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International audience; Ionizing radiation has become the most effective way to modify natural and synthetic polymers through crosslinking, degradation, and graft polymerization. This review will include an in-depth analysis of radiation chemistry mechanisms and the kinetics of the radiation-induced C-centered free radical, anion, and cation polymerization, and grafting. It also presents sections on radiation modifications of synthetic and natural polymers. For decades, low linear energy transfer (LLET) ionizing radiation, such as gamma rays, X-rays, and up to 10 MeV electron beams, has been the primary tool to produce many products through polymerization reactions. Photons and electrons interaction with polymers display various mechanisms. While the interactions of gamma ray and X-ray photons are mainly through the photoelectric effect, Compton scattering, and pair-production, the interactions of the high-energy electrons take place through coulombic interactions. Despite the type of radiation used on materials, photons or high energy electrons, in both cases ions and electrons are produced. The interactions between electrons and monomers takes place within less than a nanosecond. Depending on the dose rate (dose is defined as the absorbed radiation energy per unit mass), the kinetic chain length of the propagation can be controlled, hence allowing for some control over the degree of polymerization. When polymers are submitted to high-energy radiation in the bulk, contrasting behaviors are observed with a dominant effect of cross-linking or chain scission, depending on the chemical nature and physical characteristics of the material. Polymers in solution are subject to indirect effects resulting from the radiolysis of the medium. Likewise, for radiation-induced polymerization, depending on the dose rate, the free radicals generated on polymer chains can undergo various reactions, such as inter/intramolecular combination or inter/intramolecular disproportionation, b-scission. These reactions lead to structural or functional polymer modifications. In the presence of oxygen, playing on irradiation dose-rates, one can favor crosslinking reactions or promotes degradations through oxidations. The competition between the crosslinking reactions of C-centered free radicals and their reactions with oxygen is described through fundamental mechanism formalisms. The fundamentals of polymerization reactions are herein presented to meet industrial needs for various polymer materials produced or degraded by irradiation. Notably, the medical and industrial applications of polymers are endless and thus it is vital to investigate the effects of sterilization dose and dose rate on various polymers and copolymers with different molecular structures and morphologies. The presence or absence of various functional groups, degree of crystallinity, irradiation temperature, etc. all greatly affect the radiation chemistry of the irradiated polymers. Over the past decade, grafting new chemical functionalities on solid polymers by radiation-induced polymerization (also called RIG for Radiation-Induced Grafting) has been widely exploited to develop innovative materials in coherence with actual societal expectations. These novel materials respond not only to health emergencies but also to carbon-free energy needs (e.g., hydrogen fuel cells, piezoelectricity, etc.) and environmental concerns with the development of numerous specific adsorbents of chemical hazards and pollutants. The modification of polymers through RIG is durable as it covalently bonds the functional monomers. As radiation penetration depths can be varied, this technique can be used to modify polymer surface or bulk. The many parameters influencing RIG that control the yield of the grafting process are discussed in this review. These include monomer reactivity, irradiation dose, solvent, presence of inhibitor of homopolymerization, grafting temperature, etc. Today, the general knowledge of RIG can be applied to any solid polymer and may predict, to some extent, the grafting location. A special focus is on how ionizing radiation sources (ion and electron beams, UVs) may be chosen or mixed to combine both solid polymer nanostructuration and RIG. LLET ionizing radiation has also been extensively used to synthesize hydrogel and nanogel for drug delivery systems and other advanced applications. In particular, nanogels can either be produced by radiation-induced polymerization and simultaneous crosslinking of hydrophilic monomers in “nanocompartments”, i.e., within the aqueous phase of inverse micelles, or by intramolecular crosslinking of suitable water-soluble polymers. The radiolytically produced oxidizing species from water, •OH radicals, can easily abstract H-atoms from the backbone of the dissolved polymers (or can add to the unsaturated bonds) leading to the formation of C-centered radicals. These C-centered free radicals can undergo two main competitive reactions; intramolecular and intermolecular crosslinking. When produced by electron beam irradiation, higher temperatures, dose rates within the pulse, and pulse repetition rates favour intramolecular crosslinking over intermolecular crosslinking, thus enabling a better control of particle size and size distribution. For other water-soluble biopolymers such as polysaccharides, proteins, DNA and RNA, the abstraction of H atoms or the addition to the unsaturation by •OH can lead to the direct scission of the backbone, double, or single strand breaks of these polymers.

Synthetic rubber/thermoplastic blends were electrospun from their solutions. The rubber was a solid acrylonitrile/butadiene/acrylic acid copolymer and the thermoplastic was polyacrylonitrile. The aims of this study were to identify suitable systems and processing conditions for obtaining rubber-based electrospun nanofibers, to investigate the ability of an epoxy resin system to impregnate and swell selected hybrid rubber/thermoplastic mats, and to assess the impact of the nanofibers on the resin morphology and curing behavior. In particular, electrospinning trials were carried out varying the composition of the feed solution and process parameters, such as the applied voltage, the flow rate, and tip-to-collector distance. The morphology of the hybrid mats was characterized by scanning electron microscopy and their thermal properties by thermogravimetry. An epoxy resin-mat monolayer was also prepared and its fracture surface inspected; both rubber nanoparticles and PAN nanofibers were evident. The highly corrugated fracture surfaces suggest activation of local epoxy-resin toughening mechanisms. Altogether, the results encouraged the application of hybrid mats as interleaves in high-performance carbon/epoxy composites to contrast delamination.

Xyloglucans are highly branched, hydroxyl rich polyglucans that for their abundance in nature, biocompatibility, film forming and gelation ability may take a prominent role in the design and fabrication of biomedical devices, including in situ forming scaffolds for tissue engineering, wound dressings and epidermal sensors. The understanding and exploitation of their self-assembly behavior is key for the device performance optimization. A multi-scale analysis, conducted combining small-angle X-ray scattering, both static and dynamic light scattering at large and small angles, and rheological measurements, provides a description of the supramolecular organization of this biopolymer, from the scale of a few nano-meter, to the meso- and macro-scale both in the sol and gel states. Xyloglucan self-assembly is described as multi-step and hierarchical process with different levels of organization.

Partially degalactosylated xyloglucan from tamarind seeds (Deg-XG) is a very appealing biopolymer for the production of in situ gelling systems at physiological temperature. In this work, we observe that the morphology of hydrogels evolves towards high degrees of structural organization with time, yielding to dense stacks of thin membranes within 24 h of incubation at 37 °C. We also explore the possibility offered by gamma irradiation of controlling the time scale of this phenomenon, the final morphology and mechanical properties of the system. Structural and molecular modifications of Deg-XG with dose are investigated by FTIR, dynamic light scattering (DLS) and rotational viscosimetry. The impact on gelation ability and gel strength is studied by rheological analysis. The morphology evolution is investigated by SEM analysis, and absence of cytotoxicity verified by MTS assay and optical microscopy of neuroblastoma cells.

Electrospun mats have been applied as toughening interlayers in high performance carbon fiber epoxy composites. While the toughening mechanism exerted by the mat at the interface is the subject of several recent studies, no investigations are reported on the aging behaviour of laminates comprising these nanostructured elements. This work investigates the influence of the combined effect of water and temperature (90 °C) on laminates with Nylon 6,6 electrospun membranes placed either at the middle plane only or at each interlayer. The water-uptake behaviour is modelled by a two-stage diffusion model and compared with the behaviour of the neat resin and of the laminate without mats. Interestingly, a lower water uptake is observed for the laminates with mat-modified interfaces and this is possibly due to a significantly reduced porosity. The effect of hydrothermal aging on the thermal (Tg) and mechanical properties (transverse flexural modulus and interlaminar shear strength) of the various laminates is also investigated.

Nanogels are very promising biomedical nanodevices. The classic “radiation chemistry-based” approach to synthetize nanogels consists in the irradiation with pulsed electron beams of dilute, N2O-saturated, aqueous solutions of water-soluble polymers of the “crosslinking type”. Nanogels with controlled size and properties are produced in a single irradiation step with no recourse to initiators, organic solvents and surfactants. This paper combines experimental syntheses, performed with two e-beam irradiation setups and dose-ranges, starting from poly(N-vinyl pyrrolidone) solutions of various concentrations, both in N2O-saturated and air-saturated initial conditions, with the numerical simulations of the radiation chemistry of aqueous solutions of a radical scavanger exposed to the same irradiation conditions used in the experiments. This approach provides a methodology to predict the impact of system and irradiation conditions on the water radiation chemistry, which in turn affect the nanogel features in terms of molecular and physico-chemical properties. In particular, the crucial role of initial and transient concentration of molecular oxygen is revealed. This work also proposes a very simple and effective methodology to quantitatively measure the double bonds formed in the systems from disporportionation and chain scission reactions, competing with inter-/intra-molecular crosslinking.

In-situ generation of a nanodispersed conductive polymer within a polypropylene matrix has been pursued in order to obtain flexible, conductive films. Radiation grafting of acrylic acid to polypropylene (PP) has been applied to insert carboxyl functionalities on PP. The radiation-grafted films have been further derivatized with a variety of diamines and used as substrates for in-situ chemical oxidative polymerization of polyaniline (PANI). PANI grows as a thin skin from the surface of the film as well as an interpenetrated network in its interiors. Evidence of chemical attachment of PANI to PP has been sought by performing FTIR and XPS analyses after extraction of the unbound polymer. The influence of the nature of the substituent attached to PP on the optical and electrical properties of the films has been investigated. PANI-PP skin-core films have been also tested as flexible electrodes for further electrochemical growth of the conductive polymer.

Thin xyloglucan-based hydrogel films have been synthetized and characterized in the prospect of producing wound dressings. Polyvinyl alcohol (PVA) and glycerol (Gro) were added to have an optimal combination of softness, conformability and resilience. Physical hydrogels have been transformed into permanent covalent hydrogels by reaction with glutaraldehyde (GA). Network structure-process-property relationships are discussed on the account of the results of several complementary characterizations: FTIR, rheology, thermal analysis, morphological analysis, moisture retention and swelling measurements. Selected formulations were also subjected to preliminary in vitro cytotoxicity tests. The physical and mechanical properties of some of the xyloglucan-based hydrogel films produced, combined with absence of cytotoxicity, make them suitable candidates for integration with sensors to monitor the wound healing process and further biological investigations in animal models.

Responsive hydrogels filling the interstitial spaces of photonic crystals can form mesoscopically structured materials, which exhibit reversible shifts in the Bragg diffracted light as a response of environmental changes. These materials can be used to generate chemical or biochemical sensors. The present work reports on the synthesis and characterization of ethanol responsive hydrogels that can be used in the design of novel breathalyzers. The dynamic mechanical behavior of the macroscopic hydrogels and their swelling features in the presence of different liquids or vapors have been investigated to orientate the choice of the best responsive material and curing process. The swelling behavior of a selected hydrogel embedding the photonic crystal made of polystyrene nanoparticles as function of the concentration of ethanol vapor was studied through UV–Vis optical transmission spectroscopy and compared to the behavior of the macrogel analogue.

In this work, a new method for numerical simulation of the radiation chemistry of aqueous polymer solutions exposed to a sequence of electron pulses is presented. The numerical simulations are based on a deterministic approach encompassing the conventional homogeneous radiation chemistry of water as well as the chemistry of polymer radicals. The multitude of possible reactions in the macromolecular system is handled by allowing for a large number of macromolecular species. The speciation of macromolecular species is done to account for variations in molecular weight, number of alkyl radicals per chain, number of peroxyl radicals per chain, number of oxyl radicals per chain, and number of internal loops. As benchmarking, previously published results from a series of experiments on pulsed irradiation of aqueous poly(N-vinylpyrrolidone) (PVP) solutions are used. The numerical simulations clearly show that the pulsed nature of the radiation must be accounted for. The simulations qualitatively reproduce the experimentally observed impact of initial gas saturation (air and N2O) and polymer concentration on the molecular chain length upon irradiation. The formation of double bonds as a function of dose as well as the impact of effective dose rate on the final chain length are also qualitatively reproduced in the simulations.

In this work a DGEBF epoxy monomer was cured by electron beam radiation in the presence of an iodonium salt and the obtained system was hydrothermally aged as such and also after a thermal treatment, in order to obtain two systems having different uniformity in the cross-linking degree. On both systems, the transient stress field arising from swelling was measured and monitored by an optical Photoelastic technique and the results were commented with reference to a thermally cured epoxy system containing the same monomer and already discussed in a previous work. Beam samples with identical dimensions, obtained from the irradiated systems, have been aged at 80 °C in water, and characterised by Gravimetric and DMTA tests. The results are compared also with already reported swelling behaviour of similar thermally cured systems. It is observed that the different curing techniques (radiation curing, radiation curing followed by thermal curing and thermal curing) determine a different network structure and a different water chemical affinity, which influence the amounts of absorbed/desorbed water, and the relative amounts of bonded/free water. Such differences affect the swelling behaviour, and then the transient stress field. Photoelastic Stress Analysis has allowed to evaluate the evolving stress field, providing a different point of view on the investigation of the material transformations associated to water diffusion.

Study of macromolecular structure and dynamics of networks formed by pulsed electron-beam irradiation of poly(N-vinyl pyrrolidone) (PVP) aqueous solutions, at relatively low energy per pulse and across different concentration regimes, provides the basis for the understanding of a new generation of functional nanostructures. Networks are the result of the follow–up reactions initiated by a continuous series of electron pulse-generated hydroxyl radicals, which may have a different fate at the variance of polymer concentration. Different spectroscopic techniques, FT-IR, 13 C { 1 H} CP-MAS NMR and Raman, applied to characterize the formed networks, describe a profound modification of the chemical structure when network size is approaching the nanoscale. Static light scattering measurements provide further information on the average weight molecular weight modification of PVP when forming nanogel particles. From the simultaneous control of network size and modification of chemical functionality stems also an intrinsic fluorescence of these nanogels never observed before. Altogether the obtained radiation-sculptured nanogels exhibit interesting multifunctionality that, coupled with the already proven biocompatibility, can be exploited in the biomedical field.

Surface modification of polymeric films is a way to obtain final products with high performance for many specific and ad hoc tailored applications, e.g. in functional packaging, tissue engineering or (bio)sensing. The present work reports, for the first time, on the design and development of surface modified ethylene–acrylic acid copolymer (EAA) films with polyaniline (PANI), with the aim of inducing electrical conductivity and potentially enable the electronic control of a range of physical and chemical properties of the film surface, via a new “grafting from” approach. In particular, we demonstrate that PANI was successfully polymerized and covalently grafted onto flexible EAA substrates, previously activated. The final hybrid materials and the corresponding intermediates were fully characterized via FTIR, XPS, SEM–EDAX, mechanical and electrical tests. The mechanical properties of the films are not detrimentally affected by each treatment step, while a significant increase in electrical conductivity was achieved for the new hybrid materials.

A model epoxy resin/anhydride system, modified with a polyethersulfone (PES) engineering thermoplastic toughening agent, has been studied under hydrothermal ageing in order to investigate the modification of the thermal, morphological and mechanical behaviour through dynamical mechanical thermal analysis, SEM microscopy and fracture toughness test respectively. Two different concentrations of the toughening agent were used in the blends and two ageing conditions have been considered, consisting of the immersion of the samples in distilled water at constant temperature of 70 °C for 1 week and for 1 month. Dynamical mechanical thermal analysis results on hydrothermally aged materials indicated the occurrence of progressive segregation effects with the formation of regions with different cross-linking degrees. Fracture toughness tests showed an increase of the K IC value with the increase of the toughening agent concentration, revealing both a dramatic decrease of the same parameter after 1 week ageing for all the materials and the tendency to reach an almost constant value after 1 month ageing for all the formulations, with a slight increase with respect to 1 week ageing. These results have been interpreted on the basis of the SEM analysis, showing the presence of a well defined micrometric PES particles distribution in the epoxy/anhydride matrix, and discussed in the light of different water absorption mechanisms at short and long ageing times.

The hydrothermal ageing of epoxy–thermoplastic blends, used as matrices for carbon fibre composites, cured by electron beam, has been studied. Two different thermoplastic percentages have been adopted. A suitable choice of both curing process and formulation parameters allows to carry out irradiation at mild temperature with several advantages, coming from a “non thermal” process, for both the final properties of the materials and the environment. Nevertheless the occurring of vitrification phenomena needs the use of a short thermal treatment after irradiation on the already solid materials, in order to complete the cure reactions. Radiation cured epoxy based matrices have been subjected to a thermal and moisture absorption ageing treatment and its influence on the thermal and mechanical properties has been investigated through dynamic mechanical thermal analysis and fracture toughness tests. The results have been interpreted on the basis of the different curing degree reached by the investigated systems and in the light of their morphological structures. Plasticization, thermal curing and degradation reactions occur in different extent depending on the kind of the material. In particular, for fracture properties, a better resistance to ageing is shown by the system at higher thermoplastic concentration.

A family of poly(amino acid)-maleic anhydride hydrogels were designed and synthesized. Water soluble polymeric precursors were prepared by partially substituting the hydroxyl groups of the α,β-poly( N -2-hydroxyethyl)- dl -aspartamide backbone with maleic anhydride, so as to provide double bonds for crosslinking and carboxylic acid groups for pH and electric field responsiveness. Reaction conditions (reactive mixture composition and catalysis) were systematically varied in order to obtain PHEA–MA precursors with different and reliable graft-maleic anhydride levels. PHEA–MA precursors were characterised by titration, Nuclear Magnetic Resonance ( 1 H NMR), Fourier-Transformed Infrared Spectroscopy (FTIR) and Size Exclusion Chromatography (SEC) for structural and molecular determination. Aqueous solutions of selected PHEA–MA precursors were subjected to gamma-irradiation at different irradiation doses and polymer to water concentrations in order to induce chemical crosslinking without the addition of crosslinking agents. The yield of crosslinking reactions was evaluated by solubility tests as well as the effect of ammonium persulphate, as assistant radical initiator for gamma crosslinking. Selected hydrogels were tested through swelling measurements to prove their pH and electric field responsiveness. Structural features of the different variants produced were related to the swelling behaviour.

A novel electrically conductive composite material, consisting of polyaniline (PANI) nanoparticles dispersed in a polyvinyl pyrrolidone (PVP) hydrogel, was prepared ‘in situ’ by water dispersion polymerisation (DP) of aniline using PVP as steric stabiliser, followed by γ-irradiation induced crosslinking of the PVP component. Conversion yield of aniline into PANI particles was determined via HPLC and gas chromatography, while structural confirmation of the synthesised polymer was sought by FTIR. Morphology and dimensions of PANI particles into the coloured, optically transparent hydrogel was determined by electronic microscopy; moreover, swelling behaviour of composite hydrogels in different buffer solutions was investigated by gravimetric measurements and compared to that of pure PVP hydrogels. Cyclic voltammetry experiments were carried out both on these hydrogels and on the parent aqueous dispersions, at different pH values of the suspending/swelling medium, while conductivity of the composite hydrogels was derived from Impedance Spectroscopy; in both cases results were compared to those relative to hydrogels containing commercial-grade PANI particles.

Polymerization of an acrylate derivative of bisphenol-A by ionizing radiation in the presence of an organically modified montmorillonite was carried out in order to produce a flame-retardant composite. The measurement of the thermal effect during irradiation indicates that radiation curing of pure resin and resin-clay mixtures occurred in both cases. Moreover, differential scanning calorimetry and dynamic mechanical thermal analysis showed that a curing completion can be obtained by thermal curing after irradiation with a significant increase of the glass transition temperature. The morphology was investigated by X-ray diffraction and transmission electron microscopy. These have indicated that gamma irradiation leads to the formation of a microcomposite structure after radiation curing. The flame resistant characteristics were studied by means of thermal gravimetric analysis under nitrogen and air and by cone calorimeter tests. In particular, thermal gravimetric analysis in air showed that the presence of the dispersed clay in the polymer matrix increases the oxidation temperature. This is attributed to the formation of a more stable char, due to a protective skin of clay aggregates that builds up on the surface of the volatilizing polymer matrix during thermal degradation which protects the charred polymer from reactions with oxygen. Finally, the cone calorimeter tests show a reduction of heat release of the clay-polymer composite with respect to the neat resin. The contribution of the clay in reducing the rate of heat release is attributed to the dispersion of the filler that allows build-up of an inorganic surface layer at a rate which is sufficient for effectively compete with the feeding of the flame with combustible pyrolysis products. © 2006 Wiley Periodicals, Inc. Adv Polym Techn 25: 109–120, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20063

none 8 no Nylon 6,6 electrospun nanofibrous membranes interleaved in Carbon Fibre Reinforced Plastic (CFRP) laminates have been proposed as a means to provide a higher threshold value to delamination on structural sites where composites are more prone to develop such failure. A model, highly crosslinked thus inherently brittle, epoxy matrix was selected for its high Young’s modulus and glass transition temperature exceeding 250 °C. The influence of the Nylon 6,6 nanofibres on the curing behaviour of the matrix and on the thermal and dynamic mechanical properties of the cured resin was investigated. These properties were related to the features of the epoxy resin and of the resin impregnated nanofibrous mat. Finally, the delamination behaviour of two composite laminates interleaved with different thicknesses of Nylon interleaf was studied through Mode I delamination tests. The initial Mode I fracture toughness was increased up to about 50% by the presence of a thin mat interleaf. none S ALESSI; M Di FILIPPO; C DISPENZA; ML FOCARETE; C GUALANDI; R PALAZZETTI; G PITARRESI; A ZUCCHELLI S ALESSI; M Di FILIPPO; C DISPENZA; ML FOCARETE; C GUALANDI; R PALAZZETTI; G PITARRESI; A ZUCCHELLI

Xyloglucan is a natural polysaccharide having a cellulose-like backbone and hydroxyl groups-rich side-chains. In its native form the polymer is water-soluble and forms gel only in presence of selected co-solutes. When a given fraction of galactosyl residues are removed by enzymatic reaction, the polymer acquires the ability to form a gel in aqueous solution at physiological temperatures, a property of great interest for biomedical/pharmaceutical applications. This work presents data on the effect of a temperature increase on degalactosylated xyloglucan dispersed in water at concentration low enough not to run into macroscopic gelation. Results obtained over a wide interval of length scales show that, on increasing temperature, individual polymer chains and pre-existing clusters self-assemble into larger structures. The process implies a structural rearrangement over a few nanometers scale and an increase of dynamics homogeneity. The relation of these findings to coil-globule transition and phase separation is discussed.

In this work a "new" way to obtain "compatibilised" blends of rubber-glassy thermoplastic components is presented. Polyethylen-vinyl acetate acrylic acid terpolymer is swollen by methylmetacrylate and the system is irradiated through gamma rays in order to induce polymerisation of the monomer. Solubility and dynamic mechanical tests indicate the formation of a two phase system, even though in presence of strong interactions between the two components. Mechanical tensile behaviour is that of a ductile material with appreciable modulus values.

A high molecular weight acrylonitrile/butadiene/methacrylic acid (Nipol 1472) rubber is chosen to control processability and mechanical properties of a TGDDM (tetra glycidyl diphenyl methane) based epoxy resin formulation for aerospace composite applications. The physical blend of rubber and epoxy resin, achieved by dissolution of all the components in a common solvent, forms a heterogeneous system after solvent removal and presents coarse phase separation during cure that impairs any practical relevance of this material. A marked improvement of rubber-epoxy miscibility is achieved by reactive blending ('pre-reaction') the epoxy oligomer with the functional groups present in the rubber. The epoxy-rubber 'adduct' so obtained appears as a homogeneous system at room temperature and also after compounding with the curing agent. Depending on the nature and extent of interactions developed between the rubber and the epoxy resin during 'pre-reaction,' materials with different resin flow characteristics, distinctive morphologies and mechanical properties after curing were obtained. The effect of 'pre-reaction' on the resin cure reaction kinetics has been also investigated.

Injectable polymer scaffolds are particularly attractive for guided tissue growth and drug/cell delivery with minimally invasive intervention. In the present work, "all-polymeric" gelling systems based on pectins and water-soluble maltose-conjugated chitosans (CM) have been developed. Maltose-conjugated chitosan has been synthesized at three different molar ratios, as evaluated by FITR analysis and fluorimetric titration. A thorough rheological characterization of the blends and their parent solutions has been performed. Macroscopic gelation has been achieved by mixing the high esterification degree pectins with CM at higher maltose grafted to chitosan contents. Gels form in a few minutes and reach their full strength in less than two hours. These features encourage their further development as scaffold for tissue engineering. (C) 2014 Elsevier Ltd. All rights reserved.

Pulsed electron-beam irradiation of a semi-dilute poly(N-vinyl pyrrolidone) (PVP) aqueous solution in the presence of acrylic acid has led to a carboxyl functionalized nanogel system. Nanoparticles hydrodynamic size and surface charge density, in water and as a function of pH, were investigated by dynamic light scattering and laser doppler velocimetry, respectively. Nanogels (NGs) were proved not to be cytotoxic at the cellular level. Indeed, they rapidly bypass the cellular membrane to accumulate in specific cell portions of the cytoplasm, in the perinuclear area. The availability of pendant carboxyl groups on the crosslinked PVP NGs core prompted us to attempt their decoration with a single strand oligonucleotide, which holds a terminal amino group. The recognition ability of the attached single helix of its complementary strand was investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39774.

Aminopropyl methacrylamide chloride-graft-poly(N-vinyl pyrrolidone) nanogels (NGs) were designed to exploit the favorable properties of poly(N-vinyl pyrrolidone) (PVP), such as its high affinity to water and complexation ability of ions, molecules and macromolecules, with the availability of primary amino groups for bioconjugation reactions. A thorough structural characterization of the nanoscalar networks was performed via 1 H NMR and solid state 13 C NMR spectroscopies, while solid state NMR relaxation time measurements completed the NGs description in terms of polymer network density. Information on the hydrodynamic size and surface charge densities were sought via dynamic light scattering (DLS) and ζ-potential measurements. These measurements, carried out both in water and in buffer and at the variance of pH, temperature and time, support the excellent colloidal stability of the amino-graft PVP nanogels and their redispersability from the dry physical form. The total absence of in vitro toxicity and immunogenicity was ascertained first, and then cell localization studies in cell cultures of fluorescent variants were performed. Furthermore, the possibility of decorating the nanogels with bovine serum albumin (BSA) to obtain a stable bio-hybrid colloidal nanoconstruct was established. All the gathered evidences qualify these materials as potential candidates to be used as nanocarriers for intra-cellular delivery of protein and other biomolecular drugs.

A scalable, single-step, synthetic approach for the manufacture of biocompatible, functionalized micro- and nanogels is presented. In particular, poly(N-vinyl pyrrolidone)-grafted-(aminopropyl)methacrylamide microgels and nanogels were generated through e-beam irradiation of PVP aqueous solutions in the presence of a primary amino-group-carrying monomer. Particles with different hydrodynamic diameters and surface charge densities were obtained at the variance of the irradiation conditions. Chemical structure was investigated by different spectroscopic techniques. Fluorescent variants were generated through fluorescein isothiocyanate attachment to the primary amino groups grafted to PVP, to both quantify the available functional groups for bioconjugation and follow nanogels localization in cell cultures. Finally, a model protein, bovine serum albumin, was conjugated to the nanogels to demonstrate the attachment of biologically relevant molecules for targeting purposes in drug delivery. The described approach provides a novel strategy to fabricate biohybrid nanogels with a very promising potential in nanomedicine.

In this paper we report for the first time on the emissive behavior of two polyaniline (PANI) nanoparticle systems produced via oxidative chemical polymerization in the presence of either poly(vinyl alcohol) (PVA) or chitosan as polymeric stabilizers in water. The emission from PANI nanoparticles is irreversibly quenched by an increase of pH of the suspending medium from acid to neutral (chitosan–PANI) or alkaline (PVA–PANI). Conversely, PANI nanorods synthesized in the same conditions of the above, but in presence of poly(N-vinyl pyrrolidone), is not emissive at any pH. The role of the polymeric surfactant as a soft template is key in controlling the morphology and the properties of the obtained PANI dispersions. FTIR, UV–Vis absorption and photoluminescence excitation (PLE) spectra studies suggest that the emissive properties are related to the establishment of strong, non-covalent interactions between nanoscalar PANI particles and the polymeric surfactant at the pH of synthesis. Morphology examination of the three systems, by both dynamic light scattering (DLS) and Transmission Electron Microscopy (TEM), reveal that photoluminescence is associated to the presence of a genuinely 3D nanoscalar morphology, together with an ordered disposition of PANI chains into aligned crystal planes. Concomitant to the irreversible quenching of the emission signal with increasing pH, there is an evolution of the morphology leading to particle coalescence, coarsening and ultimately phase-separation, with consequent modification of PANI–polymeric surfactant interactions, PANI chains supra-molecular organization and optical properties of the PANI nanoparticles dispersion.

Gelled microemulsions are the subject of considerable scientific and commercial interest. Many efforts are currently devoted to improving their toxicological profile and functioning as biocompatible diffusion barrier for the controlled delivery of hydrophobic compounds. In the present investigation, a non-ionic polymeric surfactant was chosen to generate an oil-in-water microemulsion of a model fragrance in the presence of poly(N-vinyl-2-pyrrolidone) (PVP). The microemulsion was then subjected to either electron-beam or UV-irradiation to induce free-radical crosslinking of PVP at low temperature and in the absence of crosslinking agents, catalysts and initiators. Irradiation conditions with the two irradiation sources have been purposely selected to generate PVP hydrogels with similar appearances and mechanical spectra. Despite the macroscopic analogies, specific features are imparted to the two families of hydrogels by the two different irradiation methodologies. A description of the microstructure of both pure PVP and microemulsion-laden hydrogels is given starting from the dynamic light scattering (DLS) characterization of the liquid (unirradiated) formulations, followed by the study the hydrogels' dynamic mechanical, solubility and swelling properties, FTIR analysis of the water insoluble fractions, DLS measurements and cytotoxicity studies.

In the recent years recombinant technology has identified numerous protein based therapeutics. Their effective delivery, though, can be challenging due to the poor stability of most proteins along their pathway to the target site in the body. Hydrogels have been identified as good candidates for protein encapsulation and delivery thanks to both material and manufacturing process advantages. In this work we propose high energy irradiation as a synthetic methodology of choice to engineer hydrogel-based delivery devices for encapsulation and pulsatile release of proteins, triggered by pH, and for prevention of their denaturation when encapsulated. In particular, maleic anhydride functionalised poly( N -2-HydroxyEthyl)-DL-Aspartamide (PHEA-MA) hydrogels have been crosslinked without the use of toxic reagents or catalysts and in mild conditions via gamma irradiation. At the variance of the irradiation conditions, hydrogels with dramatically different crosslinked structure, thus rheological properties and swelling behaviour, have been obtained. The ability to swell and shrink cyclically upon repeated pH jumps and the absence of cytotoxicity have been demonstrated for all the hydrogels produced. Moreover some of the variants exhibited full degradability at 37 °C with degradation products that are not-toxic for the cell. Depending on the networks average mesh size, as derived by the treatment of rheological data with simple rubber elasticity equations, with respect to the characteristic dimension of the chosen model protein, substantial loading of the protein and its retention or release, controlled by pH, have been achieved. These results, coupled with the versatility of the synthetic platform, suggest the possibility to use these materials as components of intelligent/programmable devices specifically designed as to release theoretically any protein based therapeutic.

The use of ionizing radiation in order to initiate polymerization of suitable monomers has found increased interest in the last two decades due to its several advantages. In this work, carbon fiber composites through gamma radiation polymerization of epoxy matrices have been produced for aerospace and advanced automotive applications. Composite samples were produced by irradiation at room temperature using different radiation doses and, as reference, thermal curing of the same epoxy resin formulations was also carried out. Furthermore, some irradiated samples were subjected to postirradiation thermal curing to complete the polymerization reactions. The properties of the cured materials were studied by dynamic mechanical thermal analysis and mechanical flexural tests. Also the effect of moisture absorption on the thermal properties was investigated. The results indicate that irradiation at room temperature gives rise to different cross-link densities of the epoxy matrix depending on the total absorbed dose. Postirradiation thermal treatment makes the materials more “homogeneous,” resulting also in a higher glass transition temperature. Moreover, thermal analysis performed on irradiated samples, cut in both parallel and perpendicular directions to the fibers, has shown fiber--matrix interactions that are less intensive in comparison to thermally cured samples. The water absorption data show a plasticization effect of moisture on the epoxy matrix, causing a significant reduction of Tg. Flexural tests reveal a marked effect of postirradiation thermal curing on the less cross-linked samples, reflecting the higher efficiency of the thermal treatment on more mobile reactive species. © 2009 Wiley Periodicals, Inc. Adv Polym Techn 27:163–171, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20127

Nanocomposites of inherently conductive polyaniline (PANT) within a highly hydrophilic polyvinyl alcohol (PVA) based hydrogel have been produced by coupling a conventional dispersion chemical oxidative polymerization to a subsequent high energy irradiation step, in order to convert the polymer stabilizing the aqueous dispersion, namely the PVA, into a highly water swollen hydrogel incorporating the PANT particles. The incorporation of the electroactive and "pH-sensitive" polymer into a transparent and highly permeable hydrogel matrix has been pursued as a route to the development of a novel class of potentially biocompatible, smart hydrogels that can respond to changes of the surrounding environment with measurable changes in their optical properties. Absorption spectra show that the optical absorption bands typical of PANT, known to be reversibly affected by changes of the polymer oxidation state or pH or both, are well preserved in the PVA hydrogels. Even more interestingly, fluorescence is observed from the nanoparticles of PANT in its inherently conductive form, whose intensity is strongly affected by changes of pH. This has enhanced the importance of this material to a large extent from both a scientific and a practical point of view.

The aim of the present investigation is to assess the possibility of obtaining a biocompatible material device which is able to deliver oil-soluble fragrances in air over a length of time. Aqueous solutions of polyaspartamide functionalised with glycidyl methacrylate have been cross linked through gamma irradiation in the presence of a lipophilic model fragrance, emulsified prior to irradiation. Two emulsification conditions have been considered at two different concentrations of both fragrance and surfactant in water. Chemical hydrogels have been obtained in correspondence to two irradiation absorbed doses and have been characterised for their solubility properties and swelling ability in water. Both static and dynamic release experiments of the fragrance in air have been performed and the release behaviour related to the hydrogel network structure and its water retention properties.

A high molecular weight, carboxyl functionalised solid rubber was added to an epoxy resin-aromatic amino system developed for autoclave curing of honeycomb core composite structures. The achievement of an optimal balance of viscous flow and viscoelasticity of the resin, by controlling the nature and extent of cross-linking of the functionalised rubber, was proposed as a route to void-free honeycomb skins. The aim of the present investigation is to understand how the concentration of carboxylic groups of the rubber, prereacted with one of the epoxy monomers, affects the matrix resin flow properties. The concentration of carboxyl groups was changed by reacting them with a monofunctional epoxy resin. Dynamic shear viscosity profiles varying frequency, temperature and as function of time during isothermal cure have been determined for blends with differently functionalised rubbers. Carbon fibre wettability and laminate consolidation quality have been evaluated, making composite samples according to conventional prepregging and autoclave curing processes, through electron microscopy of fracture surfaces from transverse flexural strength tests.