the candidate should be in the earlier stages of their scientific career, typically within 15 years of attaining their doctorate or equivalent degree, and will have made a significant contribution to the field.

Description

The recipient of the award will be asked to present a lecture three times, one of which will be located in the home country of the recipient. The Polymer Chemistry Editorial Office will provide the sum of £1000 to the recipient for travel and accommodation costs.

The recipient will be presented with the award at one of the three award lectures. They will also be asked to contribute a lead article to the journal and will have their work showcased on the back cover of the issue in which their article is published.

Selection

The recipient of the award will be selected and endorsed by the Polymer Chemistry Editorial Board.

Nominations

Those wishing to make a nomination should send details of the nominee, including a brief C.V. (no longer than 2 pages A4) together with a letter (no longer than 2 pages A4) supporting the nomination, to the Polymer Chemistry Editorial Office by 27thJanuary 2017. Self-nomination is not permitted.

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Paper of the month: Regioselective cross metathesis for block and heterotelechelic polymer synthesis

Radlauer et al. report the regioregularity of ring-opening metathesis polymerization and cross metathesis reactions for the synthesis of block and heterotelechelic materials.

Among the two distinct olefin metathesis polymerization methods, namely acyclic diene metathesis (ADMET) polymerization and ring opening metathesis polymerization (ROMP), ROMP possesses the advantage of proceeding by a chain growth mechanism and has been demonstrated to deliver polymers with an R substituent every 8 carbons from 3-substituted cyclooctene (3RCOE) monomers. Although secondary metathesis such as cross metathesis (CM) can occur between chains during ROMP, when the selectivity of 3RCOE monomers was examined, no studies on the CM were conducted. Towards this direction, Hillmyer and co-workers determined the CM of 3RCOE derivatives to be both regio- and stereoselective, making only a small fraction of t-TT and t-HH errors. As only a marginal increase in errors over time was observed, it was concluded that the system reached an equilibrium between the formation and fixing of errors. This stereo- and regioselectivity can be extended by combining polymers with different degrees of polymerization, or by combining polymers with different R substituents leading to the formation of multiblock or statistical copolymers depending on how long the CM is allowed to proceed. In the latter case, differential scanning calorimetry (DSC) confirms the transition from two Tgs to one Tg corresponding to a multiblock and a statistical copolymer, respectively. Additionally, the location of end groups from an asymmetric chain transfer agent can be controlled, thus allowing access to predominantly heterotelechelic oligomers or polymers despite the CM reactions that can occur between the chains.

Tips/comments directly from the authors:

  1. In our experience if a polymer turned brown, it was generally caused by the presence of deactivated Grubbs catalyst. To remove this contaminant at the end of the polymerization, the polymer was dissolved in chloroform and stirred with carbon black. Subsequent filtration and reprecipitation of the polymer generally yielded clear and colorless materials.
  2. To obtain SEC data that was more easily interpreted, we used adjusted ratios of the polymers of different degrees of polymerization in the polymer-polymer cross metathesis experiments. Though the 1:1 scenario still showed immediate CM to an average N, the resolution between the two peaks was quite poor.

Any experiment involving the acetal-containing chain transfer agent required that each reaction component be filtered over basic alumina to avoid deprotection of the acetal moiety.

Read this exciting research for free until 25/11/2016 through a registered RSC account:

Regioselective cross metathesis for block and heterotelechelic polymer synthesis
M.R. Radlauer, M.E. Matta and M.A. Hillmyer,
Polym. Chem., 2016, 7, 6269-6278,
DOI: 10.1039/C6PY01231K

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About the webwriterAthina Anastasaki

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

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Lectureship winner featured on our back cover

Take a look at the back cover of our latest issue

We are immensely proud to share our back cover for Issue 40.

This beautiful image highlights research results by Professor Feihe Huang at University, Hangzhou, China. Professor Huang is the recipient of the 2016 Polymer Chemistry Lectureship award.

Pillar[5]arene-based amphiphilic supramolecular brush copolymers: fabrication,
controllable self-assembly and application in self-imaging targeted drug delivery

Guocan Yu, Feihe Huang, and co-workers fabricated the first pillar[5]arene-based amphiphilic supramolecular brush copolymer, which was utilized as a self-imaging drug delivery vehicle by taking advantage of the aggregation-induced emission effect.

In vitro and in vivo investigations demonstrated this supramolecular theranostic nanomaterial exhibited excellent antitumor efficacy with negligible systemic toxicity.

Read the full article

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