This study aims to investigate the limitations and applicability of different ion exchanged zeolites as antimicrobial additive in thermoplastic polyether type polyurethanes. These composites were designed to improve the health quality of hospitalized patients by expressing both biocompatibility and relevant antimicrobial activity. The zeolites were exchanged with silver, copper and zinc ions and single, binary and ternary ion-exchanged zeolite-polyurethane composites were prepared. The antimicrobial activity and the resistance of the composites against the human environment play vital role in the applicability of the materials as a medical device therefore these properties were investigated. The antimicrobial test were performed on Methicillin-resistant Staphylococcus aureus, Pseudomonas aeruginosa and Candida tropicalis. The tests showed that the efficiency of the silver ions is superior to the other single ionic systems. Besides, the binary and ternary ion-exchanged samples had similar antimicrobial efficiency regardless the type of the ions in the zeolite. The biocompatibility tests were carried out in-vitro in artificial body fluids for a period of 12 weeks. As a result of the invitro test, degradation of the composites were observed and the structural changes of the materials were detected and described by Scanning Electron Microscopy, Contact Angle measurements and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy
Polymers used for biomedical purposes in medical devices are usually requested to be inert to degradation. This article describes that slow irreversible changes were observed in silicone surfaces exposed to in vivo biofilms even if silicone, in general, is supposed to have excellent long-term properties. Tracheostomy tubes made of silicone rubber were exposed to in vivo biofilm environments in clinical tests for periods of 1, 3, and 6 months. The chemical degradation was monitored by MALDI-TOF MS, ATR-FTIR, and FE-SEM. In addition, the physical changes were monitored by contact angle and hardness measurements. Cyclic polydimethylsiloxane (PDMS) was detected on the surfaces of new (unaged) silicones. On the surfaces of the in vivo samples new compounds, presumably linear methyl-hydroxyl-terminated PDMS, were detected in addition to cyclic PDMS. These compounds may be formed as a result of the hydrolysis of linear dimethyl terminated PDMS, which is also present in the silicone rubber. ATR-FTIR spectroscopy confirmed that hydrolysis had indeed occurred during the in vivo exposure, since SiAOH groups were detected. Furthermore, significant changes in the topography were detected by FE-SEM, indicating the initiation of degradation. No significant changes in the contact angle of the in vivo used samples were observed, but this information may be shielded by the fact that biofilm may remain on the surface, despite the thorough cleaning before the analysis. It is also possible that the surface hydrophobicity was recovered by the diffusion of linear low-molecular-weight compounds from the bulk.
The preparation and modelling of single, binary and ternary ion exchanged zeolites that express antimicrobial efficiency is discussed. As experimental material A type zeolite was used and different variations of Ag, Cu and Zn ions were incorporated into the crystal structure. Antimicrobial efficiency is based on the ion concentration and ion release of the zeolite, therefore the maximum cation-exchange capacities (CEC) were determined for each of the single ions. After the determination of CEC the preparation of binary and ternary ion-exchanged zeolite samples were prepared by the mixture of silver, copper and zinc nitrate solutions and the composition of the samples was determined by atomic absorption spectroscopy (AAS). To verify the bioactive effect, the minimum inhibitory concentration (MIC) of single, binary and ternary ion-exchanged zeolite A was determined for bacteria strains.
In this study the degradation and ion/zeolite release processes of in vitro aged zeolite loaded polyurethane composites were evaluated. Two in vitro artificial aging solutions were used; artificial lysosomal fluid (ALF) and Gamble ́s solution and the total exposure time was 12 weeks. Periodically, SEM micrographs were taken of the surface of polyester type polyurethane-zeolite composites. After exposure to ALF solution the samples showed round holes and a rougher surface in general over time. Micrographs of the samples immersed in Gamble’s solution exhibited different signs of degradation with damage features on the surfaces, understood as black holes and a rougher surface pattern. In addition varying amount of salt was also observed on the surfaces that might influence the ion/zeolite release. Furthermore, the zeolite filler caused remarkable changes in mechanical properties after the aging process, which could not be discerned.
Based on the previously published sodium and Ag, Cu, Zn ion-exchange and re-excange experiments we took an attempt to modeling its structure. We also took in account the ion release experimental results and the rigorous survey of the literature data when we positioned the ions in zeolite crystal structure. Therefore the current study aimed to modeling the ion distribution of single, binary and ternary ion-exchanged zeolite systems used for antimicrobial purposes, where the variation of silver, copper and zinc is incorporated into the zeolite structure. The tool of modelling was “CrystalMaker6” developed by CrystalMaker Software Ltd.
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