0000000000265197
AUTHOR
Sonia Lanzalaco
Grafting of vinyl monomers on PVC and PVDF by ATRP
ATRP (atom transfer radical polymerization) has been recently used to prepare graft copolymers with regularly-spaced polymer chains from polymeric macroinitiators that have pendant chemical groups containing radically transferable halogen atoms [1]. The halogen atom serves as initiation site for the polymerization of side chains. ATRP employs the equilibrium between dormant alkyl halides and active propagating radicals to maintain a low concentration of active species. The activated radical species can either propagate or be deactivated to reform the dormant species. This process is catalyzed by a transition metal compound such as Cu-based species. The continuous development of more active …
Sterilization of macroscopic poly(l-lactic acid) porous scaffolds withdense carbon dioxide: Investigation of the spatial penetration of thetreatment and of its effect on the properties of the matrix
Abstract In this work the sterilization with dense carbon dioxide of poly( l -lactic acid) (PLLA) porous scaffolds intended for tissue engineering applications was investigated with the main objective of confirming the three-dimensional efficacy of the treatment and of analysing the scaffold properties after CO2 treatment. For this purpose the scaffold was contaminated with a conventional bacterium (Escherichia coli) and with spores (Streptomyces coelicolor), a species more fascinating and difficult to inactivate. Contamination was performed in such a way to soak the whole matrix with bacteria and spores. The effect of pressure and treatment time on the efficacy of the sterilization was eva…
Utilization of Poly(vinylchloride) and Poly(vinylidenefluoride) as Macroinitiators for ATRP Polymerization of Hydroxyethylmethacrylate. Electroanalytical and Graft-Copolymerization Studies
The utilization of poly(vinylchloride) (PVC) and poly(vinylidenefluoride) (PVDF) as macroinitiators for atom transfer radical polymerization (ATRP) of hydroxyethylmethacrylate (HEMA) was studied performing electroanalytical investigations and “grafting from” experiments in order to achieve information on the possibility of modifying such commercial polymers by this controlled free radical polymerization technique. This study was performed changing various operating parameters such as the nature of the copper salt, the ligand, the solvent, the temperature and the reaction time. Electroanalytical data suggest that PVC can be easily activated by both CuCl/ Tris(2-pyridylmethyl)amine (TPMA) and…
Sterilization of three-dimensional tissue engineering scaffolds by supercritical carbon dioxide
Medical devices, implants or patient-care equipment that will come into intimate contact with a patient must be effectively decontaminated to prevent infection or disease transmission. Non-sterile devices have significant ramifications for patient morbidity and mortality and two processes must be undertaken in order to make an item acceptable for use or implantation: cleaning and disinfection (or sterilization) [1]. Sterilization is the destruction of living organisms, and must be done without damaging the material surface and without compromising the bulk material strength or biocompatibility of implantable device. Common sterilization processes include steam autoclaving, gamma irradiation…
Crosslinking of polymers activated by electrogenerated hydroxyl radicals.
Nanogels (NGs) are systems created by crosslinking of polymers taking nanosized dimensions and they have been proposed for biomedical and pharmaceutical applications due to their soft consistency, biocompatibility and good chemical properties that make them excellent drug delivery agents (1). Differently from typical hydrogels, nanogels are able to dissolve in solvents and to swell releasing the drug molecules loaded in the nano-vector. Furthermore, if properly functionalized with reactive groups, these materials can represent a very interestingly vector for different pharmacological treatments (2). Several methods have been investigated to prepare polymeric nanogels starting from preformed…
Atom transfer radical polymerization with different halides (F, Cl, Br, and I): Is the process "living" in the presence of fluorinated initiators?
Atom transfer radical polymerization (ATRP) is often used for grafting from fluorinated polymers. Nevertheless, the possibility to initiate an ATRP from a C-F functionality and the activity of the catalysts in the presence of fluoride anions are essentially unexplored. Therefore, we investigated the thermodynamics and kinetics of C-F bond activation by ATRP catalysts and compared it with other halide systems. The ATRP equilibrium constant was estimated to be small for the reaction between [CuITPMA]+ and benzyl fluoride (TPMA = tris(2-pyridylmethyl)- amine). However, [CuITPMA] + could react with the more active initiator diethyl fluoromalonate (DEFM). With DEFM as initiator and CuIBr/TPMA as…
Modification of PVDF nanoparticles by controlled free radical graft copolymerization in supercritical carbon dioxide
PVDF (polyvinylidenefluoride) membranes are widely used in microfiltration (MF) and ultrafiltration (UF) due to their excellent processability, chemical resistance, well-controlled porosity, and good thermal properties [1]. Moreover this polymer is also frequently adopted in bio-medical devices owing to its good biocompatibility [2]. On the other hand, the use of PVDF membranes in biomedical applications is limited to some extent by the hydrophobicity of their exposed area, which mainly arises from the nature of the pore surface. Prompted by these considerations in the present work we have studied the modification of PVDF nanoparticles with hydroxyethylmethacrylate (HEMA) thus obtaining a m…
Supercritical carbon dioxide induces sterilization of PLLA scaffolds contaminated by E. coli.
The common sterilization techniques are based on physical processes that involve, for example, the use of autoclaves or systems to radiation such as γ-rays that can cause a structural change of the polymer treated. Therefore, the use of supercritical carbon dioxide (scCO2) is an excellent alternative, as it does not induce any variation of biomaterials treated (Perrut M., 2012). It's a good candidate because is readily available at low cost, non-toxic and non-flammable, it has an easily accessible critical point (7.38 MPa and 304.2 K) and excellent transport properties and wettability (White A. et al., 2005). We report the development of a supercritical CO2 based process capable of steriliz…
Poly(N-isopropylacrylamide) and Copolymers: A Review on Recent Progresses in Biomedical Applications.
The innate ability of poly(N-isopropylacrylamide) (PNIPAAm) thermo-responsive hydrogel to copolymerize and to graft synthetic polymers and biomolecules, in conjunction with the highly controlled methods of radical polymerization which are now available, have expedited the widespread number of papers published in the last decade—especially in the biomedical field. Therefore, PNIPAAm-based hydrogels are extensively investigated for applications on the controlled delivery of active molecules, in self-healing materials, tissue engineering, regenerative medicine, or in the smart encapsulation of cells. The most promising polymers for biodegradability enhancement of PNIPAAm hydrogels are probably…
ELECTROCHEMICALLY ASSISTED ATOM TRANSFER RADICAL GRAFT COPOLYMERIZATION. PRELIMINARY STUDIES
Atom transfer radical polymerization (ATRP) is a versatile technique for exerting precise control over polymer molecular weights, molecular weight distributions, and complex architectures. It has been recently shown that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process by a one-electron reduction of an initially added air-stable cubric species (Cu(II)/Ligand) [1-2]. In particular Gennaro and co-authors have shown that the polymerization kinetic can be changed modulating the external potential [1-2]. In the last years, an increasing interest has been devoted to synthesis of graft copolymers obtained from commercial polymers for inco…
Effect of interfacial area on heterogeneous free radical grafting of vinyl monomers in supercritical carbon dioxide: Grafting of acrylic acid on poly(vinylidenefluoride) nanoparticles
The role of the polymer interfacial area on free radical grafting of acrylic acid (AA) onto poly(vinylidenefluoride) (PVDF) was studied at 65°C using supercritical carbon dioxide (scCO2) as a solvent and swelling agent, benzoylperoxide (BPO) as chemical initiator and PVDF nanoparticles as polymer matrix. Under adopted conditions PVDF particles do not melt neither dissolve in the reaction medium and FTIR analyses performed on carefully washed nanoparticles confirmed the achievement of high grafting levels. The mass fraction of grafted AA increased with the grafting time and the BPO concentration while it decreased when the density of the fluid phase was enhanced. Collected results suggest th…
Synthesis of polymer nanogels by electro-Fenton process: investigation of the effect of main operation parameters
Recently, electro-Fenton (EF) process has been shown as a promising, facile, effective, low cost and environmentally-friendly alternative for synthesizing polymer nanogels suitable as biocompatible nanocarriers for emerging biomedical applications. Here, the electrochemically-assisted modification of poly(vinylpyrrolidone) (PVP) by EF process was studied to assess the role of key operation parameters for a precise modulation of polymer crosslinking and its functionalization with [sbnd]COOH and succinimide groups. The dimensions of the nanogels, in terms of hydrodynamic radius (Rh) and weight-average molecular weight (Mw), can be tuned up by controlling the electrolysis time, current density…
Facile crosslinking of poly(vinylpyrrolidone) by electro-oxidation with IrO2-based anode under potentiostatic conditions
Abstract: The modification of polymer architectures by reaction with chemically adsorbed hydroxyl radicals has been thoroughly investigated by electrolyzing dilute aqueous solutions of the biocompatible polymer poly(vinylpyrrolidone) (PVP), using an undivided electrolytic cell with a Ti/IrO2–Ta2O5(DSA®) anode. Several electrolyses were performed to assess the influence of the applied potential, the circulated charge and the PVP concentration, which was always kept low to avoid chain overlapping. From the results obtained, it can be concluded that the electro-oxidation of PVP solutions using a cheap anode is an effective method to crosslink initially isolated polymer chains, eventually incre…
Crosslinking of poly(vinylpyrrolidone) activated by electrogenerated hydroxyl radicals: a first step towards a simple and cheap synthetic route of nanogel vectors
A facile electrosynthesis route for the preparation of polymer nanogels based on the in situ production of hydroxyl radicals is reported for the first time. Electro-Fenton process with continuous H2O2 electrogeneration and Fe2+ regeneration performs better than electro-oxidation with a boron-doped diamond or dimensionally stable anode for promoting crosslinking of poly(vinylpyrrolidone). Keywords: Electrogenerated hydroxyl radicals, BDD, DSA, Electro-Fenton, Polymer modification, Nanogel
Study of Atrp Process for the Grafting of Vinyl Monomers on PVC and PVDF
STUDY OF ATRP PROCESS FOR THE GRAFTING OF VINYL MONOMERS ON PVC AND PVDF Sonia Lanzalaco, Onofrio Scialdone, Alessandro Galia, Rosalia Mauro, Flavia Lazzano Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Viale delle Scienze, Palermo e-mail: sonia.lanzalaco@unipa.it ATRP (atom transfer radical polymerization) has been recently used to prepare graft copolymers with regularly-spaced polymer chains from polymeric macroinitiators that have pendant chemical groups containing radically transferable halogen atoms [1]. The halogen atom serves as initiation site for the polymerization of side chains. Furthermore, Matyjaszewsky and Gennaro showed that an externally applied ele…