Hydrogel Based on Polyhydroxyalkanoate Sulfonate: Control of the Swelling Rate by the Ionic Group Content.

Hydrogels based on poly(3-hydroxyalkanoate) (PHA) sulfonate and poly(ethylene glycol) diacrylate, PEGDA, are prepared. First, PHA sulfonate is synthesized from unsaturated PHA by a thiol-ene reaction in the presence of sodium-3-mercapto-1-ethanesulfonate. The hydrophilicity of PHAs is considerably increased by adding sulfonate functions, and three amphiphilic PHAs are synthesized, containing 10, 22, or 29% sulfonate functions. Then, hydrogels are formed in the presence of PEGDA having different molar masses, that is, 575 or 2000 g mol-1. The hydrogels show fibrillar and porous structures observed in cryo-MEB with pore sizes that vary according to the content of sulfonated groups (10 to 29 mol %) ranging from 50 to more than 150 nm. Furthermore, depending on the proportions of the two polymers, a variable rigidity is observed from 2 to 40 Pa. In fact, the evaluation of the dynamic mechanical properties of the hydrogel determined by DMA reveals that the less rigid hydrogels hinder the adhesion of Pseudomonas aeruginosa PaO1 bacteria. Finally, these hydrogels swelling up to 5000% are noncytotoxic, allowing the adhesion and amplification of immortalized C2C12 cells, and they are therefore seen as promising materials both for repelling PaO1 bacteria and for amplifying myogenic cells.

Synthesis of Fluorinated Polyhydroxyalkanoates from Marine Bioresources as a Promising Biomaterial Coating.

By successive enzymatic and chemical modifications, novel fluorinated polyhydroxyalkanoates were synthesized and characterized. Unsaturated polyhydroxyalkanoate, PHAU, was first produced by fermentation using marine bacteria Pseudomonas raguenesii, and a graft copolymer PHAU-g-C8F17 was further prepared by controlled thiol-ene reaction in the presence of perfluorodecanethiol (PFDT). The PFDT grafting is realized by two different processes. In the first method, PHAU was previously solubilized in toluene. The grafting in solution is more efficient than the direct heterogeneous grafting onto a PHAU film. The degrees of grafting were determined by 1H NMR. The characterization of the microstructure by SEM-EDX and modulated and conventional DSC showed the formation of microdomains due to the organization of the hydrophobic segments of graft PFDT. Biomaterials prepared by 3D printing and coated by PHAU-g-C8F17 have the potential to be used as novel contrast agents as shown by Hahn echo experiments.

Water-Soluble Poly(3-hydroxyalkanoate) Sulfonate: Versatile Biomaterials Used as Coatings for Highly Porous Nano-Metal Organic Framework.

Water-soluble poly(3-hydroxyalkanoate) containing ionic groups were designed by two successive photoactivated thiol-ene reactions. Sodium-3-mercapto-1-ethanesulfonate (SO3-) and poly(ethylene glycol) (PEG) methyl ether thiol were grafted onto poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate) PHO(67)U(33) to introduce both ionic groups and hydrophilic moieties. The grafted copolymers PHO(67)SO3-(20)PEG(13) were then used as biocompatible coatings of nano-metal organic frameworks (nanoMOFs) surfaces. Scanning electron microscopy and scanning transmission electron microscopy coupled with energy dispersive X-ray characterizations have clearly demonstrated the presence of the copolymer on the MOF surface. These coated nanoMOFs are stable in aqueous and physiological fluids. Cell proliferation and cytotoxicity tests performed on murine macrophages J774.A1 revealed no cytotoxic side effect. Thus, biocompatibility and stability of these novel hybrid porous MOF structures encourage their use in the development of effective therapeutic nanoparticles.

Photoinduced development of antibacterial materials derived from isosorbide moiety.

A straightforward method for immobilizing in situ generated silver nanoparticles on the surface of a photoactivable isosorbide-derived monomer is developed with the objective to design a functional material having antibacterial properties. The photoinduced thiol-ene mechanism involved in these syntheses is described by the electron spin resonance/spin trapping technique. The resulting materials with or without silver nanoparticles (Ag NPs) were used as films or as coatings on glass substrate. The surface of the synthesized materials was characterized by X-ray photoelectron spectroscopy and scanning electron microscopy, and their thermal and mechanical properties were evaluated by dynamic-mechanical thermal tests, differential scanning calorimetry, thermogravimetric analyses, along with pencil hardness, nanoindentation, and scratch resistance tests. The photoinduced formation of Ag NPs is also confirmed by UV spectrophotometry. Finally, a primary investigation demonstrates the antibacterial properties of the isosorbide-derived material against Staphylococcus aureus and Escherichia coli, as well as its cytocompatibility toward NIH 3T3 fibroblastic cells.

From design of bio-based biocomposite electrospun scaffolds to osteogenic differentiation of human mesenchymal stromal cells.

Electrospinning coupled with electrospraying provides a straightforward and robust route toward promising electrospun biocomposite scaffolds for bone tissue engineering. In this comparative investigation, four types of poly(3-hydroxybutyrate) (PHB)-based nanofibrous scaffolds were produced by electrospinning a PHB solution, a PHB/gelatin (GEL) mixture or a PHB/GEL/nHAs (hydroxyapatite nanoparticles) mixed solution, and by electrospinning a PHB/GEL solution and electrospraying a nHA dispersion simultaneously. SEM and TEM analyses demonstrated that the electrospun nHA-blended framework contained a majority of nHAs trapped within the constitutive fibers, whereas the electrospinning-electrospraying combination afforded fibers with a rough surface largely covered by the bioceramic. Structural and morphological characterizations were completed by FTIR, mercury intrusion porosimetry, and contact angle measurements. Furthermore, an in vitro investigation of human mesenchymal stromal cell (hMSC) adhesion and proliferation properties showed a faster cell development on gelatin-containing scaffolds. More interestingly, a long-term investigation of hMSC osteoblastic differentiation over 21 days indicate that hMSCs seeded onto the nHA-sprayed scaffold developed a significantly higher level of alkaline phosphatase activity, as well as a higher matrix biomineralization rate through the staining of the generated calcium deposits: the fiber surface deposition of nHAs by electrospraying enabled their direct exposure to hMSCs for an efficient transmission of the bioceramic osteoinductive and osteoconductive properties, producing a suitable biocomposite scaffold for bone tissue regeneration.

Straightforward Way to Provide Antibacterial Properties to Healthcare Textiles through N-2-Hydroxypropyltrimethylammonium Chloride Chitosan Crosslinking.

A straightforward and cost-effective way to coat polypropylene fibers, designed for healthcare textiles, was developed through chitosan crosslinking for antibacterial purposes. As polypropylene is an inert material, the goal was to physically trap the inert fibers through a network of crosslinked chitosan or a quaternized derivative (to enhance the antibacterial action). First, chitosan or its quaternized derivative was physically deposited by impregnation or spraying. Then, chitosan was crosslinked in glutaraldehyde solution followed by its quaternized derivative with a diisocyanate. Coated fabrics were characterized by infrared spectroscopy (IR), weight gain measurements, and scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX). This led us to conclude that spraying provides uniform deposition while maintaining the fabric's porosity. Acidic washing allowed us to prove that chitosan and its quaternized derivative were successfully immobilized on the fabric. Biological assays were conducted against two major strains of bacteria responsible for nosocomial infections: Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). Chitosan-crosslinked samples did not show significant antibacterial activity, but the quaternized derivative allowed a significant decrease in S. aureus colonization. This study presents a simple and scalable process to coat inert fabrics with a polymer containing reactive functions potentially available to graft various additional antimicrobial agents.

Distinct Electrogram Features and Ventricular Arrhythmia Induction Modes Between Repolarization and Conduction Heterogeneities.

BACKGROUND: Recent clinical studies have indicated the presence of localized electrical abnormalities in idiopathic ventricular fibrillation and J-wave syndrome patients. OBJECTIVES: This study aims to characterize the specific electrical signatures of localized repolarization and conduction heterogeneities and their respective role in vulnerability to arrhythmias. METHODS: Optical mapping was performed in porcine right ventricles with local: 1) repolarization shortening; 2) conduction slowing; or 3) structural heterogeneity induced by locally perfusing: 1) pinacidil (20 µmol/L, n = 13); or 2) flecainide (2 µmol/L, n = 13) via an epicardial catheter; or 3) by local epicardial tissue destruction (9 radiofrequency lesions n = 12). Electrograms were recorded (n = 5 in each group) and spontaneous and induced arrhythmias were quantified and optically mapped. RESULTS: Electrograms were normal in (1) but showed local fragmentation in 40% of preparations in (2) with greater effects observed at high pacing frequencies dependent on the wavefront direction. In (3), the structural substrate alone increased the width and number of peaks in the electrograms, and addition of flecainide induced pronounced fragmentation (≥3 peaks and ≥70 ms) in all cases. Occurrence of spontaneous arrhythmias was significantly increased in (1) and (2) (P < 0.0001 and 0.05, respectively, vs baseline) and were triggered by ectopies. Vulnerability to arrhythmias at high pacing frequencies (≥2 Hz) was the lowest in (1) and greatest in (2). CONCLUSIONS: Microstructural substrates have the most pronounced impact on electrograms, especially when combined with sodium channel blockers, whereas local action potential duration shortening does not lead to electrogram fragmentation even though it is associated with the highest prevalence of spontaneous arrhythmias.

Facile synthesis of multicompartment micelles based on biocompatible poly(3-hydroxyalkanoate).

In this paper, a straightforward method to produce poly(3-hydroxyalkanoate)-based multicompartment micelles (MCMs) is presented. Thiol-ene addition is used to graft sequentially perfluorooctyl chains and poly(ethylene glycol) oligomers onto poly(3-hydroxyoctanoate-co-hydroxyundecenoate) oligomers backbone. Well-defined copolymers are obtained as shown by ¹H NMR and size-exclusion chromatography. After nanoprecipitation in water, novel PHA-based MCMs are evidenced by cryo-transmission electron microscopy. Moreover, the cytocompatibility of MCMs is demonstrated in vitro via cell viability assay.

Electrografting of a biodegradable layer as a primer adhesion coating onto a metallic stent: in vitro and in vivo evaluations.

Drug-eluting stents have been developed to reduce the risk of restenosis after angioplasty. To facilitate the adhesion of a poly(lactic acid) (PLA) overlayer loaded with rapamycin (20 wt%), a biodegradable macromonomer based on poly(lactic acid) (HEMA-PLA) was grafted onto the metallic stent by electrografting in a one-step reaction involving the immobilization of aryl diazonium onto the metal followed by an in situ surface electro-polymerization. The HEMA-PLA coating was chemically characterized. Mechanical performance during stent expansion was tested. Morphology examinations showed a strong adhesion of PLA topcoat in the presence of the electrografted layer. Biocompatibility and degradation of the coating were studied in vitro and in vivo in rabbit iliac arteries. These 28 days implantations resulted in a minimal inflammatory process with a partial degradation of the coating. These results suggest that this kind of anchoring of a biodegradable layer shows great potential for drug-eluting stents.

Green Physical Modification of Polypropylene Fabrics by Cross-Linking Chitosan with Tannic Acid and Postmodification by Quaternary Ammonium Grafting to Improve Antibacterial Activity.

A green cross-linking and straightforward method to physically trap inert fibers in a network of chitosan was implemented. The cross-linking reaction involved a biosourced and biocompatible cross-linker [tannic acid (TA)] and mild conditions in water (pH = 8.5, O2 bubbling, 60 °C, 3 h). The steric hindrance of TA led to a low but effective cross-linking rate leaving parts of primary amines of chitosan available for postmodification such as the grafting of quaternary ammoniums for antibacterial purposes. Fabric's coatings were characterized by scanning electron microscopy coupled with energy-dispersive X-ray, infrared spectroscopy, and weight gain measurements. This allowed the optimization of process conditions. No significant antioxidant activity was observed on fabrics coated with chitosan cross-linked with TA, confirming the low cross-linking rate. This low cross-linking rate allowed grafting of quaternary ammoniums for antibacterial purposes, but it is possible to consider grafting other active molecules. Biological assays were conducted on this coating to assess its antibacterial properties. Reduction of bacterial colonization on both Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative), two of the major strains responsible for nosocomial infections, confirmed the potential of the coating for antibacterial purposes. This study displays a simple and ecofriendly process to coat inert fabrics with a chitosan network containing reactive functions (primary amines) available for grafting active molecules for various purposes.

Functional Epicardial Conduction Disturbances Due to a SCN5A Variant Associated With Brugada Syndrome.

BACKGROUND: Brugada syndrome is a significant cause of sudden cardiac death (SCD), but the underlying mechanisms remain hypothetical. OBJECTIVES: This study aimed to elucidate this knowledge gap through detailed ex vivo human heart studies. METHODS: A heart was obtained from a 15-year-old adolescent boy with normal electrocardiogram who experienced SCD. Postmortem genotyping was performed, and clinical examinations were done on first-degree relatives. The right ventricle was optically mapped, followed by high-field magnetic resonance imaging and histology. Connexin-43 and NaV1.5 were localized by immunofluorescence, and RNA and protein expression levels were studied. HEK-293 cell surface biotinylation assays were performed to examine NaV1.5 trafficking. RESULTS: A Brugada-related SCD diagnosis was established for the donor because of a SCN5A Brugada-related variant (p.D356N) inherited from his mother, together with a concomitant NKX2.5 variant of unknown significance. Optical mapping demonstrated a localized epicardial region of impaired conduction near the outflow tract, in the absence of repolarization alterations and microstructural defects, leading to conduction blocks and figure-of-8 patterns. NaV1.5 and connexin-43 localizations were normal in this region, consistent with the finding that the p.D356N variant does not affect the trafficking, nor the expression of NaV1.5. Trends of decreased NaV1.5, connexin-43, and desmoglein-2 protein levels were noted; however, the RT-qPCR results suggested that the NKX2-5 variant was unlikely to be involved. CONCLUSIONS: This study demonstrates for the first time that SCD associated with a Brugada-SCN5A variant can be caused by localized functionally, not structurally, impaired conduction.

An efficient thiol-ene chemistry for the preparation of amphiphilic PHA-based graft copolymers.

We present a straightforward method to prepare amphiphilic graft copolymers consisting of hydrophobic poly(3-hydroxyalkanoates) (PHAs) backbone and hydrophilic α-amino-ω-methoxy poly(oxyethylene-co-oxypropylene) (Jeffamine®) units. Poly(3-hydroxyoctanoate)-co-(3-hydroxyundecenoate) (PHOU) was first methanolyzed to obtain the desired molar mass. The amino end groups of Jeffamine were converted into thiol by a reaction with N-acetylhomocysteine thiolactone and subsequently photografted. This "one-pot" functionalization prevents from arduous and time-consuming functionalization of the hydrophilic precursor or tedious modifications of PHAs, thus simplifying the process. The amphiphilic nature of modified PHAs leads to water-soluble copolymers exhibiting thermoresponsive behavior.

Biocompatible Semi-Interpenetrating Materials Based on Poly(3-hydroxyalkanoate)s and Poly(ethyleneglycol) Diacrylate.

Biocompatible gels based on poly(3-hydroxyalkanoate)s (PHAs) were developed by radical polymerization in the presence of poly(ethylene glycol) diacrylate (PEGDA). In order to elaborate cross-linked networks based on PEGDA and PHAs, several PHAs were tested; saturated PHAs, such as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) or poly(3-hydroxyoctanoate) (PHO), and an unsaturated PHA, poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate) PHOU. The PHAxPEGDA1-x networks obtained in this work were studied by FTIR, Raman spectroscopy, DSC, TGA and NMR. The microscopic structure varied according to the mass proportions between the two polymers. Time Domain 1H DQ NMR measurements demonstrated that in the case of the unsaturated PHA, it was chemically crosslinked with PEGDA, due to the presence of double bonds in the lateral groups. The organogels were able to swell in organic solvents, such as THF, up to 2000% and in water up to 86%. It was observed by rheological analysis that the stiffness of the networks was dependent on the content of PHA and on the degree of cross-linking. The biocompatible characters of PHOU and PEGDA were not affected by the formation of the networks and these networks had the advantage of being non-cytotoxic to immortalized C2C12 myoblast cells.

Improved Processability and Antioxidant Behavior of Poly(3-hydroxybutyrate) in Presence of Ferulic Acid-Based Additives.

Poly(3-hydroxybutyrate), PHB, has gathered a lot of attention for its promising properties-in particular its biobased nature and high biodegradability. Although PHB is prime candidate for the packaging industry, the applications are still limited by a narrow processing window and thermal degradation during melt processing. In this work, three novel additives based on ferulic acid esterified with butanediol, pentanediol, and glycerol (BDF, PDF, and GTF, respectively) were used as plasticizers and antioxidative additives to improve mechanical properties of PHB. Elongation at break up to 270% was obtained in presence of BDF and the processing window was improved nearly 10-fold. The Pawley method was used to identify the monoclinic space group P2 of the BDF. The estimated crystallite size (71 nm) agrees with a crystalline additive. With PHB70BDF30 blends, even higher elongations at break were obtained though dwindled with time. However, these properties could be recovered after thermal treatment. The high thermal stability of this additive leads to an increase in the fire retardancy property of the material, and the phenolic structure induced antioxidant properties to the samples as demonstrated by radical scavenging tests, further highlighting the possibilities of the PHB/additive blends for packaging applications.

Antioxidant Network Based on Sulfonated Polyhydroxyalkanoate and Tannic Acid Derivative.

A novel generation of gels based on medium chain length poly(3-hydroxyalkanoate)s, mcl-PHAs, were developed by using ionic interactions. First, water soluble mcl-PHAs containing sulfonate groups were obtained by thiol-ene reaction in the presence of sodium-3-mercapto-1-ethanesulfonate. Anionic PHAs were physically crosslinked by divalent inorganic cations Ca2+, Ba2+, Mg2+ or by ammonium derivatives of gallic acid GA-N(CH3)3 + or tannic acid TA-N(CH3)3 +. The ammonium derivatives were designed through the chemical modification of gallic acid GA or tannic acid TA with glycidyl trimethyl ammonium chloride (GTMA). The results clearly demonstrated that the formation of the networks depends on the nature of the cations. A low viscoelastic network having an elastic around 40 Pa is formed in the presence of Ca2+. Although the gel formation is not possible in the presence of GA-N(CH3)3 +, the mechanical properties increased in the presence of TA-N(CH3)3 + with an elastic modulus G' around 4200 Pa. The PHOSO3 -/TA-N(CH3)3 + gels having antioxidant activity, due to the presence of tannic acid, remained stable for at least 5 months. Thus, the stability of these novel networks based on PHA encourage their use in the development of active biomaterials.

Study of Mechanical Properties of PHBHV/Miscanthus Green Composites Using Combined Experimental and Micromechanical Approaches.

In recent years the interest in the realization of green wood plastic composites (GWPC) materials has increased due to the necessity of reducing the proliferation of synthetic plastics. In this work, we study a specific class of GWPCs from its synthesis to the characterization of its mechanical properties. These properties are related to the underlying microstructure using both experimental and modeling approaches. Different contents of Miscanthus giganteus fibers, at 5, 10, 20, 30 weight percent's, were thus combined to a microbial matrix, namely poly (3-hydroxybutyrate)-co-poly(3-hydroxyvalerate) (PHBHV). The samples were manufactured by extrusion and injection molding processing. The obtained samples were then characterized by cyclic-tensile tests, pycnometer testing, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, and microscopy. The possible effect of the fabrication process on the fibers size is also checked. In parallel, the measured properties of the biocomposite were also estimated using a Mori-Tanaka approach to derive the effective behavior of the composite. As expected, the addition of reinforcement to the polymer matrix results in composites with higher Young moduli on the one hand, and lower failure strains and tensile strengths on the other hand (tensile modulus was increased by 100% and tensile strength decreased by 23% when reinforced with 30 wt % of Miscanthus fibers).

Amphiphilic and Perfluorinated Poly(3-Hydroxyalkanoate) Nanocapsules for 19F Magnetic Resonance Imaging.

Nanoparticles have recently emerged as valuable tools in biomedical imaging techniques. Here PEGylated and fluorinated nanocapsules based on poly(3-hydroxyalkanoate) containing a liquid core of perfluorooctyl bromide PFOB were formulated by an emulsion-evaporation process as potential 19F MRI imaging agents. Unsaturated poly(hydroxyalkanoate), PHAU, was produced by marine bacteria using coprah oil and undecenoic acid as substrates. PHA-g-(F; PEG) was prepared by two successive controlled thiol-ene reactions from PHAU with firstly three fluorinated thiols having from 3 up to 17 fluorine atoms and secondly with PEG-SH. The resulting PHA-g-(F; PEG)-based PFOB nanocapsules, with a diameter close to 250-300 nm, are shown to be visible in 19F MRI with an acquisition time of 15 min. The results showed that PFOB-nanocapsules based on PHA-g-(F; PEG) have the potential to be used as novel contrast agents for 19F MRI.

A Review on Ion-Exchange Membrane Fouling during the Electrodialysis Process in the Food Industry, Part 1: Types, Effects, Characterization Methods, Fouling Mechanisms and Interactions.

Electrodialysis (ED) was first established for water desalination and is still highly recommended in this field for its high water recovery, long lifetime and acceptable electricity consumption. Today, thanks to technological progress in ED processes and the emergence of new ion-exchange membranes (IEMs), ED has been extended to many other applications in the food industry. This expansion of uses has also generated several problems such as IEMs' lifetime limitation due to different ageing phenomena (because of organic and/or mineral compounds). The current commercial IEMs show excellent performance in ED processes; however, organic foulants such as proteins, surfactants, polyphenols or other natural organic matters can adhere on their surface (especially when using anion-exchange membranes: AEMs) forming a colloid layer or can infiltrate the membrane matrix, which leads to the increase in electrical resistance, resulting in higher energy consumption, lower water recovery, loss of membrane permselectivity and current efficiency as well as lifetime limitation. If these aspects are not sufficiently controlled and mastered, the use and the efficiency of ED processes will be limited since, it will no longer be competitive or profitable compared to other separation methods. In this work we reviewed a significant amount of recent scientific publications, research and reviews studying the phenomena of IEM fouling during the ED process in food industry with a special focus on the last decade. We first classified the different types of fouling according to the most commonly used classifications. Then, the fouling effects, the characterization methods and techniques as well as the different fouling mechanisms and interactions as well as their influence on IEM matrix and fixed groups were presented, analyzed, discussed and illustrated.

A Review on Ion-Exchange Membranes Fouling during Electrodialysis Process in Food Industry, Part 2: Influence on Transport Properties and Electrochemical Characteristics, Cleaning and Its Consequences.

Ion-exchange membranes (IEMs) are increasingly used in dialysis and electrodialysis processes for the extraction, fractionation and concentration of valuable components, as well as reagent-free control of liquid media pH in the food industry. Fouling of IEMs is specific compared to that observed in the case of reverse or direct osmosis, ultrafiltration, microfiltration, and other membrane processes. This specificity is determined by the high concentration of fixed groups in IEMs, as well as by the phenomena inherent only in electromembrane processes, i.e., induced by an electric field. This review analyzes modern scientific publications on the effect of foulants (mainly typical for the dairy, wine and fruit juice industries) on the structural, transport, mass transfer, and electrochemical characteristics of cation-exchange and anion-exchange membranes. The relationship between the nature of the foulant and the structure, physicochemical, transport properties and behavior of ion-exchange membranes in an electric field is analyzed using experimental data (ion exchange capacity, water content, conductivity, diffusion permeability, limiting current density, water splitting, electroconvection, etc.) and modern mathematical models. The implications of traditional chemical cleaning are taken into account in this analysis and modern non-destructive membrane cleaning methods are discussed. Finally, challenges for the near future were identified.

Preparation of Clickable Poly(3-hydroxyalkanoate) (PHA): Application to Poly(ethylene glycol) (PEG) Graft Copolymers Synthesis.

A new synthesis of amphiphilic biodegradable copolymers consisting of hydrophobic poly(3-hydroxyalkanoate) (PHA) backbone and hydrophilic poly(ethylene glycol) (PEG) units as side chains is described. Poly[(3-hydroxyoctanoate)-co-(3-hydroxyundecenoate)] (PHOU) was first methanolyzed and its unsaturated side chains were quantitatively oxidized to carboxylic acid. Esterification with propargyl alcohol led to an alkyne-containing "clickable" PHA in 71% conversion. Its reactivity was successfully demonstrated by grafting azide-terminated PEG chains of 550 and 5 000 g · mol(-1) , respectively. All products were fully characterized using GPC, (1) H, and COSY NMR.