Paper of the week: polypeptide-grafted magnetite nanoparticles

Magnetite and maghemite are of particular interest is their use in the biomedical area, especially for applications related to targeted drug delivery, immunoassays, biomacromolecule purification, clinical diagnosis and therapy, such as magnetic resonance imaging (MRI), and magnetic fluid hyperthermia (MFH). For biomedical applications, the surface of the magnetite nanoparticles needs to be suitably engineered to acquire improved colloidal stability in physiological media (avoiding agglomeration), biocompatibility, drug encapsulation ability, and specific target ability to ensure desirable interactions with cells or tissues.

Graphical abstract: Hybrid materials achieved by polypeptide grafted magnetite nanoparticles through a dopamine biomimetic surface anchored initiator

Having that in mind, the study of Marcelo and co-workers presents the synthesis of hybrid magnetic–polypeptide nanoparticles using a novel approach; that is the combination of dopamine employed as a bioinspired adhesive for a hydrophobic magnetite surface, acting at the same time as an initiator of the ring opening polymerization of g-benzyl-L-glutamate N-carboxyanhydride. Further deprotection allowed the authors to achieve poly(glutamic acid) chains, leading to pH sensitive hybrid materials. In addition, to explore the potential application of this system for drug carriers, the incorporation of a drug model compound, procaine, was also performed. Therefore, the resulting novel hybrid magnetite–polypeptide materials could be considered as good candidates for biomedical applications, such as contrast agents for magnetic resonance imaging, hyperthermia and drug delivery.

Hybrid materials achieved by polypeptide grafted magnetite nanoparticles through a dopamine biomimetic surface anchored initiator by G. Marcelo, A. Muñoz-Bonilla, J. Rodríguez-Hernández and M. Fernández-García, Polym. Chem., 2013, 4, 558-567.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Author of the Week: Prof. Xiangyang Shi

Prof. Xiangyang Shi graduated with a B.Sc. in chemistry from Henan Normal University, a M.E. in applied chemistry from Beijing Institute of Technology, and Ph.D. in organic chemistry from the Institute of Photographic Chemistry, Chinese Academy of Sciences in 1992, 1995, and 1998, respectively. He worked as a Postdoctoral Fellow at Tsinghua University (1998-2000) in Beijing and Max-Planck Institute of Colloids and Interfaces (2000-2001) in Potsdam, Germany. He then moved to California State University, Los Angeles (2001-2002) as a visiting scholar. From 2002-2008, he worked as a Research Fellow, Research Associate II, Research Investigator, and Research Assistant Professor at the University of Michigan, Ann Arbor. He then became a professor of special appointment both in Donghua University and in Shanghai Institutions of High Learning (Eastern Scholar) in 2008. Since 2010, Prof. Shi has also been appointed as an Invited Chair in Nanotechnology at the University of Madeira, Funchal, Portugal. Prof. Shi has authored or coauthored more than 145 referred journal articles and 118 technical conference abstracts or proceeding papers, along with 6 invited book chapters and 9 approved patents. His current research interests include dendrimer chemistry and related nanomedicinal applications, in particular cancer diagnosis and therapy. He is also developing nanofiber-based technology with an emphasis on the synthesis and fabrication of bioscaffolding materials in tissue engineering and pharmaceutical applications and the immobilization of reactive nanoparticles within nanofibrous mats for environmental applications.

Research website: http://www3.dhu.edu.cn/rschu/professor/shixiangyang.htm

What was your inspiration in becoming a chemist?

I started to love chemistry when I was a high-school student, because chemistry course learning was always able to fullfil my curiosity. With the years, I have been enjoying very much doing research in different disciplines of chemistry, in particular in polymer chemistry, from which I am able to lead a group of students to creat new polymer-based functional materials for various biomedical and environmental applications.

What was the motivation to write your Polymer Chemistry article? (DOI: 10.1039/C2PY20993D)

With the continuation of my research work in the area of dendrimer-based nanomedicine at the Michigan Nanotechnology Institute for Medicine and Biological Sciences (headed by Prof. James R. Baker, Jr.), University of Michigan, Ann Arbor, our group has been fully involved in the creation of various dendrimer-based nanoparticles for biomedical imaging applications since 2008. In most of our earlier research, generation 5 (G5) poly(amidoamine) dendrimers were used as either templates or stabilizers to create dendrimer-entrapped gold nanoparticles or dendrimer-stabilized gold nanoparticles. The high cost of high generation dendrimers (generation > 4) really limits the practical applications of the formed dendrimer-based organic/inorganic hybrid nanoparticles.

Our group has worked on seeking a new way to create stable dendrimer/gold nanocomposite particles using low generation dendrimers. Fortunately, via a facile hydrothermal approach we are able to generate G2 dendrimer-stablized gold nanoparticles that can be further acetylated to neutralize the positive surface potential of the particles for in vivo computed tomography imaging applications.

Why did you choose Polymer Chemistry to publish your work?

Polymer Chemistry has been recognized as one of the leading journals in the area of polymer science with a high initial impact factor. We therefore thought that it would be an ideal forum for publication of our research.

In which upcoming conferences may our readers meet you?

At the 245th ACS National Meeting & Exposition, New Orleans, LA, April 7-11, 2013 (http://acs.org/meetings), at the 7th International Coference on Materials for Advanced Technilogies in Singapore, 30 June-5 July, 2013 (http://www.mrs.org.sg/icmat2013/public.asp?page=home.asp), and also at The 2013 International Conference on Advances in Nano Research, COEX, Seoul, South Korea, August 25-28, 2013 (http://anbre.cti3.com/anbre13.htm).

How do you spend your spare times?

In my spare times, my favorite activity is to travel with my family (wife, and two lovely sons, one 10 years old, and the other 8 years old).

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

I would be an accountant.

Cyrille Boyer is a guest web-writer for Polymer Chemistry. He is currently a Senior Lecturer and an ARC-Future Fellow at the Australian Centre for NanoMedicine (School of Chemical Engineering, University of New South Wales (Australia)).

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Introducing Polymer Chemistry Editorial Board Member Masami Kamigaito

Masami Kamigaito was born in 1965 in Nagoya, Japan. He received his Ph.D. in polymer chemistry from Kyoto University under the direction of Professor Toshinobu Higashimura in 1993. After conducting postdoctoral research with Professor Mitsuo Sawamoto, he joined the faculty of Kyoto University in 1995. In 2003, he moved to Nagoya University and worked as an Associate Professor with Professor Yoshio Okamoto. In 2004, he was promoted to Professor. From 1997–1998, he worked as a visiting scientist at Stanford University with Professor Robert M. Waymouth. He was the recipient of the 2001 Arthur K. Doolittle Award of the ACS PMSE Division, the 2009 Wiley Polymer Science Award of the Society of Polymer Science, Japan, and the 2010 Japan IBM Science Award (Chemistry). His research interests include controlled radical and cationic polymerizations, the development and application of new polymerizations to precision polymer synthesis, and controlled polymerizations of renewable vinyl monomers.

His recent papers include:

Nanocellular foaming of fluorine containing block copolymers in carbon dioxide: the role of glass transition in carbon dioxide
RSC Adv., 2012,2, 2821-2827

From-syndiotactic-to-isotactic stereogradient methacrylic polymers by RAFT copolymerization of methacrylic acid and its bulky esters
Polym. Chem., 2012,3, 1750-1757

Random copolymer of styrene and diene derivatives via anionic living polymerization followed by intramolecular Friedel–Crafts cyclization for high-performance thermoplastics
Polym. Chem., 2012,3, 190-197

Follow the latest journal news on Twitter @PolymChem or go to our Facebook page.

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Paper of the week: A functional polymer with chemically switchable crystallinity

Synthetic polymers have experienced an exponential growth over the last sixty years, in part due to their combined low density and exceptional mechanical properties. Along with chain architecture and microdomain morphology, polymer crystallinity is one of the determining parameters which control these properties. Recently, there has been a flurry of activity regarding the possibility of altering mechanical properties by changing chain architecture or microdomain morphology upon the action of a chemical stimulus, a property which can be exploited for the fabrication of mechanically adaptive objects as well as sensors.

Graphical abstract: A functional polymer with chemically switchable crystallinity

In this context, Claverie and co-workers reported a functional polymer with chemically switchable crystallinity. Linear polyethylenes containing pendant diacetone acrylamide groups were prepared using Pd phosphine sulfonate catalysts. These polymers are easily cross-linked upon reaction with hydrazine, and the cross-links can be cleaved by ozonolysis to regenerate the original polymer. The cross-linked polymer, once heated above the melting point, becomes permanently amorphous, as the crosslinks prevent the chains from packing. Crystallinity can only be recovered with the cleavage of the cross-links. Thus, the polymeric material exhibits two states (crystalline and amorphous) which are triggered upon action of simple chemicals. This study thus offers a proof of principle that crystallinity responds to the action of a chemical stimulus.

A functional polymer with chemically switchable crystallinity by Jean-Christophe Daigle, Alexandre A. Arnold, Laurence Piche and Jerome P. Claverie, Polym. Chem., 2013, 4, 449-452.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Paper of the week: Heterogeneous modification of chitosan via nitroxide-mediated polymerization

Chitosan (CS) is a natural polysaccharide which displays excellent biological properties such as biocompatibility, biodegradability, and antibacterial and wound-healing activity. CS has thus promising applications in many fields such as biomedicine, wastewater treatment, functional membranes and flocculation. In order to circumvent the main drawbacks of CS such as its solubility only in acid solutions and its poor mechanical properties compared to synthetic polymers, CS has been modified by chemical treatments and more efficiently by graft copolymerization. However, these methods of grafting do not generally allow controlling the molecular weight and the number of grafted chains. Controlled/living radical polymerization have therefore opened new prospects in this domain.

Graphical abstract: Heterogeneous modification of chitosan via nitroxide-mediated polymerization

In this context, Lefay and co-workers reported an efficient CS modification method based on nitroxide-mediated polymerization (NMP) under heterogeneous conditions. After introduction of acrylamide and/or acrylate functions onto the CS backbone followed by intermolecular 1,2 radical addition of the BlocBuilder alkoxyamine, methyl methacrylate in the presence of a small amount of acrylonitrile or sodium 4-styrenesulfonate was successfully polymerized by NMP under the SG1 nitroxide control. Analyses revealed that 20-30 wt% of synthetic polymers were grafted onto the CS backbone, yielding a hybrid material with potential applications such as a biocompatibilizer.

Heterogeneous modification of chitosan via nitroxide-mediated polymerization by Catherine Lefay, Yohann Guillaneuf, Guillaume Moreira, Joel J. Thevarajah, Patrice Castignolles, Fabio Ziarelli, Emily Bloch, Mohamed Major, Laurence Charles, Marianne Gaborieau, Denis Bertin and Didier Gigmes, Polym. Chem., 2013, 4, 322-328.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Author of the Week: Dr. François Tournilhac

François Tournilhac received a Master’s degree in engineering at Ecole Centrale des Arts et Manufactures, Paris (1984) and PhD in Physical Chemistry at Université Pierre et MarieCurie, Paris (1989). Since 1989 he is a researcher at the Centre National de la Recherche Scientifique (CNRS), As a soft matter chemist, he has been working to design materials and demonstrate new effects in organic semiconductors, liquid crystals, block copolymers and composites. Presently, he is working in the team of Ludwik Leibler, Soft Matter and Chemistry at ESPCI-ParisTech, where he is developing new activities in polymer and supramolecular chemistry with a double ambition: design new materials with unusual combination of properties and in the same time identifying practical synthetic routes to make them faisible at the industrial scale.

Website of the lab: www.mmc.espci.fr

What was your inspiration in becoming a chemist?

The inspiration came to me after studying engineering without particular skills in chemistry. I wanted to do research, it seemed to me that it was a good way to remain a student during my whole life but I also wanted to make something creative by my own hands. Then I remembered these practical organic chemistry sessions of my undergraduate studies where azo dyes or aspirin are synthesized from raw material and this eventually determined my choice to launch out into chemistry.

What was the motivation to write your Polymer Chemistry article?

To the best of our knowledge, the topic of this paper, a supramolecular initiator, is a new concept. We apply it for the cationic polymerization of a commercial epoxy resin with practical application in mind but we think that this concept can be adapted to most of the polymerization processes that involve an initiation step. The motivation was also to highlight a leading work, made by a PhD student.

Why did you choose Polymer Chemistry to publish your work? (DOI: 10.1039/C2PY21140H)

Because we are ourselves readers of Polymer Chemistry and we wanted to reach a broad audience. In addition, we had excellent experience of our previous submissions to this journal: very constructive reviewers comments which helped a lot to improve the quality of the papers as well as very quick publication.

In which upcoming conferences may our readers meet you?

I will be present in Batsheva de Rothschild Seminar on Soft Matter and Biophysics in Israël in February and in the International Conference on Self Healing Materials in Belgium in June.

How do you spend your spare times?

Drawing and etching

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

Illustrator

Cyrille Boyer is a guest web-writer for Polymer Chemistry. He is currently a Senior Lecturer and an ARC-Future Fellow at the Australian Centre for NanoMedicine (School of Chemical Engineering, University of New South Wales (Australia)).

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Paper of the week: Macrocyclic regioregular poly(3-hexylthiophene)

Macrocyclic non-collapsible p-conjugated structures are known to be useful in the preparation of 1D nanotubes, 2D porous networks and 3D inclusion complexes through either unique pp stacking or concave–convex interactions. In particular for medium to giant cyclic structures, i.e. larger than 2 nm in diameter, the p-conjugated system allows benzene, thiophene, pyridine and acetylene-based macrocycles to exhibit peculiar optical, electronic, and self-assembly properties compared to their linear homologues. Structures with fully conjugated p-systems are particularly appealing because of the absence of edge effects in the p-system due to chain ends. To date, only a few examples of fully conjugated cyclic periphery have been reported. Among those, several kinds of macrocyclic oligothiophenes have attracted considerable attention since such macrocycles exhibit interesting electronic properties such as non-linear optical effects.

Graphical abstract: Macrocyclic regioregular poly(3-hexylthiophene): from controlled synthesis to nanotubular assemblies

In this study, Coulembier and co-workers have demonstrated that the preparation of giant regioregular poly(3-hexylthiophene) (P3HT) cyclics is possible with a simple but unperfected aldol reaction from a pre-formed telechelic P3HT. The four-step synthetic strategy is based on a non-metallic aldol cyclization of a designed Luscombe-type regioregular P3HT. AFM analyses highlight that linear and macrocyclic P3HTs give different self-assembled nanostructures. Interestingly, the tubular assembly of the macrocyclic P3HT, with an estimated diameter of 5 nm, could be exploited to incorporate nano-sized structures such as carbon nanotubes or fullerenes, with potential application as a compatibilizer for bulk heterojunction photovoltaic diodes for instance.

Macrocyclic regioregular poly(3-hexylthiophene): from controlled synthesis to nanotubular assemblies by Olivier Coulembier, Gaelle Deshayes, Mathieu Surin, Julien De Winter, Florian Boon, Cecile Delcourt, Philippe Leclere, Roberto Lazzaroni, Pascal Gerbaux and Philippe Dubois, Polym. Chem., 2013, 4, 237-241.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Paper of the week: Functionalized cyclic polymers in high yield

Although the primitive single-cyclic form conceptually represents the simplest cyclic topology, the synthetic constraints in general prevent from the clean and easy production of uniform cyclic polymers, particularly when availability of a specific functional group for further topological upgrade is desired. The common syntheses of single-cyclic polymers employ end-to-end ring-closure and ring-expansion polymerization.

Graphical abstract: Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone–disulfide chemistry

In this study, Du Prez and co-workers reported on an efficient synthetic pathway toward cyclic polymers based on the combination of thiolactone and disulfide chemistry. First, heterotelechelic linear polystyrene (PS) containing an a-thiolactone (TLa) and an w-dithiobenzoate group was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization, employing a newly designed TLa-bearing chain transfer agent (CTA). The subsequent reaction of this heterotelechelic polymer with an amine, which acts as a nucleophile for both the TLa and dithiobenzoate units, generated the a,w-thiol-telechelic PS under ambient conditions without the need for any catalyst or other additives. The arrangement of thiols under a high dilution afforded single cyclic PS (c-PS) through an oxidative disulfide linkage. Moreover, the authors demonstrated a controlled ring opening via either disulfide reduction or thiol–disulfide exchange to enable easy and clean topology transformation. Furthermore, to illustrate the broad utility of this synthetic methodology, different amines including functional ones were employed, allowing for the one-step preparation of functionalized cyclic polymers with high yields.

Straightforward synthesis of functionalized cyclic polymers in high yield via RAFT and thiolactone–disulfide chemistry by Milan M. Stamenović, Pieter Espeel, Eisuke Baba, Takuya Yamamoto, Yasuyuki Tezuka and Filip E. Du Prez, Polym. Chem., 2013, 4, 184-193.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

Paper of the week: Block polymer miktobrushes

Block polymers can spontaneously self-assemble into well-defined nanostructures in block selective solvents and in the bulk, offering a powerful ‘bottom up’ approach towards precisely engineered materials for many diverse applications including; microelectronics, tissue engineering, drug delivery and water purification. The increased understanding of self-assembled block polymers with varied architectures is of both fundamental and technological importance. Towards this goal, AB diblock copolymers have been studied in depth and it has been shown that adding more blocks and functional groups increases architectural and functional complexity and can lead to more exotic self-assembled morphologies.

Graphical abstract: Synthesis of block polymer miktobrushes

In this study, Lodge and Hillmyer reported an innovative synthetic strategy towards a wide compositional range of structurally well defined “miktobrush” block terpolymers, m-A(BC)n obtained using rather mild and facile reaction conditions with three separate polymer building blocks. The copolymers were synthesized utilizing the alternating radical copolymerization of two hydrophobic and incompatible macromonomer (MM) building blocks;  a maleimide (MI) end functionalized poly(methyl-caprolactone) block (MI-PMCL) or ‘C’ and a styrene (Sty) end functionalized poly(perfluoro propylene oxide) block (Sty-PFPO) or ‘F’. Polymerizations were mediated by a poly(ethylene oxide) (PEO) functionalized reversible addition–fragmentation chain transfer (RAFT) agent (PEO–CTA) or ‘O’ to control the chain growth of the MMs from the O block to form O(CF)nmiktobrush” terpolymers. The synthesis of a range of well defined m-O(CF)n terpolymers with various compositions was achieved by simply changing the feed of MMs. This new strategy offers a powerful route towards a block polymer architecture that can enable the formation of multi-domain hierarchical nanostructures with features on multiple length scales due to the incompatibility and unique connectivity of the building blocks incorporated.

Synthesis of block polymer miktobrushes by Adam O. Moughton, Takanori Sagawa, William M. Gramlich, Myungeun Seo, Timothy P. Lodge, and Marc A. Hillmyer, Polym. Chem., 2013, 4, 166-173.

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

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)

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!

Digg This
Reddit This
Stumble Now!
Share on Facebook
Bookmark this on Delicious
Share on LinkedIn
Bookmark this on Technorati
Post on Twitter
Google Buzz (aka. Google Reader)