Reusable fibrous adsorbent prepared via Co-radiation induced graft polymerization for iodine adsorption.

Volatile iodine released from nuclear power plant reactors is radiological hazard to environment and human's health because of their high fission yield and environmental mobility. The complexity of nuclear waste management motivated the development of solid-phase adsorbents. Herein, co-radiation induced graft polymerization (CRIGP) was employed in the graft polymerization of N-vinyl-2-pyrrolidone (NVP) onto polyethylene-coated polypropylene skin-core (PE/PP) fibers using electron beam (EB) irradiation. This work provides a one-step green synthetic approach to prepare iodine fibrous adsorbents without any chemical initiators or large amount of organic solvent. The original and modified PE/PP fibers were characterized by fourier transform infrared spectrometry (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and scanning electron microscopy (SEM) to demonstrate the grafting of NVP onto the PE/PP fibers. The capacity of iodine absorbed by the PE/PP-g-PNVP fibers was 1237.8 mg/g after 180 min. Meanwhile, absorbents can be regenerated efficiently by two different means of ethanol elution and heating at 120 °C, respectively. Within 10 min, 94.17% and 90.12% of the iodine can be released from the PE/PP-g-PNVP fibers with these two methods, respectively. The adsorbent exhibited a long service life of at least ten adsorption-desorption cycles, suggesting that PE/PP-g-PNVP fibers might be a promising adsorbent for volatile iodine adsorption from fission products in nuclear power plant reactors.

Supercritical CO2 Foaming of Radiation Cross-Linked Isotactic Polypropylene in the Presence of TAIC.

Since the maximum foaming temperature window is only about 4 °C for supercritical CO2 (scCO2) foaming of pristine polypropylene, it is important to raise the melt strength of polypropylene in order to more easily achieve scCO2 foaming. In this work, radiation cross-linked isotactic polypropylene, assisted by the addition of a polyfunctional monomer (triallylisocyanurate, TAIC), was employed in the scCO2 foaming process in order to understand the benefits of radiation cross-linking. Due to significantly enhanced melt strength and the decreased degree of crystallinity caused by cross-linking, the scCO2 foaming behavior of polypropylene was dramatically changed. The cell size distribution, cell diameter, cell density, volume expansion ratio, and foaming rate of radiation-cross-linked polypropylene under different foaming conditions were analyzed and compared. It was found that radiation cross-linking favors the foamability and formation of well-defined cell structures. The optimal absorbed dose with the addition of 2 wt % TAIC was 30 kGy. Additionally, the foaming temperature window was expanded to about 8 °C, making the handling of scCO2 foaming of isotactic polypropylene much easier.

Surface barrier discharges for Escherichia coli biofilm inactivation: Modes of action and the importance of UV radiation.

Cold plasma generated in air at atmospheric pressure is an extremely effective antimicrobial agent, with proven efficacy against clinically relevant bacterial biofilms. The specific mode of bacterial inactivation is highly dependent upon the configuration of the plasma source used. In this study, the mode of microbial inactivation of a surface barrier discharge was investigated against Escherichia coli biofilms grown on polypropylene coupons. Different modes of exposure were considered and it was demonstrated that the long-lived reactive species created by the plasma are not solely responsible for the observed microbial inactivation. It was observed that a synergistic interaction occurs between the plasma generated long-lived reactive species and ultraviolet (UV) photons, acting to increase the antimicrobial efficacy of the approach by an order of magnitude. It is suggested that plasma generated UV is an important component for microbial inactivation when using a surface barrier discharge; however, it is not through the conventional pathway of direct DNA damage, rather through the synergistic interaction between liquid in the biofilm matrix and long-lived chemical species created by the discharge.

Photoactivation of alkyl C-H and silanization: a simple and general route to prepare high-density primary amines on inert polymer surfaces for protein immobilization.

Surface modification through implanting functional groups has been demonstrated to be extremely important to biomedical applications. The usage of organic polymer phase is often required to achieve satisfactory results. However, organic surfaces usually have poor chemical reactivity toward other reactants and target biomolecules because these surfaces usually only consist of simple alkyl (C-H) and/or alkyl ether (ROR') structures. For the first time, we here report the potential to perform silanization techniques on alkyl polymer surface, which provide a simple, fast, inexpensive, and general method to decorate versatile functional groups at the molecular level. As an example, high-density primary amines could be obtained on a model polymer, polypropylene substrate, through the reaction between amine-capped silane, 3-aminopropyltriethoxysilane (APTES) and hydroxylated polypropylene surface. A model protein, immunoglobulin (IgG), could be effectively immobilized on the surface after transforming amines to aldehydes by the aldehyde-amine condensation reaction between glutaraldehyde (GA) and amines. The routes we report here could directly make use of the benefits from well-developed silane chemistry, and hereby are capable of grafting any functionalities on inert alkyl surfaces via changing the terminal groups in silanes, which should instantly stimulate the development of many realms such as microarrays, immunoassays, biosensors, filtrations, and microseparation.

Effect of macromer molecular weight on in vitro ophthalmic drug release from photo-crosslinked matrices.

The objective of this study was to investigate the effect of poly(propylene fumarate) (PPF) molecular weight on the release kinetics of two ophthalmic model drugs, acetazolamide (AZ) and timolol maleate (TM), from matrices prepared by photo-induced copolymerization of PPF with N-vinyl pyrrolidone (NVP). PPF macromers of different number average molecular weight (M(n)) and polydispersity index (PI) were used in the experiments. Photo-crosslinked matrices were loaded with 5wt.% AZ or TM. The amounts of released drug and NVP were determined using high-performance liquid chromatography (HPLC). The release kinetics of both drugs was influenced by the molecular weight of the constituent PPF macromer. An increased M(n) led to an increased burst release and an accelerated drug release. Dependent on the PPF M(n), the initial AZ loading was released within periods ranging from 35 days (M(n) = 3670, PI = 1.9) to 220 days (M(n) = 2050, PI=1.5). TM-loaded matrices revealed similar release kinetics dependent on the PPF M(n). The amount of released NVP from photo-crosslinked matrices during the course of a release experiment was independent of the PPF M(n) for both drugs. Matrix swelling and erosion were determined gravimetrically. The network structures of non-loaded matrices were further characterized by determining their crosslinking densities and the relative double bond conversions of fumaric acid (FAA) and NVP. Independent of PPF M(n), PPF and NVP similarly participated in the formation of the PPF/polyNVP copolymer network. The observed differences in drug release might therefore be explained by differences in the microstructural organization of the copolymer networks. Overall, the results demonstrate that drug release kinetics from photo-crosslinked PPF/polyNVP matrices is strongly dependent on the M(n) of the PPF macromer.

Biodegradable and photocrosslinkable polyphosphoester hydrogel.

A new biodegradable, photocrosslinkable and multifunctional macromer, poly(6-aminohexyl propylene phosphate) (PPE-HA)-ACRL, was synthesized by conjugation of acrylate groups to the side chains of PPE-HA. By controlling the synthetic conditions, different weight fractions of acrylate in the macromers were achieved as confirmed by 1H NMR. The hydrogels obtained from PPE-HA-ACRL through photocrosslinking were dominantly elastic. With increasing acrylate contents in the macromers, the hydrogels exhibited a lower swelling ratio and higher mechanical strength. The hydrogels with different crosslinking densities lost between 4.3% and 37.4% of their mass in 84 days when incubated in phosphate-buffered saline at 37 degrees C. No significant cytotoxicity of the macromers against bone marrow-derived mesenchymal stem cells from goat (GMSC) was observed at a concentration up to 10mg/ml. Finally, GMSCs encapsulated in the photopolymerized gel maintained their viability when cultured in osteogenic medium for three weeks. Clear mineralization in the hydrogel scaffold was revealed by Von Kossa staining. This study suggests the potential of these biodegradable and photocrosslinkable as injectable tissue engineering scaffolds.

Modification of polypropylene fibers by plasma and preparation of hybrid luminescent and rodlike CdS nanocrystals/polypropylene fibers.

A simple method for the preparation of hybrid luminescence and rodlike CdS nanoclusters/poly (propylene-grafted-(2-methylacrylic acid 3-(bis-carboxymethyl amino-2-hydroxy-propyl ester) (GMA-IDA fibers, by plasma induced method following chemical deposition method, is presented in this study. GMA-IDA chelating groups which are grafted onto the poly(propylene) fibers are the coordination sites for chelating Cd+2, on which nano-sized CdS nanocrystals grew. TEM observations demonstrate that the mean diameter of CdS nanocrystals inside the poly(PP-graft-GMA-IDA) fibers alters from 2 nm to 8 nm at various concentrations of S2- solution. Additionally, SEM presents that the CdS nanocrystals on the surface have rod-like structure. The UV-vis absorption spectra provide the information of the absorption edges, band-gaps, and average diameter of CdS nanocrystals, the results of which are coincidence with the TEM observations. Furthermore, the photoluminescence (PL) shows the maximum peaks are 495 nm, 571 nm, 657 nm, and 675 nm corresponding to the mean particle sizes 2.6 nm, 3.5 nm, 4.8 nm, and 7.7 nm, respectively, at an excitation wavelength of 366 nm.

Evaluation of the migration of chemicals from baby bottles under standardised and duration testing conditions.

After the prohibition of bisphenol-A-containing polycarbonate baby bottles in the European Union (EU), alternative materials, such as polypropylene, polyethersulphone, Tritan™ copolyester, etc., have appeared on the market. Based on an initial screening and in vitro toxicity assessment, the most toxic migrating compounds were selected to be monitored and quantified using validated GC- and LC-QqQ-MS methods. The effect of several 'real-life-use conditions', such as microwave, sterilisation and dishwasher, on the migration of different contaminants was evaluated by means of duration tests. These results were compared with a reference treatment (filling five times with pre-heated simulant at 40°C) and with the legal EU 'repetitive-use conditions' (three migrations, 2 h at 70°C). Analysis of the third migration step of the EU repetitive-use conditions (which has to comply with the EU legislative migration limits) showed that several non-authorised compounds were observed in some baby bottles exceeding 10 µg kg(-1). However, all authorised compounds were detected well below their respective specific migration limits (SMLs). The reference experiment confirmed the migration of some of the compounds previously detected in the EU repetitive-use experiment, though at lower concentrations. Analysis of extracts from the microwave and dishwasher experiments showed a reduction in the migration during the duration tests. In general, the concentrations found were low and comparable with the reference experiment. Similar observations were made for the two sterilisation types: steam and cooking sterilisation. However, steam sterilisation seems to be more recommended for daily use of baby bottles, since it resulted in a lower release of substances afterwards. Repeated use of baby bottles under 'real-life' conditions showed no increase in the migration of investigated compounds and, after some time, the migration of these compounds even became negligible.

Photo-immobilization of a phospholipid polymer for surface modification.

A photo-reactive polymer having a phospholipid polar group was prepared, and the polymer was photo-immobilized on polymeric surfaces, where its interactions with biocomponents were investigated. By using a photo-immobilization method, the polymer was used for surface modification of polyethylene and polypropylene, polymers whose surfaces were not treated in our previous development of the phosphorylcholine-derived polymer. The photo-reactive polymer was synthesized by a coupling reaction involving copolymer consisting of 2-methacryloyloxyethyl phosphorylcholine and methacrylic acid with 4-azidoaniline. When the polymer was unpattern immobilized on the surface, X-ray photo-electron spectroscopic analysis and static contact angle measurements were performed. It was shown that the surface was covered with phospholipid polar groups. Micropattern immobilization was carried out using a micropatterned photo-mask. Measurements using atomic force microscopy showed that the swelled micropatterned polymer was five times as thick as the dried one. Protein adsorption and platelet adhesion were reduced on the polymer-immobilized regions. Mammalian cells did not adhere, and formed aggregates on the immobilized regions. In conclusion, the photo-reactive phospholipid polymer was covalently immobilized on the conventional polymer surfaces and it tended to reduce interactions with proteins and cells.

Gamma sterilization of UHMWPE articular implants: an analysis of the oxidation problem. Ultra High Molecular Weight Poly Ethylene.

Gamma irradiation of Ultrahigh Molecular Weight Polyethylene (UHMWPE) leads to long-lived free radicals which react with oxygen. Diffusion of oxygen, occurring over months or years, controlled by the permeability characteristics of the polymer, results in progressive oxidation, breaking of polymer chains, alteration of the crystalline portion of the polymer, and deterioration of the mechanical properties of the polymer. This paper reviews the observations in the literature on this issue and then presents a conceptual model concerning the interplay of radical diffusion, oxygen diffusion, non-uniform permeability, and free-radically driven chain reactions in order to explain these observations. The suggested model is based on literature that is available on the oxidation of linear polyethylenes during and after irradiation. The model directs the attention of researchers in the field of orthopaedic implants to the complexity of the process and the variety of issues and parameters to be considered while studying the long-term effects of radiation sterilization on UHMWPE.

Creep rupture of polypropylene sutures as a function of diameter, radiation dose and temperature.

The failure of polypropylene (PP) sutures was studied via creep rupture tests. Linear relationships were generated from plots of log time to break (tB) versus stress (sigma). At a constant sigma the results showed that tB was inversely proportional to the suture diameter (7-0, 6-0, 5-0 and 4-0) and to the radiation dose (0, 15, 20, 25 and 50 Mrad). Moreover, for the 6-0 suture size at a 15 Mrad dose, tB decreased with increasing temperature (26, 37, 44, 50 and 60 degrees C). For this creep rupture process the activation energy equalled 91.2 kJ/mol (21.8 kcal/mol). A mechanism for failure was presented which assumes that these sutures are bundles of oriented, semicrystalline microfibrils.

Ageing of radiation-sterilized polypropylene: changes in semicrystallinity.

Studies on radiation sterilization of isotactic polypropylene intended for biomedical applications were carried out for uncovered and covered samples. The effect of ageing on these samples was studied by determining the changes in relative crystallinity. The semicrystalline nature of the polymer is responsible for the changes in crystallinity. The transitions between short- and long-range order and short- and long-duration stiffness in both covered and uncovered samples, reflected in changes in relative crystallinity, were highly affected by the formation of branches in the backbone of the polymer. The high degree of branching in covered samples resulted in greater long-duration stiffness in the transition between short- and long-duration stiffness. The high degree of branching in covered samples was attributed to the high diffusion of energized oxygen into the polymer matrix compared with uncovered samples. The changes in relative crystallinity were rapid in uncovered samples (70% max; 34% min) but rather slow in covered samples (87% max; 43% min).

Detection of peroxy species in ultra-high-molecular-weight polyethylene by Raman spectroscopy.

Samples of gamma-sterilized ultra-high-molecular-weight polyethylene (UHMWPE) have been examined using infrared and Raman spectroscopies. Infrared spectra of microtomed sections of a thick segment of material exhibited carbonyl bands whose intensity was consistent with published data. Raman spectroscopy has been used for the first time to detect oxidized precursors to the commonly found carbonyl species. Gamma-sterilized plates examined as soon as possible after sterilization exhibited bands consistent with epoxide, alcohol and three different peroxy-containing species. The detection of these species in irradiated UHMWPE is reported for the first time and demonstrates that oxidation of this material proceeds via a gamma-induced free radical mechanism, as has been widely assumed.

Influence of gamma-irradiation sterilization and temperature on the fracture toughness of ultra-high-molecular-weight polyethylene.

Surface damage of the tibial plateau components of knee prostheses made from medical grade ultra-high-molecular-weight polyethylene (UHMW-PE) has been attributed to delamination wear caused by a fatigue fracture mechanism. It has been proposed that factors such as component design and method of sterilization contribute to such failure mechanisms. Understanding the fracture behaviour of UHMW-PE is therefore critical in optimizing the in vivo life-span of total joint components. The elastic-plastic fracture toughness parameter J was consequently determined for a commercial UHMW-PE at ambient and body temperatures, before and after gamma-irradiation sterilization in air at a minimum dose of 29 kGy. Both ductile stability theory and experimental data suggest that cracks propagate in a stable manner, although stability is affected by the sterilization process. Sterilization with gamma-irradiation results in a loss in fracture toughness JIc of 50% and a decrease in tearing modulus (Tm) of 30%. This dramatic reduction could result in a 50% decrease in the residual strength of the components, maximum permissible crack size under service loading and service life (assuming flaws such as fusion defects exist). The time required for a crack to grow from its original size to the maximum permissible size could be decreased by 30%, resulting in earlier failure. In terms of the design of joint replacement components the critical factor to envisage is the design stress level, which should be halved to account for the irradiation process. A scanning electron microscope study reveals that the material fails in layers parallel to the fracture surface.

Cell attachment to laser-induced AAm- and HEMA-grafted ethylene-propylene rubber as biomaterial: in vivo study.

With the purpose of improved tissue compatibility, ethylene-propylene rubber (EPR)-based vulcanizates have been surface grafted with acrylamide (AAm) and 2-hydroxyethyl methacrylate (HEMA) using CO2-pulsed laser as excitation source. Grafted surfaces were characterized by performing scanning electron microscopy combined with energy dispersive X-ray analysis and attenuated total reflectance infrared spectroscopy to study the surface morphology and grafting. Surface hydrophilicity (measured by water drop contact angle) increased for the grafted samples. Fractal type of morphology is formed by the grafted poly(AAm) and poly(HEMA) chains on the surface of EPR, which provides both hydrophilic and hydrophobic sites. In vivo tissue compatibility was assessed by implanting test samples in the deep intramuscular and peritoneal layers of rabbits. After 8 weeks of implantation, comparative results indicate that the adhesion of macrophages to EPR samples modified with AAm and HEMA, with no respiratory burst and cellular damage, is significantly lower than their adhesion on unmodified surfaces which show an activated state of the attached macrophages. Also, no acute or chronic inflammatory reaction was observed at the site of implantation and a thinner fibrous tissue capsule formed around the modified samples, whereas foreign body giant cells adhered to unmodified EPR.

FT-IR microspectroscopic study of shot formation in melt-blown webs.

We used Fourier transform infrared (FT-IR) microspectroscopy to investigate the chemical nature of fibers and defects called "shot" in melt-blown webs. Spectral differences were observed and evaluated in light of known thermal and oxidative degradation reactions for conditions comparable to those we used for melt blowing. Three different isotactic polypropylene polymers were evaluated in terms of the amount of shot produced and the amount of oxidative degradation exhibited by fibers and shot particles from each polymer. Little oxidative degradation was observed in fibers and the amount of degradation in fibers varied little for the three polymers we evaluated. Substantially more degradation was observed in shot particles, and the amount of degradation varied among the three polymers. Compared to polymer bound for fibers, we concluded that high temperature and mechanical shear in the extruder may introduce more chain scission in polymer bound for shot particles. Autoxidation reactions may occur after melt exits the die, and our data indicated that more oxidative degradation occurred in polymer that became shot particles than polymer that became fibers. The most favorable site for oxidation seemed to be tertiary rather than methylene hydrogen. Overall, the thermal history of polymer that becomes shot particles may be significantly different than the thermal history of polymer that becomes fibers, and this difference may have influenced shot formation.

Radiation effects on polypropylene for sterilization.

In order to improve the resistance of gamma-radiation sterilization of polypropylene (PP), the formulations of the additives such as antioxidants, crosslinking agent, and trans-stilbene oxide (StO) have been carried out. The irradiated PP and ethylene-propylene copolymer samples with control and additives were characterized by mechanical tester, colorimetry, and Fourier transform infrared spectroscopy with total attenuated reflectance mode (FTIR-ATR). Crosslinking agent and StO formulated PP showed remarkable radiation resistance and minimum discoloration. Also, radiation resistance of ethylene-propylene copolymers with 3% of ethylene contents was better than that of PP homopolymers in the case of no additives. The proposed mechanisms of radiation stabilization with additives are also discussed.

Analysis of volatile radiolysis products in gamma-irradiated LDPE and polypropylene films by thermal desorption-gas chromatography-mass spectrometry.

Low-molecular-weight ('volatile') radiolysis products of low-density polyethylene (LDPE) and polypropylene (PP) films were investigated by thermal desorption-(TDS)-GC-MS after absorbed doses of up to 25 kGy. The films produce fingerprint chromatograms with highly characteristic patterns of groups of radiation-induced peaks; these are mainly hydrocarbons, aldehydes, ketones, and carboxylic acids with concentrations (after 25 kGy) ca one order of magnitude below that of the residual hydrocarbons (oligomers). PP additionally produces very substantial amounts of three degradation products of phenol-type antioxidants. The low molecular-weight (MW) radiolysis products are retained for considerable times in LDPE films and they are retained in PP films much longer than had been expected. Besides product identification, the following topics are addressed: Effects of the absorbed dose and the desorption temperature; comparison of several commercial (proprietary) films; high-temperature thermal desorption; the question whether TDS analyzes radiation-induced artifacts rather than genuine products; the possible existence of cyclic radiolysis products; the possibility of identifying an LDPE film as irradiated after a dose of only 1 kGy; and atypical trace fragments of antioxidants. Finally, the geometry and efficiency of the thermal desorption system is briefly discussed, and the implications of our findings for irradiation detection and for the safety of irradiated materials are considered.

Radiation-induced physical changes in UHMWPE implant components.

Post-irradiation aging of ultra-high molecular weight polyethylene (UHMWPE) is not well understood. Retrieval studies and in vitro aged specimens have shown oxidative changes along with increases in crystallinity. Critical analysis and review of the polymer science and polymer physics literature shows that while oxidation may be important during the first year post-irradiation, subsequent aging occurs because of initial gamma radiation-induced chain scission leading to eventual isothermal crystallization of polymer chains in the amorphous regions of the UHMWPE bulk. Mechanical properties of aged UHMWPE are not as yet clear and, until such data become available, gamma irradiation sterilization must be used with caution.

[Study of polyolefine plastics for the manufacture of medical and bacteriological equipment to be sterilized in electron accelerators]. / Badania tworzyw poliolefinowych do wyrobu sprzetu medycznego i mikrobiologicznego wyjalawianego w akceleratorach elektronów

The resistance of several kinds of polyethylenes and polyproylenes to sterilizing doses of accelerated electron radiation was studied. Polypropylene Polypro J-600 articles were shown to be unfit for sterilization using isotope sources with low-power dosages, and the use of electron accelerator was found to enable their radiation sterilization.