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Eingeladener Vortrag
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Materials that confer antimicrobial activity, be that by innate property, leaching of biocides or design features (e.g., non-adhesive materials) continue to gain popularity to combat the increasing and varied threats from microorganisms, e.g., replacing inert surfaces in hospitals with copper. To understand how efficacious these materials are at controlling microorganisms, data is usually collected via a standardised test method. However, standardised test methods vary, and often the characteristics and methodological choices can make it difficult to infer that any perceived antimicrobial activity demonstrated in the laboratory can be confidently assumed to an end-use setting. This review provides a critical analysis of standardised methodology used in academia and industry, and demonstrates how many key methodological choices (e.g., temperature, humidity/moisture, airflow, surface topography) may impact efficacy assessment, highlighting the need to carefully consider intended antimicrobial end-use of any product.
New antibacterial agents are urgently required to fight the emergence of antibiotic-resistant bacteria. We recently synthesized the first thioimidazolium ionene, which has antibacterial properties and can degrade in various media. This dual functionality is crucial in order to limit the environmental impact of these biocides. We have found that our polymer is stronger than benzalkonium chloride (BAC) against Pseudomonas aeruginosa and also readily degrades in the presence of base, while remaining stable in acidic environments. These results highlight a new emerging class of antibacterial degradable polymers.
The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.
Improved Durability of Wood Treated with Nano Metal Fluorides against Brown-Rot and White-Rot Fungi
(2022)
Low-water soluble metal fluorides such as magnesium fluoride (MgF2) and calcium Fluoride (CaF2) were evaluated for decay protection of wood. Initially, the biocidal efficacy of nano metal fluorides (NMFs) against wood destroying fungi was assessed with an in-vitro agar test. The results from the test showed that agar medium containing MgF2 and CaF2 was more efficient in preventing fungal decay than stand-alone MgF2 or CaF2. These metal fluorides, in their nanoscopic form synthesized using fluorolytic sol-gel synthesis, were introduced into the sapwood of Scots pine and beech wood and then subjected to accelerated ageing by leaching (EN 84). MAS 19F NMR and X-ray micro CT images showed that metal fluorides were present in treated wood, unleached and leached. Decay resistance of Scots pine and beech wood treated with NMFs was tested against Wood destroying fungi Rhodonia placenta and Trametes versicolor in accordance with EN 113. Results revealed that mass losses were reduced to below 3% in wood treated with the combination of MgF2 and CaF2.
It is concluded that NMFs provide full protection to wood even after it has been leached and can be used as wood preservatives in outdoor environments.
Test methods for efficacy assessment of antimicrobial coatings are not modelled on a hospital environment, and instead use high humidity (>90%) high temperature (37 ◦C), and no airflow. Therefore, an inoculum will not dry, resulting in an antimicrobial surface exhibiting prolonged antimicrobial activity, as moisture is critical to activity. Liquids will dry quicker in a hospital ward, resulting in a reduced antimicrobial efficacy compared to the existing test, rendering the test results artificially favourable to the antimicrobial claim of the product. This study aimed to assess how hospital room environmental conditions can affect the drying time of an inoculum, and to use this data to inform test parameters for antimicrobial efficacy testing based on the hospital ward. The drying time of different droplet sizes, in a range of environmental conditions likely found in a hospital ward, were recorded (n = 630), and used to create a model to inform users of the experimental conditions required to provide a drying time similar to what can be expected in the hospital
ward. Drying time data demonstrated significant (p < 0.05) variance when humidity, temperature, and airflow were assessed. A mathematical model was created to select environmental conditions for in vitro antimicrobial efficacy testing. Drying time in different environmental conditions demonstrates that experimental set-ups affect the amount of time an inoculum stays wet, which in turn may affect the efficacy of an antimicrobial surface. This should be an important consideration for hospitals and other potential users, whilst future tests predict efficacy in the intended end-use environment.
Im Rahmen des Forschungsvorhabens wurde die biologische Prüfmethode der Checkliste zur stoffli-chen Bewertung im Rahmen des Aufnahmeverfahrens für weitere Topfkonservierungsmittel in den Anhang 1 zur Vergabegrundlage RAL-UZ102 „Emissionsarme Innenwandfarben“ überarbeitet. Der Test für den Einsatz von Konservierungsmitteln in seiner jetzigen Fassung besteht seit nahezu 20 Jah-ren und erfolgt ausschließlich an weißer Dispersionsfarbe für den Innenraum. Die hierbei ermittelten Höchstmengen für den Einsatz von Topfkonservierern werden z.Zt. auch auf andere Innenraumbau-produkte übertragen. Ziel war es zu klären, ob die Anforderungen an die Topfkonservierung bei Far-ben tatsächlich für andere Innenraumbauprodukte übernommen werden können. Die im Vorhaben durchgeführten Versuche deuten darauf hin, dass dies nicht ohne weiteres möglich ist. Nach Rückspra-che mit Vertretern aus der Industrie wurde das Keimspektrum für die Prüfung zudem um Hefe- und Schimmelpilze erweitert. Des Weiteren wurde eine künstliche Alterung eingeführt und überprüft, ob dies einen Einfluss auf den Gehalt an Isothiazolinonen hat. Die Konzentration von Isothialzolinonen wurde mittels Ultra-Hochleistungsflüssigkeitschromatographie kontrolliert und hinsichtlich einer Kor-relation mit dem Wachstum von Mikroorganismen ausgewertet. Da die in den Innenraumbauproduk-ten zugesetzten Isothiazolinone als Kontaktallergene bekannt sind, ist es ein Ziel des „Blauen Engel“-Umweltzeichens, die geringste erforderliche Menge an Konservierungsmittel in den Produkten zu ver-wenden, ohne die positive Auswirkung der Topfkonservierung zu gefährden. Daher sind die Optimie-rung der Leistungsstärke von Konservierungsmitteln und die Kontrolle der Hygiene im Herstellungs-prozess von zunehmender Bedeutung. Um Einblicke in den Herstellungsprozess von Farben zu gewin-nen, wurden im Rahmen des Vorhabens vier Farbwerke besichtigt, in denen weiße Innenraumfarben produziert werden, die mit dem Umweltzeichen „Blauer Engel“ ausgezeichnet sind. Gemeinsam mit den Fachleuten vor Ort wurde diskutiert, welche Maßnahmen zur Verbesserung der Werkshygiene er-griffen werden können, um den Einsatz von Topfkonservierern möglichst gering zu halten. Des Weite-ren wurde in dem Forschungsvorhaben untersucht, ob eine schnellere Bestimmung der Keimzahl in den Rohstoffen mittels quantitativer Polymerasekettenreaktion bereits im Farbwerk realisierbar ist.
Verschiedene Labor- und Freilandstudien zeigen, dass Antrodia vaillantii ein Braunfäuleerreger ist, der chemisch geschütztes Holz (gemäss den Anforderungen der Gefährdungsklasse 4) stark abbauen kann. Hierbei spielt die erhöhte Oxalsäureproduktion des Pilzes und die daraus resultierende Kupferoxalatausfällung im Holz die entscheidende Rolle. Das Kupfer wird auf diese Weise für den Pilz weitgehend unschädlich gemacht und andere Holzschutzmittelbestandteile wie z.B. Chrom- und Arsenverbindungen verlieren ihre Fixierung im Holz und werden wasserlöslich. Dies führt zu Frühausfällen von chemisch geschütztem Holz im Erdkontakt innerhalb weniger Jahre. Laboruntersuchungen haben gezeigt, dass der Holzabbau durch A. vaillantii bei hoher Wasserverfügbarkeit außerhalb des Holzes angeregt werden kann. Das hohe Feuchtigkeitsbedürfnis des Pilzes ist möglicherweise die Ursache für den Befall von Holz in bis zu 1,2 m Bodentiefe. Neben der hohen Bodenfeuchte gibt es Anhaltspunkte für weitere Parameter, die zur positiven Selektion von A. vaillantii und damit seiner stellenweise starken Ausbreitung führen. Diese sind hohe Toleranz gegenüber bereits vorhandenen niedrigen pH-Werten im Boden, das aktive Einstellen niedriger pH-Werte im Boden durch Säureabgabe und die Festlegung von Kuper als Kupferoxalat.
Most research in the last few decades has focused on the development of new strategies to control biological attack and the means to quantify this. Comparatively little work has been done to examine the effect that treated timber might have on its surrounding environment. This presentation will describe a methodology that attempts to detect any changes which might occur in the soil microflora following the introduction of timber treated with a number of chemical agents containing organic active ingredients (a.i.). It was also the purpose to isolate organisms that can break down organic a.i.. A technique was developed to determine whether the presence and nature of a timber preservative influenced the size and composition of a microbial population that colonised timber when buried in soil. Samples of treated timber were incubated in a solution eluted from soil that contained a diverse, viable microbial population. After incubation, the size and composition of the microflora both in the eluate and adhering to the timber was examined.
The paper descibes a novel method to detoxify pine wood (Pinus silvestris L.) treated with CCB-, CCF- CC-, and Cu-HDO-type salt preservatives. In the process of biological detoxification organic acids produced by strains of Antrodia vaillantii and other brown rot fungi are used for the dissolution of the previously fixed inorganic compounds. These findings are the basis for applying an acid pulping process (FORMACELL) developed by Nimz and Schone (1992) at the BFH, Hamburg, to detoxify salt impregnated wood waste with a mixture of acetic and formic acid. First results achieved with wood chips from treated poles after approximately 20 years of service life show that the obtained pulp contains less than 100 ppm of Cr and Cu. The pulp properties were neither influenced by the Cr and Cu ions nor by the age of the poles. The extracted quantities of Cr and Cu remain with the lignin whereas the acids are evaporated and recycled in the pulping process.
The fungus cellar test is a common means to get reliable data on the long term performance of treated wood in soil contact. A constantly high humidity and a suitable of water holding capacity for a range of micro-organisms provide high decay rates in untreated wood and produce intensive microbial pressures on wood treated with biocides. Presently a range of biocides are under test in the BAM fungus cellar and the results will be presented for the following types of biocides: Tebuconazole in combination with copper and boron (5 years fungus cellar), quats with copper and boron (5 years fungus cellar) and Cu-organic compound combined with copper and boron (3 years fungus cellar). Figures will be shown on the development of the Modulus of Elasticity (MOE) over the years and on an assessment of the stakes according to EN 252.
Environmental Risk Assessment of Treated Timber in Service - the Environment Focus Group Approach
(2000)
In the context of the Biocidal Products Directive (98/8/EC), and of the OECD work on wood preservatives, the Environment Focus Group (EFG), comprising 8 institutes and the European Wood Preservative Manufacturers Group, has been working on the environmental risk assessment of treated timber in service. A literature review of emissions from treated timber has revealed that very little existing data is usable for environmental risk assessment; the most relevant data are kinetic curves of emissions over time, which show clearly the non-linear emissions behaviour of treated wood over time. The EFG has suggested real exposure conditions for treated timber in the environment, and listed typical exposure scenarios. Five representative scenarios are characterised in detail, for use in the calculation of Predicted Environmental Concentrations (PECs). The existing methods to determine emissions from treated wood have been reviewed. Most existing experimental models cannot be used to predict environmental emissions. Monitoring of commodities in service has its specific constraints. Chemical analysis and ecotoxicity testing have also been reviewed and their relationship has been discussed. Principles for the design of experimental models, for the determination of emission fluxes from treated wood to the environment, have been established.
Die komplexe Wirkung von Schimmelpilz und Klima auf Polymeroberflächen und ihre Simulation im Labor
(2004)
Fungizide in Beschichtungen
(2007)