New Family of Water-Soluble Sulfo–Fluoro Polyphosphazenes and Their Assembly within Hemocompatible Nanocoatings

Albright, Victoria; Marin, Alexander; Kaner, Papatya; Sukhishvili, Svetlana A.; Andrianov, Alexander K.

doi:10.1021/acsabm.9b00485

Cited by 11 publications

(6 citation statements)

References 64 publications

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“…We have previously introduced a family of water-soluble polyphosphazene polyanions, which contained fluorinated side groups and have been successfully employed to produce nanocoatings from aqueous solutions using the LbL deposition technique. − These fluoro-coatings displayed remarkable biocompatibility and bactericidal activity. Here, we aimed to additionally impart antithrombotic activity to this type of ionic nanoassemblies by including negatively charged heparin into such nanofilms.…”

Section: Introductionmentioning

confidence: 99%

Cationic Fluoropolyphosphazenes: Synthesis and Assembly with Heparin as a Pathway to Hemocompatible Nanocoatings

Marin

Brito

Sukhishvili

et al. 2021

ACS Appl. Bio Mater.

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The development of state-of-the-art blood-contacting devices can be advanced through integrating hemocompatibility, durability, and anticoagulant functionalities within engineered nanoscale coatings. To enable all-aqueous assembly of nanocoatings combining omniphobic fluorinated features with the potent anticoagulant activity of hydrophilic heparin, two fluoropolymers containing cationic functionalities were synthesizedpoly[(trifluoroethoxy)(dimethylaminopropyloxy)phosphazene], PFAP-O, and poly[(trifluoroethoxy)(dimethylaminopropylamino)phosphazene], PFAP-A. Despite a relatively high content of fluorinated pendant groupsapproximately 50% (mol) in eachboth polymers displayed solubility in aqueous solutions and were able to spontaneously form stable supramolecular complexes with heparin, as determined by dynamic light scattering and asymmetric flow field-flow fractionation methods. Heparin-containing coatings were then assembled by layer-by-layer deposition in aqueous solutions. Nanoassembled coatings were evaluated for potential thrombogenicity in three important categories of in vitro testscoagulation by thrombin generation, platelet retention, and hemolysis. In all assays, heparin-containing fluoro-coatings consistently displayed superior performance compared to untreated titanium surfaces or fluoro-coatings assembled using poly(acrylic acid) in the absence of heparin. Short-term stability studies revealed the noneluting nature of these noncovalently assembled coatings.

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Section: Introductionmentioning

confidence: 99%

Cationic Fluoropolyphosphazenes: Synthesis and Assembly with Heparin as a Pathway to Hemocompatible Nanocoatings

Marin

Brito

Sukhishvili

et al. 2021

ACS Appl. Bio Mater.

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“…For example, important findings on the effect of the link between backbone and side groups (e.g., phosphorus–nitrogen links appear to be more hydrolytically labile than phosphorus–oxygen), as well as the shielding effect of bulky side groups, were first established for hydrophobic polymers, ,− and still need to be validated for water-soluble polymers. Water-soluble mixed PPZ copolymers with a high content of hydrophobic fluorinated moieties and only a small fraction of ionic groups, which are capable of electrostatic self-assembly into nanocoatings or nanoparticles, − open additional possibilities in bridging this gap.…”

Section: Factors Governing Polymer Degradation: Solution Versus Solid...mentioning

confidence: 99%

Factors Controlling Degradation of Biologically Relevant Synthetic Polymers in Solution and Solid State

Brito

Andrianov

Sukhishvili

2022

ACS Appl. Bio Mater.

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The field of biodegradable synthetic polymers, which is central for regenerative engineering and drug delivery applications, encompasses a multitude of hydrolytically sensitive macromolecular structures and diverse processing approaches. The ideal degradation behavior for a specific life science application must comply with a set of requirements, which include a clinically relevant kinetic profile, adequate biocompatibility, benign degradation products, and controlled structural evolution. Although significant advances have been made in tailoring materials characteristics to satisfy these requirements, the impacts of autocatalytic reactions and microenvironments are often overlooked resulting in uncontrollable and unpredictable outcomes. Therefore, roles of surface versus bulk erosion, in situ microenvironment, and autocatalytic mechanisms should be understood to enable rational design of degradable systems. In an attempt to individually evaluate the physical state and form factors influencing autocatalytic hydrolysis of degradable polymers, this Review follows a hierarchical analysis that starts with hydrolytic degradation of water-soluble polymers before building up to 2D-like materials, such as ultrathin coatings and capsules, and then to solid-state degradation. We argue that chemical reactivity largely governs solution degradation while diffusivity and geometry control the degradation of bulk materials, with thin “2D” materials remaining largely unexplored. Following this classification, this Review explores techniques to analyze degradation in vitro and in vivo and summarizes recent advances toward understanding degradation behavior for traditional and innovative polymer systems. Finally, we highlight challenges encountered in analytical methodology and standardization of results and provide perspective on the future trends in the development of biodegradable polymers.

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“…The amassed data suggest both antithrombotic and superior healing characteristics for PPz coated stents, which is thought to be due to its ability to bind albumin, forming a "biomimetic" layer, which results in superior anti-inflammatory and thromboresistant properties compared to uncoated stents and indeed alternative clinical coatings [85]. Co-substitution can also be used to enhance the properties of such polymers with a view to their use in blood-contacting medical devices [189,190], for example water-soluble hemocompatible, sulfo-fluoropolymers [191]. In an alternative approach to antithrombotic effects, degradable amino acid ester-substituted polyphosphazenes have been investigated as NO-releasing coatings via cosubstitution with S-nitrosothiols [192,193].…”

Section: Thromboresistant Coatingsmentioning

confidence: 99%

Main-Chain Phosphorus-Containing Polymers for Therapeutic Applications

Strasser

Teasdale

2020

Molecules

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Polymers in which phosphorus is an integral part of the main chain, including polyphosphazenes and polyphosphoesters, have been widely investigated in recent years for their potential in a number of therapeutic applications. Phosphorus, as the central feature of these polymers, endears the chemical functionalization, and in some cases (bio)degradability, to facilitate their use in such therapeutic formulations. Recent advances in the synthetic polymer chemistry have allowed for controlled synthesis methods in order to prepare the complex macromolecular structures required, alongside the control and reproducibility desired for such medical applications. While the main polymer families described herein, polyphosphazenes and polyphosphoesters and their analogues, as well as phosphorus-based dendrimers, have hitherto predominantly been investigated in isolation from one another, this review aims to highlight and bring together some of this research. In doing so, the focus is placed on the essential, and often mutual, design features and structure–property relationships that allow the preparation of such functional materials. The first part of the review details the relevant features of phosphorus-containing polymers in respect to their use in therapeutic applications, while the second part highlights some recent and innovative applications, offering insights into the most state-of-the-art research on phosphorus-based polymers in a therapeutic context.

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New Family of Water-Soluble Sulfo–Fluoro Polyphosphazenes and Their Assembly within Hemocompatible Nanocoatings

Cited by 11 publications

References 64 publications

Cationic Fluoropolyphosphazenes: Synthesis and Assembly with Heparin as a Pathway to Hemocompatible Nanocoatings

Cationic Fluoropolyphosphazenes: Synthesis and Assembly with Heparin as a Pathway to Hemocompatible Nanocoatings

Factors Controlling Degradation of Biologically Relevant Synthetic Polymers in Solution and Solid State

Main-Chain Phosphorus-Containing Polymers for Therapeutic Applications

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