Archive for December, 2012

Happy holidays from Polymer Chemistry!

All of us in the Polymer Chemistry Editorial team would like to wish you all a merry Christmas and a happy new year! The Editorial office will be closed from 21 December 2012 and will reopen on 2 January 2013.

We’re really looking forward to 2013, which will see more high quality articles from top international polymer chemists, some great themed issues and much more.

Don’t miss out on all the journal news – follow us on twitter @PolymChem and like us on Facebook!

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Author of the Week: Dr. Massimo Benaglia

Dr. Massimo Benaglia graduated in Pharmacy at the University of Bologna in 1995. He started his professional career in 1986 joining the CNR (National Research Council) as a Technical Assistant becoming a Full Researcher in 2006. Having already acquired a strong background in organic synthesis, he spent 2002 at the CSIRO (Commonwealth Scientific and Industrial Research Organization) in Melbourne (Australia) working as a Visiting Scientist in Dr. Rizzardo’s group studying the RAFT (Reversible Addition-Fragmentation chain Transfer) process. Realizing the enormous potentialities of this technique led him to pursue his work in the controlled radical polymerization field. In 2006 he spent another year at CSIRO studying new RAFT agents with “switchable” properties and in 2007 started studying polymeric micelles obtained through the self-assembly of “pseudo-amphiphilic” block-copolymers. His current research interests focus upon the post-polymerization modifications of poly(glycidyl methacrylate) in order to obtain materials suitable for delivery of therapeutic (drugs, nucleic acids) and/or diagnostic agents (fluorescent probes).

Website: www.isof.cnr.it/?q=content/benaglia-massimo

What was your inspiration in becoming a chemist?

As a child one of my most frequent requests as a birthday present was the “Little Chemist” but I never actually received it. Later on, however, at high school, I chose chemistry as my main subject. It was actually at school that I discovered my passion for the chemistry lab doing experiments where I could “transform” something into something else. During my studies at Uni I applied for a job at the CNR (National Research Council) and when I was 21 I found myself actually working in a lab in a research group. I consider chemistry as a way of expressing my creativity since I don’t have a great artistic predisposition. Now, through studying and applying the RAFT process, I can enjoy designing and creating new materials capable of performing special and specific functions.

What was the motivation to write your Polymer Chemistry article?

The RAFT technique is a very versatile way to synthesize functional polymers with a defined architecture. The basic problem, however, is that polymerization conditions have to be optimized for each monomer/RAFT agent system. The use of glycidyl methacrylate might provide a way of overcoming this issue. Starting from the same pre-synthesized PGMA the article shows that it is possible to obtain many different kinds of polymers whose properties depend upon the nucleophilic agent chosen.

Why did you choose Polymer Chemistry to publish your work? (DOI:10.1039/C2PY20646C)

Polymer Chemistry is a journal that highlights all the novel aspects of polymer synthesis. Here, it is possible to follow the state of the art in this field. When I first came across the journal I was impressed by the high quality of the papers. Another great advantage is the very rapid review process.

In which upcoming conferences may our readers meet you?

I haven’t decided yet which conferences I will attend in 2013. I usually find small/medium-sized  conferences more fruitful in terms of scientific interactions and my choice will probably depend upon this aspect.

How do you spend your spare time?

Mostly with my relatives and friends. I like music and movies, but I also like food. Therefore, besides resting after tiring days, I go out to the cinema or to listen to live music or enjoy good food/wine in the company of friends.

Which profession would you choose if you were not a scientist?

I didn’t mention that I also like cooking and I would definitely have been a chef. I consider the “art” of cooking another very interesting way of expressing creativity with the advantage of the results being promptly verifiable, especially in a convivial way.

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Paper of the week: In situ stereocomplexing polymerization of methyl methacrylate

Stereocomplex poly(methyl methacrylate), sc-PMMA, is a crystalline material formed via van der Waals interactions between diastereomeric, isotactic (it) and syndiotactic (st), PMMA chains. It represents a rare example of helical supramolecular structures derived from a commodity polymer and is typically obtained in a 1/2 it/st ratio either in the solid state, when annealed, or in suitable solvents, when crystallized. In this study, Chen and co-workers hypothesized that, with the advent of stereospecific and living coordination polymerization by chiral metallocene catalysts, it is possible to combine the synthesis of highly stereoregular PMMAs with the fabrication of their crystalline stereocomplex into a one-step procedure, thereby producing such important crystalline materials in a rapid and cost/energy-saving fashion.

Graphical abstract: In situ stereocomplexing polymerization of methyl methacrylate by diastereospecific metallocene catalyst pairs

The authors demonstrate the first in situ stereocomplexing polymerization of  MMA using a pair of diastereospecific coordination polymerization catalysts for rapid, high-yield, ambient-temperature production of crystalline sc-PMMA. The diastereospecific catalyst pair is conveniently generated by in situ activation of a mixture of C2- and Cs -ligated metallocene bis(ester enolate)s with [Ph3C][B(C6F5)4], which is highly active, stereospecific, and controlled for coordination–addition polymerization of MMA. The isotactic/syndiotactic (it/st) composition of the sc-PMMA materials can be modulated by simply adjusting the relative ratio of the diastereospecific catalysts. The dynamic light scattering (DLS) results of the in situ stereocomplexing polymerization by a diastereospecific catalyst pair, obtained by monitoring the reaction in real time with DLS, indicate that stereocomplexation occurs as the diastereomeric PMMA chains are continuously growing. The presence of nanocages such as POSS and C60, which can be encapsulated by st-PMMA, in the stereocomplexing MMA polymerization system can completely disrupt or have no effect on the stereocomplexation, or enable both stereocomplexation and inclusion complexation processes to occur, depending on the type of nanocage employed.
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In situ stereocomplexing polymerization of methyl methacrylate by diastereospecific metallocene catalyst pairs by Nicole C. Escudé, Yalan Ning and Eugene Y.-X. Chen, Polym. Chem., 2012, 3, 3247-3255.

Julien Nicolas is a guest web-writer for Polymer Chemistry. He currently works at Univ. Paris-Sud (FR) as a CNRS researcher

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Paper of the week: Necklace- and donut-like poly(propylene imine) glycodendrimers

Over the past 30 years, dendrimers have attracted great attention in plenty of studies stimulated by the high symmetry and monodispersity of these branched macromolecules with well-defined size and shape. Today, these dendritic structures are tailor-made for achieving specific properties and for potential applications e.g. in bionanotechnology. In this context, one pivotal key issue is the indispensable use of non-covalent interactions and forces for establishing (self-)assembled and self-organized 0D, 1D, 2D and 3D structures. The understanding and control of these non-covalent interactions is also essential for successful application of functional dendrimers in (bio-)medical applications.

Graphical abstract: Self-assembly of poly(propylene imine) glycodendrimers: role of aromatic interactions in the formation of necklace- and donut-like nanostructures

In this study, the authors reported on the formation of necklace- and donut-like structures of water-soluble glycodendrimers bearing a small number of phenyl units as a time-dependent process in aqueous solution starting from self-assembled glycodendrimers to higher hierarchically assembled structures initially triggered by ultrasound treatment. For this study, they designed and synthesized new spherical poly(propylene imine) dendrimer structures by introducing on their peripheral amino groups: (i) hydrophilic bio-tolerable oligosaccharide units (maltose) and (i) hydrophobic groups (adamantyl or phenyl) capable of modifying the physical properties of these glycodendrimers. The glyco-conjugation of dendritic polyamines enabled the authors to enhance the water solubility and biocompatibility of the nanoconstructs which makes them potentially useful as drug delivery systems, therapeutic agents and artificial tubulating proteins.

Self-assembly of poly(propylene imine) glycodendrimers: role of aromatic interactions in the formation of necklace- and donut-like nanostructures by Marco Paolino, Franka Ennen, Hartmut Komber, Mihaela Cernescu, Andrea Cappelli, Bernhard Brutschy, Brigitte Voit and Dietmar Appelhans, Polym. Chem., 2012, 3, 3239-3242.

Julien Nicolas is a guest web-writer for Polymer Chemistry. He currently works at Univ. Paris-Sud (FR) as a CNRS researcher

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Author of the Week: Prof. Kristi L. Kiick

Kristi Kiick is a Professor of Materials Science and Engineering and a Professor of Biomedical Engineering at the University of Delaware (UD), and also serves as Deputy Dean of the UD College of Engineering.  She joined the UD faculty in August 2001.  She received a B.S. in Chemistry from the University of Delaware in 1989, and an M.S. in Chemistry as an NSF Predoctoral Fellow from the University of Georgia in 1991. In 1996, after working in industry at Kimberly Clark Corporation, she rejoined the academic ranks as a doctoral student. She received a Ph.D. in Polymer Science and Engineering from the University of Massachusetts Amherst in 2001 under the direction of David Tirrell, after completing her doctoral research as an NDSEG Fellow at the California Institute of Technology.  Her current research programs are focused on combining biosynthetic techniques, chemical methods, and bioinspired assembly strategies for the production of novel polymer architectures with advanced multifunctional behaviors. Kiick’s honors have included a Camille and Henry Dreyfus Foundation New Faculty Award, a Beckman Young Investigator Award, an NSF CAREER Award, a DuPont Young Professor Award.  Kiick has delivered a variety of keynote, plenary, and memorial lectureships, and serves on the editorial advisory boards of multiple journals.  She has recently been inducted into the College of Fellows of the American Institute for Medical and Biological Engineering, has published over 80 articles and book chapters, and holds over 15 US patents.

What was your inspiration in becoming a chemist?

I first became interested in chemistry when in high school, when I was introduced to the chemical composition and behaviors of molecules. I was fascinated by the possibility of understanding events at the macroscale because of their chemical behavior at the molecular level. I have always been interested in the biological aspects of chemistry, and have been fortunate that I can combine these interests in the macromolecular problems that we study in my group’s research.

What was the motivation to write your Polymer Chemistry article?

The triggered degradation of hydrogels as a result of differences in retro Michael-type addition kinetics will hopefully be a very useful tool for our community. We have been employing traditional thiol-maleimide Michael-type addition reactions in the formation of PEG-heparin hydrogels for several years now, and have been looking at how the mechanical properties of these hydrogels can control drug delivery and cellular behavior. We use this chemistry for the same reasons that many in our field do – because of its rapid rate and selectivity and resulting product stability. When we employed aryl thiols in the formation of PEG-LMWH hydrogels via these addition reactions, however, we observed puzzling degradation behavior of the hydrogels with variations in solution conditions. This motivated us to look at the chemical details of degradation, which indicated that in these PEG-LMWH hydrogels, the retro reaction of the aryl thiol-maleimide adducts liberated free maleimide that could be captured by endogenous thiols in solution. We have been developing this approach to make hydrogels that are sensitive to reductant load, and hope that these approaches will be similarly useful to others in our community.

Why did you choose Polymer Chemistry to publish your work? (DOI:10.1039/C2PY20576A)

We have appreciated the forward-looking focus of the articles and authors in Polymer Chemistry, and the range of macromolecular chemistry approaches that are published in this journal. We thought that this audience would be the perfect one for utilizing these chemical approaches and expanding them into areas that we may not be considering.

In which upcoming conferences may our readers meet you?

I am a regular at the American Chemical Society and Materials Research Society national meetings, and also attend other polymer and biomaterials-related meetings that are more targeted in scope. I will be serving as a Meeting Chair for the Fall 2013 MRS meeting, at which we will have a range of symposia with polymer-related themes.

How do you spend your spare time?

When I am not at the University of Delaware or traveling, my husband and I spend our time with our two boys (ages 7 and 8), two dogs (ages 8 and 9), and one cat (age 17). This time is usually spent hanging around (or more often working on) the house and yard, playing games involving balls of various shapes and sizes, building things from legos, playing card games, riding bikes, and taking walks as a family. We also are trying to expose the boys to cuisines and cooking from multiple cultures, although the boys don’t (yet) enjoy this as much as my husband and I do.

Which profession would you choose if you were not a scientist?

I was a scientist in industry for a few years before I attended graduate school, and was attracted to a career in academia because I believe in the value of education to our society. If I were not in a scientific career at a research university, I would probably work either in secondary education or in social service of some kind.

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Paper of the week: Dynamic supramolecular poly(isobutylene)s for self-healing materials

Polymers with self-healing or self-repairing properties have gained increasing importance in the past years, often relying on capsule-based concepts, mechanophores and supramolecular concepts. In all cases the basic concept of such materials relies on the use of crosslinking processes which enables repair of a mechanically induced damage by subsequent network-formation. Based on recent observations of hydrogen-bonded supramolecular poly(isobutylene)s (PIBs), where clustering effects were observed due to the interplay of supramolecular association and microphase separation between the polar hydrogen-bonding moieties and the non-polar PIB chains, the authors sought to systematically investigate the clustering and potential use of hydrogen-bonded PIBs for self-healing materials.

Graphical abstract: Dynamic supramolecular poly(isobutylene)s for self-healing materials

Mono- and bifunctional supramolecular PIBs bearing hydrogen-bonding motifs (barbituric acid or a Hamilton wedge) were prepared by a combination of living carbocationic polymerization (LCCP) and azide–alkyne ‘‘click’’ reactions to investigate their dynamics and self-healing behaviour. Temperature-dependent rheology in the melt revealed thermoreversible formation of supramolecular clusters. Stoichiometric mixing of the polymers by solution blending affected the extent of clustering by specifically interacting barbituric acid/Hamilton wedge moieties. Frequency-dependent measurements on bifunctional barbituric acid functionalized PIBs revealed a strong rubbery plateau and terminal flow, caused by the formation of dynamically bridged clusters. Small discs of these polymers showed self-healing at room temperature after being cut and brought into contact at the fractured surface.

Dynamic supramolecular poly(isobutylene)s for self-healing materials by Florian Herbst, Sebastian Seiffert and Wolfgang H. Binder, Polym. Chem., 2012, 3, 3084-3092.

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