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.

To keep up-to-date with all the latest research, sign up for the journal’s e-alerts or RSS feeds or follow Polymer Chemistry on Twitter or Facebook.

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Paper of the week: Single chain polymeric nanoparticles as compartmentalised sensors

The unique physical properties of supramolecular polymers resulted in a myriad of potential applications ranging from electronics to healthcare and high performance materials. The large spectrum of available self-assembling molecules allows the properties of supramolecular polymers to be tuned to specific requirements of the desired applications. It has been recently shown that linear polymers grafted with non-covalent (or dynamic covalent) interacting groups lead, under selected conditions, to the folding of single polymeric chains into what are now termed single chain polymeric nanoparticles (SCPNs). Due to the unique properties of SCPNs, these well-defined nanometer-sized objects are actively investigated for use in advanced applications in low viscosity coatings, catalytic systems and nanomedicine.

Graphical abstract: Single chain polymeric nanoparticles as compartmentalised sensors for metal ions

In this context, Palmans and co-workers envisionned chemosensing of metal ions as an interesting application of SCPNs. The authors prepared 3,3′-bis(acylamino)-2,2′-bipyridine substituted benzene-1,3,5-tricarboxamide (BiPy-BTA) grafted polynorbornene polymers. The polymers fold intramolecularly via pp interactions into fluorescent, compartmentalised particles of nanometer-size. Spectroscopic and light scattering techniques show that the compact conformation of the folded polymer is affected by increasing the BiPy-BTA functionalisation degree and by changing the solvent polarity. Changes in the conformation are accompanied by changes in the fluorescence intensity. Due to the affinity of the BiPy units for metal ions such as copper, the particles obtained are effective sensors for these metals. The compartmentalisation of the binding motifs in SCPNs proves to be advantageous in sensor applications of these particles.

Single chain polymeric nanoparticles as compartmentalised sensors for metal ions by Martijn A. J. Gillissen, Ilja K. Voets, E. W. Meijer and Anja. R. A. Palmans, Polym. Chem., 2012, 3, 3166-3174.

To keep up-to-date with all the latest research, sign up for the journal’s e-alerts or RSS feeds or follow Polymer Chemistry on Twitter or Facebook.

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Author of the Week: Dr. Olivier Coulembier

Dr. Olivier Coulembier received his PhD degree from University of Mons-Hainaut (Belgium) in 2005 and joined Professor Robert M. Waymouth at the University of Stanford (United States) for his postdoctoral research in 2006.  He is currently a Research Associate by Belgian F.N.R.S. in the Laboratory of Polymeric and Composite Materials (LPCM) of Professor Philippe Dubois at University of Mons.  The objective of his research is devoted to the application of different polymerization techniques to generate original polymer materials of various topologies and issued from the macromolecular engineering fine-tuning. He has (co-)authored 62 scientific papers in international journals, 2 patents and 2 book chapters. Website: http://morris.umh.ac.be/smpc/

What was your inspiration in becoming a chemist?

Quite honestly, I didn’t fall into chemistry by real passion, I was just not really sure to fix my choice since all sciences disciplines were very interesting to me. I didn’t realize the importance of chemistry until my third year at University where polymer chemistry really peaked my interest and fed my passion. Polymer chemistry is for me the most interesting scientific field since it allows playing and creating small molecules but also fine-tune their association into simple to complex macromolecular structures and of course use a plethora of techniques to characterize them.

What was the motivation to write your Polymer Chemistry article?

In my young career, I spent almost 90% of my time to control the preparation of original polyester structures. Quite recently, by developing metal-free catalytic systems, we were able to prepare pure cyclic polyesters which proved their interest in the field by showing up physical properties different than their linear homologues.  Because people in my group are also preparing polyelectroconjugate structures, I simply wanted to merge those two activities.

Why did you choose Polymer Chemistry to publish your work? (DOI:10.1039/C2PY20647A)

Polymer Chemistry is an excellent and very promising European polymer journal. Importantly, the review process is very fast and serious.

How do you spend your spare times?

With my wife and my two daughters, of course, but also in the gym.

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

Younger, I was dreaming becoming a professional basketball player …

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Paper of the week: Role of multitopicity in hydrogen bonded supramolecular polymers

Hydrogen bonding interactions in aqueous media are often very weak because of the competition from water molecules, but they can still have a decisive effect on self-assemblies when used in combination with other interactions. In the case of amphiphiles with a hydrophobic part made from flexible alkyl chains, the introduction of hydrogen bonds within the hydrophobic domains through urea groups has been shown to dramatically increase the viscosity of aqueous solutions, and to enable self-sorting between amphiphiles of distinct structures. Another popular approach to synthesise viscous solutions or gels consists in decorating water soluble high molar mass polymers with hydrophobic groups.

Graphical abstract: Hydrogen bonded supramolecular polymers in protic solvents: role of multitopicity

In this article, Bouteiller and co-workers investigated the properties of systems combining both design elements, i.e. macromolecules with hydrophobic groups able to form very long anisotropic hydrophobic domains. A strong influence of both the number of associative groups per chain and the polydispersity has been demonstrated. In water, where the interactions between stickers are strong, the monomer self-assembles into filaments, but all other compounds with more than one sticker per chain are insoluble. In methanol, where the interactions between stickers are weaker, neither the monomer nor the monodispersed dimer is assembled, whereas polydispersed chains with an average number of stickers per chain of 2 or 3 self-assemble into filaments, leading to macroscopic gelation.

Hydrogen bonded supramolecular polymers in protic solvents: role of multitopicity by Marion Tharcis, Thomas Breiner, Joël Belleney, François Boué and Laurent Bouteiller, Polym. Chem., 2012, 3, 3093-3099.

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Paper of the week: Fluorescence resonance energy transfer in recognition-mediated polymer-quantum dot assemblies

Graphical abstract: Fluorescence resonance energy transfer in recognition-mediated polymer-quantum dot assemblies

Organization of nanoparticles (NPs) into morphologically controlled and organised structures is a central issue for bottom-up fabrication of functional devices in optoelectronics, sensing, catalysis and medicine. Directed host–guest assembly of NPs into polymer matrices is an effective route to form structured NP assemblies with advantageous optical, electronic, magnetic, and mechanical properties. In this article, Cooke, Rotello and co-workers reported recognition mediated assembly of ZnSe quantum dots (QDs) with a chromophore-functionalized polymer, facilitating fluorescence resonance energy transfer (FRET) from QDs to the chromophore. The authors designed and synthesized a polyfunctional copolymer featuring a solubilising methyl methacrylate (MMA) element, a diamidopyridine (DAP) recognition element and a flavin (Fl) chromophore. Thymine functionalized ZnSe QDs (Thy-QDs) were used as the guest in the assembly. Due to the spectral overlap and close proximity of the QDs and flavin units in the assembly, FRET was observed from QDs to flavin. This methodology of producing self-assembled structures both in solution and solid state provides a powerful tool for the creation of highly structured multifunctional materials and devices.

Fluorescence resonance energy transfer in recognition-mediated polymer-quantum dot assemblies by Vikas Nandwana, Brian Fitzpatrick, Qian Liu, Kyril M. Solntsev, Xi Yu, Gülen Yesilbag Tonga, Serkan Eymur, Murat Tonga, Graeme Cooke and Vincent M. Rotello, Polym. Chem. 2012, 3, 3072-3076.

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Paper of the week: Towards ionic-liquid containing polymers

Graphical abstract: Mild and efficient bromination of poly(hydroxyethyl acrylate) and its use towards ionic-liquid containing polymers

Ionic liquids (ILs) have been of widespread use in the world of chemical synthesis for two decades as substitutes for classical solvents, but it is only recently that IL polymers have raised interest in the field of materials sciences. In this context, their unique properties have been taken advantage of in various applications dealing with electric charge transportation. However, the direct controlled polymerization of IL monomers is not straightforward. In this communication, Monnereau and co-workers reported a simple two-step methodology to prepare IL-containing polymers. Their approach relies on a key hydroxy-to-bromine substitution on poly(hydroxyethyl acrylate), followed by the addition of a nucleophile on the resulting polymer. This constitutes an unprecedented simple and quite versatile approach towards the synthesis of a variety of monodisperse ionic liquid containing polymers by atom-transfer radical polymerization (ATRP).

Vinu Krishnan Appukuttan, Anais Dupont, Sandrine Denis-Quanquin, Chantal Andraud and Cyrille Monnereau
Polym. Chem20123, 2723-2726.

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Author of the Week: Prof. Michael J. Monteiro

Prof. Michael J. Monteiro is currently an Australian Research Council Future Fellow at The University of Queensland, Brisbane, Australia. He completed his PhD with Prof. Ken Busfield at Griffith University, Brisbane, on nitroxide trapping of small radical intermediates in polymerization systems. His first Postdoctoral Fellowship was with Prof. Ken O’Driscoll at the University of Waterloo on determining the effects of solvent on kp by PLP. His work on emulsion polymerization started as an Associate Researcher with Prof. Bob Gilbert, The University of Sydney. In 1999, he was an Assistant Professor at Eindhoven University of Technology, The Netherlands, where he started with living radical polymerization using RAFT in both solution and emulsion. His group was the first to study and synthesize polymer nanoparticles in water with controlled composition and morphology using the RAFT technology. He worked with Prof. Virgil Percec (University of Pennsylvania) in 2001 on SET-LRP. His current research interests include, drug and vaccine delivery, interactions between nanoparticles and proteins, building complex architectures from polymer building blocks and nanoreactors. He was awarded the Queen Elizabeth II Fellowship in 2004-2009, J. G. Russell award from the Australian Academy of Sciences, and The University of Queensland Research Excellence Award.

What was your inspiration in becoming a chemist?

I fell into chemistry after high school, and it was not until my postdoc with Ken O’Driscoll that chemistry and especially polymer chemistry peaked my interest and became a passion. Realizing the versatility and usefulness of polymers in everyday life made me want to research the subject.

What was the motivation to write your Polymer Chemistry article (entitled: “Reversible Polymer Nanostructures by Regulating SDS/PNIPAM“,  DOI: 10.1039/C2PY20628E )?

A key aspect in using nanostructures (e.g. worms, spheres, vesicles) for many applications is scale. We previously showed using a temperature directed morphology transformation (TDMT) process (Angew. Chemie. 2011, 50, 8082-8085) that such nanostructures could be made at high weight fractions of polymer. In this work, we further extended the system to make these nanostructures reversible by using so-called ‘dormant’ spheres that could be transformed on-demand to the desired nanostructure, and transformed back to the dormant sphere. We found that the surfactant SDS played an important role not only to stabilize the nanostructures in water but to change the packing parameters to direct the transformations to either worms, vesicles or even donuts. The great advantage of our system is that once all plasticizer (i.e. toluene) has been removed, these nanostructures are stable for years in solution and solid state due to the glassy polystyrene core. We are now trialing these structures in biomedical applications.

Why did you choose Polymer Chemistry to publish your work?

Polymer Chemistry has a vibrant and young editorial board. The research published in this journal is of a very high quality and the focus of the journal is very much in my area.

In which upcoming conferences may our readers meet you?

I will be attending the ACS conference in New Orleans (2013) on ‘Cyclic Polymers’ chaired by Prof. Scott Grayson. I will also attend the IUPAC conference (2013) in Stellenbosch, SA, chaired by Prof. Bert Klumperman. I will attend and be co-vice chair with Prof Stefan Bonn for the IPCG Research Conference 2013 – Diverse Synthesis and Applications of Polymer Colloids, chaired by Dr Dieter Urban (BASF, Germany).

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

If I were not a scientist, I would have probably worked as a politician. I enjoy debating and friendly arguments. I suppose this is not too different to polymer science. The RAFT mechanism debate on intermediate radical termination was just one example.

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Top 10 most-read Polymer Chemistry articles in September

This month sees the following articles in Polymer Chemistry that are in the top ten most accessed for September :

Thiol-ene “click” reactions and recent applications in polymer and materials synthesis 
Andrew B. Lowe  
Polym. Chem., 2010, 1, 17-36 
DOI: 10.1039/b9py00216b 

Recent advances in RAFT dispersion polymerization for preparation of block copolymer aggregates 
Jiao-Tong Sun ,  Chun-Yan Hong and Cai-Yuan Pan  
Polym. Chem., 2013, Advance Article 
DOI: 10.1039/c2py20612a 

Thiol–epoxy ‘click’ polymerization: efficient construction of reactive and functional polymers 
Andreas Brändle and Anzar Khan  
Polym. Chem., 2012, Advance Article 
DOI: 10.1039/c2py20591b 

Waterborne polymer nanogels non-covalently crosslinked by multiple hydrogen bond arrays 
Yunhua Chen ,  Nicholas Ballard and Stefan A. F. Bon 
Polym. Chem., 2012, Advance Article 
DOI: 10.1039/c2py20615c 

Synthesis of block polymer miktobrushes 
Adam O. Moughton ,  Takanori Sagawa ,  William M. Gramlich ,  Myungeun Seo ,  Timothy P. Lodge and Marc A. Hillmyer  
Polym. Chem., 2012, Advance Article 
DOI: 10.1039/c2py20656k 

Linear–dendritic biodegradable block copolymers: from synthesis to application in bionanotechnology 
Chang-Ming Dong and Gang Liu  
Polym. Chem., 2013, Advance Article 
DOI: 10.1039/c2py20441j 

Progress on multi-compartment polymeric capsules 
Xin Huang and Brigitte Voit  
Polym. Chem., 2013, Advance Article 
DOI: 10.1039/c2py20636f 

Novel polythiophene derivatives functionalized with conjugated side-chain pendants comprising triphenylamine/carbazole moieties for photovoltaic cell applications 
Hsing-Ju Wang ,  Jiann-Yu Tzeng ,  Chen-Wei Chou ,  Chien-Yi Huang ,  Rong-Ho Lee and Ru-Jong Jeng  
Polym. Chem., 2012, Advance Article
DOI: 10.1039/c2py20477k 

Effect of TiO2 nanoparticle surface functionalization on protein adsorption, cellular uptake and cytotoxicity: the attachment of PEG comb polymers using catalytic chain transfer and thiol–ene chemistry 
Roslyn Tedja ,  Alexander H. Soeriyadi ,  Michael R. Whittaker ,  May Lim ,  Christopher Marquis ,  Cyrille Boyer ,  Thomas P. Davis and Rose Amal  
Polym. Chem., 2012, 3, 2743-2751 
DOI: 10.1039/c2py20450a 

Synthesis of block copolymers via the combination of RAFT and a macromolecular azo coupling reaction 
Yaning He ,  Wei He ,  Dan Liu ,  Tonghan Gu ,  Renbo Wei and Xiaogong Wang  
Polym. Chem., 2012, Advance Article 
DOI: 10.1039/c2py20653f 

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

Fancy submitting an article to Polymer Chemistry? Then why not submit to us today!

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