Exploiting sequence to control the hydrolysis behavior of biodegradable PLGA copolymers.

Monomer sequence is a potentially powerful but underutilized tool for the control of copolymer properties. Sequence is demonstrated to dramatically affect the hydrolysis profile for the degradation of poly(lactic-co-glycolic acid) (PLGA), a member of the most widely used class of biodegradable polymers employed in biomedical applications. The nearly linear molecular weight loss profile and uniform thermal behavior throughout the course of the hydrolysis differ dramatically from the behavior that is exhibited by random copolymer controls with the same comonomer ratio.

[1]  N. Spassky,et al.  Ring‐opening oligomerization reactions using aluminium complexes of schiff's bases as initiators , 1993 .

[2]  S. Allison.  Effect of structural relaxation on the preparation and drug release behavior of poly(lactic-co-glycolic)acid microparticle drug delivery systems. , 2008, Journal of pharmaceutical sciences.

[3]  A. Lendlein,et al.  Knowledge‐Based Approach towards Hydrolytic Degradation of Polymer‐Based Biomaterials , 2009, Advanced materials.

[4]  Ryan M. Stayshich,et al.  New insights into poly(lactic-co-glycolic acid) microstructure: using repeating sequence copolymers to decipher complex NMR and thermal behavior. , 2010, Journal of the American Chemical Society.

[5]  G. Coates.  Precise control of polyolefin stereochemistry using single-site metal catalysts. , 2000, Chemical reviews.

[6]  Suming Li,et al.  Hydrolytic degradation of devices based on poly(DL-lactic acid) size-dependence. , 1995, Biomaterials.

[7]  Ryan M. Stayshich,et al.  Synthesis of repeating sequence copolymers of lactic, glycolic, and caprolactic acids , 2011 .

[8]  J. Lutz,et al.  Controlled folding of synthetic polymer chains through the formation of positionable covalent bridges , 2011, Nature Chemistry.

[9]  N. Rebert.  Synthesis of O-(2'-Bromopropionyl)glycolic Acid and Its Polymerization: Synthesis of an Alternating Lactic and Glycolic Acid Copolymer , 1994 .

[10]  Drug delivery: the heart of the matter. , 2008, Nature materials.

[11]  Michael J. Campolongo,et al.  Drug delivery: Old polymer learns new tracts. , 2009, Nature materials.

[12]  T. Park,et al.  Degradation of poly(lactic-co-glycolic acid) microspheres: effect of copolymer composition. , 1995, Biomaterials.

[13]  Odile Dechy-Cabaret,et al.  Controlled ring-opening polymerization of lactide and glycolide. , 2004, Chemical reviews.

[14]  K. Wagener,et al.  Modeling branched polyethylene: copolymers possessing precisely placed ethyl branches. , 2004, Journal of the American Chemical Society.

[15]  K. Marra,et al.  Incorporation of double-walled microspheres into polymer nerve guides for the sustained delivery of glial cell line-derived neurotrophic factor. , 2010, Biomaterials.

[16]  S. Allison.  Analysis of initial burst in PLGA microparticles , 2008 .

[17]  Suming Li,et al.  Hydrolytic degradation characteristics of aliphatic polyesters derived from lactic and glycolic acids. , 1999 .

[18]  G. Coates,et al.  Stereochemistry of lactide polymerization with chiral catalysts: new opportunities for stereocontrol using polymer exchange mechanisms. , 2002, Journal of the American Chemical Society.

[19]  J. Kasperczyk,et al.  Synthesis of biodegradable glycolide/L-lactide copolymers using iron compounds as initiators , 2002 .

[20]  Jean-François Lutz,et al.  Sequence control in polymer synthesis. , 2009, Chemical Society reviews.

[21]  M. Stanford,et al.  Stereocontrolled ring-opening polymerisation of lactide. , 2010, Chemical Society reviews.

[22]  M. Ouchi,et al.  Selective radical addition with a designed heterobifunctional halide: a primary study toward sequence-controlled polymerization upon template effect. , 2009, Journal of the American Chemical Society.

[23]  R. A. Jain,et al.  The manufacturing techniques of various drug loaded biodegradable poly(lactide-co-glycolide) (PLGA) devices. , 2000, Biomaterials.

[24]  Z. Gu,et al.  Synthesis of poly(D,L‐lactic acid‐alt‐glycolic acid) from D,L‐3‐methylglycolide , 2000 .

[25]  T. Kissel,et al.  New poly(lactic-co-glycolic acid) derivatives: Modular polymers with tailored properties. , 2005, Drug discovery today. Technologies.

[26]  Diane J Burgess,et al.  Effect of acidic pH on PLGA microsphere degradation and release. , 2007, Journal of controlled release : official journal of the Controlled Release Society.

[27]  Manmohan J. Singh,et al.  Enhancing the therapeutic efficacy of CpG oligonucleotides using biodegradable microparticles. , 2009, Advanced drug delivery reviews.

[28]  J. Kasperczyk,et al.  Stereoselective polymerization of racemic dl-lactide in the presence of butyllithium and butylmagnesium. Structural investigations of the polymers , 2000 .

[29]  Kanji Nagai,et al.  AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: an end-to-end sequence-regulated copolymer. , 2010, Journal of the American Chemical Society.

[30]  G. Coates,et al.  Polymerization of enantiopure monomers using syndiospecific catalysts: a new approach to sequence control in polymer synthesis. , 2009, Journal of the American Chemical Society.

[31]  M. Ouchi,et al.  Template-assisted selective radical addition toward sequence-regulated polymerization: lariat capture of target monomer by template initiator. , 2010, Journal of the American Chemical Society.

[32]  J. Benoit,et al.  How to achieve sustained and complete protein release from PLGA-based microparticles? , 2008, International journal of pharmaceutics.

[33]  Robert Langer,et al.  Self-assembled lipid--polymer hybrid nanoparticles: a robust drug delivery platform. , 2008, ACS nano.