An Approach for the Sphere-to-Rod Transition of Multiblock Copolymer Micelles.

The shape of polymer micelles is important for pharmaceutical applications as drug delivery. In this article, an approach inducing sphere-to-rod transition of multiblock polyurethane micelles has been developed through introducing a second hydrophilic component phosphatidylcholine group into the polymer chains. Time-resolved dynamic light scattering (DLS), combined with transmission electron microscopy (TEM), was employed to investigate the kinetics of morphology transition. Moreover, a dissipative particle dynamics (DPD) simulation method was applied to study the mechanism of sphere-to-rod transition. These experimental and simulation studies revealed that the hydrophilic phosphatidylcholine groups can create defects on the surfaces of spherical polyurethane micelles, thus, making positive contribution to adhesive collisions and leading to the fusion of spherical micelles into rod-like micelles. This finding provides new insight into the origins of rod-like polymer micelles, which is valuable for the des...

[1]  T. Azzam,et al.  Control of vesicular morphologies through hydrophobic block length. , 2006, Angewandte Chemie.

[2]  S. Ludwigs,et al.  Self-assembly of functional nanostructures from ABC triblock copolymers , 2003, Nature materials.

[3]  V. Torchilin,et al.  Micellar Nanocarriers: Pharmaceutical Perspectives , 2006, Pharmaceutical Research.

[4]  Stephen Z. D. Cheng,et al.  Temperature-induced reversible morphological changes of polystyrene-block-poly(ethylene oxide) micelles in solution. , 2007, Journal of the American Chemical Society.

[5]  I. Manners,et al.  Self-Assembly of Organometallic Block Copolymers: The Role of Crystallinity of the Core-Forming Polyferrocene Block in the Micellar Morphologies Formed by Poly(ferrocenylsilane-b-dimethylsiloxane) in n-Alkane Solvents , 2000 .

[6]  Hua Ai,et al.  Multifunctional polymeric micelles as cancer-targeted, MRI-ultrasensitive drug delivery systems. , 2006, Nano letters.

[7]  Vanessa Schmidt,et al.  Diblock copolymer micellar nanoparticles decorated with annexin-A5 proteins. , 2006, Journal of the American Chemical Society.

[8]  Jiehua Li,et al.  Self-assembly of biodegradable polyurethanes for controlled delivery applications , 2012 .

[9]  Silvia Muro,et al.  Endothelial targeting of antibody-decorated polymeric filomicelles. , 2011, ACS nano.

[10]  Jiehua Li,et al.  Effect of PEG content on the properties of biodegradable amphiphilic multiblock poly(ε-caprolactone urethane)s , 2011 .

[11]  H. Deng,et al.  Cellular uptake of polyurethane nanocarriers mediated by gemini quaternary ammonium. , 2011, Biomaterials.

[12]  Jiehua Li,et al.  Synthesis and micellization of new biodegradable phosphorylcholine-capped polyurethane , 2011 .

[13]  Ick Chan Kwon,et al.  Polymeric nanomedicine for cancer therapy , 2008 .

[14]  Hongwei Shen,et al.  Thermodynamics of Crew-Cut Micelle Formation of Polystyrene-b-Poly(acrylic acid) Diblock Copolymers in DMF/H2O Mixtures , 1997 .

[15]  J. Koelman,et al.  Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics , 1992 .

[16]  Lijuan Zhang,et al.  Effect of composition on the formation of poly(dl-lactide) microspheres for drug delivery systems: Mesoscale simulations , 2007 .

[17]  Jiehua Li,et al.  Simulation of self-assembly behaviour of fluorinated phospholipid molecules in aqueous solution by dissipative particle dynamics method , 2009 .

[18]  K. Kataoka,et al.  Block copolymer micelles for drug delivery: design, characterization and biological significance. , 2001, Advanced drug delivery reviews.

[19]  A. Eisenberg,et al.  Multiple Morphologies and Characteristics of “Crew-Cut” Micelle-like Aggregates of Polystyrene-b-poly(acrylic acid) Diblock Copolymers in Aqueous Solutions , 1996 .

[20]  Qiang Fu,et al.  Preparation and rapid degradation of nontoxic biodegradable polyurethanes based on poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) and l -lysine diisocyanate , 2011 .

[21]  Lifeng Zhang,et al.  Thermodynamic vs kinetic aspects in the formation and morphological transitions of crew-cut aggregates produced by self-assembly of polystyrene-b-poly(acrylic acid) block copolymers in dilute solution , 1999 .

[22]  I. Manners,et al.  Monodisperse cylindrical micelles by crystallization-driven living self-assembly. , 2010, Nature chemistry.

[23]  Hongwei Shen,et al.  Block Length Dependence of Morphological Phase Diagrams of the Ternary System of PS-b-PAA/Dioxane/H2O , 2000 .

[24]  Chongli Zhong,et al.  Understanding Multicompartment Micelles Using Dissipative Particle Dynamics Simulation , 2007 .

[25]  John Samuel,et al.  Poly(ethylene oxide)-block-poly(L-amino acid) micelles for drug delivery. , 2002, Advanced drug delivery reviews.

[26]  R. Zhuo,et al.  Synthesis and characterization of a biodegradable amphiphilic copolymer based on branched poly(ε-caprolactone) and poly(ethylene glycol) , 2007 .

[27]  Stephanie E. A. Gratton,et al.  The effect of particle design on cellular internalization pathways , 2008, Proceedings of the National Academy of Sciences.

[28]  Lifeng Zhang,et al.  Morphogenic Effect of Added Ions on Crew-Cut Aggregates of Polystyrene-b-poly(acrylic acid) Block Copolymers in Solutions , 1996 .

[29]  D. Bucknall,et al.  Polymers Get Organized , 2003, Science.

[30]  S. Kuo,et al.  Micellar morphologies of self-associated diblock copolymers in acetone solution , 2007 .

[31]  Sung Ho Kim,et al.  Hierarchical supermolecular structures for sustained drug release. , 2009, Small.

[32]  R. Haag,et al.  Supramolecular drug-delivery systems based on polymeric core-shell architectures. , 2004, Angewandte Chemie.

[33]  Hongbo Du,et al.  Effect of selective solvent addition rate on the pathways for spontaneous vesicle formation of ABA amphiphilic triblock copolymers. , 2010, Journal of the American Chemical Society.

[34]  L. Ye,et al.  The self-aggregation behaviour of amphotericin B-loaded polyrotaxane-based triblock copolymers and their hemolytic evaluation , 2009 .

[35]  Xia Jiang,et al.  Synthesis and self-assembly of an amino-functionalized hybrid hydrocarbon/fluorocarbon double-chain phospholipid. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[36]  A. Eisenberg,et al.  Morphogenic Effect of Solvent on Crew-Cut Aggregates of Apmphiphilic Diblock Copolymers , 1998 .

[37]  T. Lodge,et al.  Multicompartment micelles from A2-star-(B-alt-C) block terpolymers in selective solvents , 2011 .

[38]  H. Deng,et al.  Molecular Engineered Super‐Nanodevices: Smart and Safe Delivery of Potent Drugs into Tumors , 2012, Advanced materials.

[39]  S. Bhatia,et al.  Magnetic Iron Oxide Nanoworms for Tumor Targeting and Imaging , 2008, Advanced materials.

[40]  Ke-Xin Zhang,et al.  Shape effects of nanoparticles conjugated with cell-penetrating peptides (HIV Tat PTD) on CHO cell uptake. , 2008, Bioconjugate chemistry.

[41]  D. Discher,et al.  Hydrolytic degradation of poly(ethylene oxide)-block-polycaprolactone worm micelles. , 2005, Journal of the American Chemical Society.

[42]  A. Eisenberg,et al.  Kinetics and Mechanisms of the Sphere-to-Rod and Rod-to-Sphere Transitions in the Ternary System PS310-b-PAA52/Dioxane/Water , 2001 .

[43]  Teruo Okano,et al.  Polymeric micelles as new drug carriers , 1996 .

[44]  Jiehua Li,et al.  Biodegradable gemini multiblock poly(ε-caprolactone urethane)s toward controllable micellization , 2010 .

[45]  Jiehua Li,et al.  Synthesis and characterization of novel biodegradable folate conjugated polyurethanes. , 2011, Journal of colloid and interface science.

[46]  Yuanwei Chen,et al.  Enhancement of cellular uptake and antitumor efficiencies of micelles with phosphorylcholine. , 2011, Macromolecular bioscience.

[47]  M. Zilberman,et al.  Long-term in vitro study of paclitaxel-eluting bioresorbable core/shell fiber structures. , 2008, Journal of controlled release : official journal of the Controlled Release Society.

[48]  S. Ikeda Sphere-rod transition of surfactant micelles and size distribution of rodlike micelles , 1984 .

[49]  Hua Ai,et al.  Manganese ferrite nanoparticle micellar nanocomposites as MRI contrast agent for liver imaging. , 2009, Biomaterials.

[50]  J. Koelman,et al.  Dynamic simulations of hard-sphere suspensions under steady shear , 1993 .

[51]  Kai Yang,et al.  Computer simulation of the translocation of nanoparticles with different shapes across a lipid bilayer. , 2010, Nature nanotechnology.

[52]  U. Schubert,et al.  Tuning the morphologies of amphiphilic metallo-supramolecular triblock terpolymers: from spherical micelles to switchable vesicles , 2009 .

[53]  Michael Schick,et al.  Stable and Unstable Phases of a Linear Multiblock Copolymer Melt , 1994 .

[54]  Self‐Assembly of Two Agents in a Core‐Shell‐Corona Multicompartment Micelle Studied by Dissipative Particle Dynamics Simulations , 2006 .

[55]  Samir Mitragotri,et al.  Designer Biomaterials for Nanomedicine , 2009 .

[56]  Jiehua Li,et al.  The degradation and biocompatibility of pH-sensitive biodegradable polyurethanes for intracellular multifunctional antitumor drug delivery. , 2012, Biomaterials.

[57]  Dennis E Discher,et al.  Flexible filaments for in vivo imaging and delivery: persistent circulation of filomicelles opens the dosage window for sustained tumor shrinkage. , 2009, Molecular pharmaceutics.

[58]  Andrew L. Schmitt,et al.  Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles. , 2012, ACS macro letters.

[59]  C. Tyler,et al.  Linear elasticity of cubic phases in block copolymer melts by self-consistent field theory , 2002 .

[60]  S. K. Agrawal,et al.  Novel drug release profiles from micellar solutions of PLA-PEO-PLA triblock copolymers. , 2006, Journal of controlled release : official journal of the Controlled Release Society.

[61]  S. Armes,et al.  Phosphorylcholine-based pH-responsive diblock copolymer micelles as drug delivery vehicles: light scattering, electron microscopy, and fluorescence experiments. , 2006, Biomacromolecules.

[62]  Tao Chen,et al.  A Strategy in The Design of Micellar Shape for Cancer Therapy , 2012, Advanced healthcare materials.

[63]  M. Rubinstein,et al.  Diblock copolymer micelles in a dilute solution , 2005 .

[64]  Paula T Hammond,et al.  The effects of polymeric nanostructure shape on drug delivery. , 2011, Advanced drug delivery reviews.

[65]  I. Manners,et al.  Non-Centrosymmetric Cylindrical Micelles by Unidirectional Growth , 2012, Science.

[66]  D. Discher,et al.  Shape effects of filaments versus spherical particles in flow and drug delivery. , 2007, Nature nanotechnology.

[67]  Mitchell A. Winnik,et al.  Cylindrical Block Copolymer Micelles and Co-Micelles of Controlled Length and Architecture , 2007, Science.

[68]  Jiehua Li,et al.  Synthesis, degradation, and cytotoxicity of multiblock poly(epsilon-caprolactone urethane)s containing gemini quaternary ammonium cationic groups. , 2009, Biomacromolecules.

[69]  Simon J. Holder,et al.  New micellar morphologies from amphiphilic block copolymers: disks, toroids and bicontinuous micelles , 2011 .