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Full-Text Articles in Physical Sciences and Mathematics

Poly(Ethyl Glyoxylate)-Poly(Ethylene Oxide) Nanoparticles: Stimuli- Responsive Drug Release Via End-To-End Polyglyoxylate Depolymerization, Bo Fan, Elizabeth Gillies Mar 2017

Poly(Ethyl Glyoxylate)-Poly(Ethylene Oxide) Nanoparticles: Stimuli- Responsive Drug Release Via End-To-End Polyglyoxylate Depolymerization, Bo Fan, Elizabeth Gillies

Chemistry Publications

The ability to disrupt polymer assemblies in response to specifi c stimuli provides the potential to release drugs selectively at certain sites or conditions in vivo. However, most stimuli-responsive delivery systems require many stimuli initiated events to release drugs. Self-immolative polymers offer the potential to provide amplifi ed responses to stimuli as they undergo complete end-to-end depolymerization following the cleavage of a single end-cap. Herein, linker end-caps were developed to conjugate self-immolative poly(ethyl glyoxylate) (PEtG) with poly(ethylene oxide) (PEO) to form amphiphilic block copolymers. These copolymers were self-assembled to form nanoparticles in aqueous solution. Cleavage of the linker …


Phosphonium-Functionalized Polymer Micelles With Intrinsic Antibacterial Activity, Benjamin Hisey, Paul J. Ragogna, Elizabeth Gillies Feb 2017

Phosphonium-Functionalized Polymer Micelles With Intrinsic Antibacterial Activity, Benjamin Hisey, Paul J. Ragogna, Elizabeth Gillies

Chemistry Publications

New approaches to treat bacterial infections are badly needed to address the increasing problem of antibiotic resistance. This study explores phosphonium-functionalized block copolymer micelles as intrinsically antibacterial polymer assemblies. Phosphonium cations with varying alkyl lengths were conjugated to the terminus of a poly(ethylene oxide)− polycaprolactone block copolymer, and the phosphonium-functionalized block copolymers were self-assembled to form micelles in aqueous solution. The size, morphology, and ζ -potential of the assemblies were studied, and their abilities to kill Escherichia coli and Staphylococcus aureus were evaluated. It was found that the minimum bactericidal concentration depended on the phosphonium alkyl chain length, and different …


End-Capping Strategies For Triggering End-To-End Depolymerization Of Polyglyoxylates, Bo Fan, John Trant, Elizabeth Gillies Dec 2016

End-Capping Strategies For Triggering End-To-End Depolymerization Of Polyglyoxylates, Bo Fan, John Trant, Elizabeth Gillies

Chemistry Publications

Polymers that undergo end-to-end depolymerization in response to the cleavage of a stimuli-responsive end-cap are promising for diverse applications from drug delivery to responsive coatings and plastics. It is critical that the end-cap is designed to respond to an appropriate stimulus for the application. In the current work, end-caps for triggering the depolymerization of poly(ethyl glyoxylate) (PEtG) were explored. First, a phenylboronate, a disulfi de, and an azobenzene were utilized to impart redox-responsive properties to PEtG. Then, methoxy-substituted trityl groups were used to provide sensitivity to mild acid. A multiresponsive platform was also introduced, allowing PEtG to respond to multiple …


Post-Polymerization Functionalization Of Poly (Ethylene Oxide)–Poly (Β-6-Heptenolactone) Diblock Copolymers To Tune Properties And Self-Assembly, Elizabeth Gillies, Brooke M. Raycraft, Jarret Macdonald Nov 2016

Post-Polymerization Functionalization Of Poly (Ethylene Oxide)–Poly (Β-6-Heptenolactone) Diblock Copolymers To Tune Properties And Self-Assembly, Elizabeth Gillies, Brooke M. Raycraft, Jarret Macdonald

Chemistry Publications

Polyester-based amphiphilic block copolymers and their nanoassemblies are of significant interest for a wide range of applications due to the degradability of the polyester block. However, the commonly used polyesters lack functional groups on their backbones, limiting the possibilities to chemically modify these polymers. Described here are new poly(ethylene oxide) (PEO)–poly(β-6-heptenolactone) (PHEL) block copolymers having pendant alkenes at each repeat unit on the PHEL block. First, the self-assembly of these block copolymers in aqueous solution was studied and it was found that they formed solid nanoparticles and vesicles depending on the relative block lengths. Next the alkene moieties of the …


Synthesis, Self-Assembly, And Immunological Activity Of Α-Galactose-Functionalized Dendron–Lipid Amphiphiles, John Trant, Namrata Jain, D. M. Mazzuca, J Trevor Mcintosh, Bo Fan, S M Mansour Haeryfar, Sebastien Lecommandoux, Elizabeth Gillies Sep 2016

Synthesis, Self-Assembly, And Immunological Activity Of Α-Galactose-Functionalized Dendron–Lipid Amphiphiles, John Trant, Namrata Jain, D. M. Mazzuca, J Trevor Mcintosh, Bo Fan, S M Mansour Haeryfar, Sebastien Lecommandoux, Elizabeth Gillies

Chemistry Publications

Nanoassemblies presenting multivalent displays of biologically active carbohydrates are of significant interest for a wide array of biomedical applications ranging from drug delivery to immunotherapy. In this study, glycodendronlipid hybrids were developed as a new and tunable class of dendritic amphiphiles. A modular synthesis was used to prepare dendronlipid hybrids comprising distearylglycerol and 0 through 4th generation polyester dendrons with peripheral protected amines. Following deprotection of the amines, an isothiocyanate derivative of C-linked α-galactose (α-Gal) was conjugated to the dendron peripheries, affording amphiphiles with 1 to 16 α-Gal moieties. Self-assembly in …


Photocontrolled Degradation Of Stimuli-Responsive Poly(Ethyl Glyoxylate): Differentiating Features And Traceless Ambient Depolymerization, Bo Fan, John Trant, Rebecca Yardley, Andrew Pickering, Francois Lagugne-Labarthet, Elizabeth Gillies Sep 2016

Photocontrolled Degradation Of Stimuli-Responsive Poly(Ethyl Glyoxylate): Differentiating Features And Traceless Ambient Depolymerization, Bo Fan, John Trant, Rebecca Yardley, Andrew Pickering, Francois Lagugne-Labarthet, Elizabeth Gillies

Chemistry Publications

The depolymerization of coatings prepared from a 6-nitroveratryl carbonate end-capped poly(ethyl glyoxylate) (PEtG) self-immolative polymer was studied. This polymer undergoes end-to-end depolymerization following cleavage of the end-cap by UV light. Several important fundamental diff erences between this class of polymers and conventional degradable polymers were revealed. For example, polymer backbone cleavage and depolymerization exhibited different dependencies on pH, emphasizing the decoupling of these processes. Probing of the coating erosion mechanism illustrated an interesting combination of features from surface erosion and bulk degradation mechanisms that arise from the end-to-end depolymerization mechanism and further differentiate these polymers from convention degradable polymers. It …


Synthesis, Properties, And Antibacterial Activity Of Polyphosphonium Semi-Interpenetrating Networks, Tyler John Cuthbert, Tristan Harrison, Paul J. Ragogna, Elizabeth Gillies Jun 2016

Synthesis, Properties, And Antibacterial Activity Of Polyphosphonium Semi-Interpenetrating Networks, Tyler John Cuthbert, Tristan Harrison, Paul J. Ragogna, Elizabeth Gillies

Chemistry Publications

The development of new approaches to antibacterial surfaces is of growing interest to combat the spread of harmful bacterial infections. Relative to polyammoniums, polyphosphoniums can exhibit enhanced chemical and thermal stability, but have not yet been widely explored for the preparation of antibacterial surfaces. In this work, polyphosphoniums of varying chain lengths were synthesized by reversible addition-fragmentation chain-transfer polymerization of 4-vinylbenzyl derivatives of triethyl, tributyl, and trioctylphosphonium. These polyphosphoniums were then incorporated into semi-interpenetrating networks (SIPNs) based on tetra(ethylene glycol) diacrylate (TEGDA) via a UV light-initiated curing process. Measurements of cure percentage, gel content, water contact angle, and surface charge …


Resin-Supported Arylstannanes As Precursors For Radiolabeling With Iodine: Benzaldehydes, Benzoic Acids, Benzamides, And Nhs Esters, Mustafa Janabi, Catherine M. Pollock, Ann-Marie Chacko, Duncan H. Hunter Sep 2014

Resin-Supported Arylstannanes As Precursors For Radiolabeling With Iodine: Benzaldehydes, Benzoic Acids, Benzamides, And Nhs Esters, Mustafa Janabi, Catherine M. Pollock, Ann-Marie Chacko, Duncan H. Hunter

Chemistry Publications

A highly cross-linked polystyrene resin bearing a reactive chlorostannane moiety 1 has been used to generate a variety of arylstannane radiopharmaceutical precursors for no-carrier-added radioiodination. The resins were characterized for their solvent compatibility and sensitivity to acid cleavage. Resin-supported arylstannanes synthesized via their aryl lithium analogues include 3- and 4-stannylbenzaldehydes, 3- and 4-stannylbenzoic acids, and 3- and 4-N-succinimidyl benzoates. A three-step route to the resin-supported stannylbenzoic acids 12a/b was developed through resin-supported benzaldehydes 11a/b. The aldehyde to acid conversion efficiency is >90%, and acid loading capacities of 0.66–0.94 mmol/g were obtained. Resin-supported N-succinimidyl benzoates 16a/b …