Contact-active surfaces have been created by means of the layer-by-layer (LbL) modification technique, which is based on previous observations that cellulose fibers treated with polyelectrolyte multilayers with polyvinylamine (PVAm) are perfectly protected against bacteria. Several different cationic polyelectrolytes were applied, including PVAm, two different poly(diallyl dimethyl ammonium chloride) polymers and two different poly(allylamine hydrochloride) polymers. The polyelectrolytes were self-organized in one or three layers on cellulosic fibers in combination with polyacrylic acid by the LbL method, and their antibacterial activities were evaluated. The modified cellulose fibers showed remarkable bacterial removal activities and inhibited bacterial growth. It was shown that the interaction between bacteria and modified fibers is not merely a charge interaction because a certain degree of bacterial cell deformation was observed on the modified fiber surfaces. Charge properties of the modified fibers were determined based on polyelectrolyte titration and zeta potential measurements, and a correlation between high charge density and antibacterial efficiency was observed for the PVAm and PDADMAC samples. It was demonstrated that it is possible to achieve antibacterial effects by the surface modification of cellulosic fibers via the LbL technique with different cationic polyelectrolytes.

A contact-active antibacterial approach based on the physical adsorption of a cationic polyelectrolyte onto the surface of a cellulose material is today regarded as an environment-friendly way of creating antibacterial surfaces and materials. In this approach, the electrostatic charge of the treated surfaces is considered to be an important factor for the level of bacteria adsorption and deactivation/killing of the bacteria. In order to clarify the influence of surface charge density of the cellulose on bacteria adsorption as well as on their viability, bacteria were adsorbed onto cellulose model surfaces, which were modified by physically adsorbed cationic polyelectrolytes to create surfaces with different positive charge densities. The surface charge was altered by the layer-by-layer (LbL) assembly of cationic polyvinylamine (PVAm)/anionic cellulose nanofibril/PVAm onto the initially differently charged cellulose model surfaces. After exposing the LbL-treated surfaces to Escherichia coli in aqueous media, a positive correlation was found between the adsorption of bacteria as well as the ratio of nonviable/viable bacteria and the surface charge of the LbL-modified cellulose. By careful colloidal probe atomic force microscopy measurements, it was estimated, due to the difference in surface charges, that interaction forces at least 50 nN between the treated surfaces and a bacterium could be achieved for the surfaces with the highest surface charge, and it is suggested that these considerable interaction forces are sufficient to disrupt the bacterial cell wall and hence kill the bacteria.

Bacterial growth is a risk of infection.  Antibiotics did long time seem to be a soln. to the problem, but now the consequences are seen, as antibiotic-resistant strains are evolving.  The substances are also eventually released into the environment, where they often are harmful to living organisms.  Antibacterial surfaces state another option.  However, a majority of the now existing surfaces are of leaching type i.e. assocd. with the same problems as the antibiotics.  The non-leaching are a safer option, but until now the fabrication has been a problem with use of e.g. org. solvents.  We present a sustainable way of forming an antibacterial material onto cellulose by using the polyelectrolyte multilayer technique.  By step-wise adsorbing oppositely charged polyelectrolytes in an aq. soln. contg. fibers, at room-temp., the surface of the fibers are modified.  The result is a non-leaching material with bacteria inhibiting properties.  Also the fabrication is quite safe, as polymers have shown lower toxicity to humans than their monomeric counterparts.  Cellulose is an excellent substrate for antibacterial surfaces.  It is easy to modify with the present technique and is in itself a sustainable materials, with multiple applications.  Combined this gives us in total a new, antibacterial material which also opens up for sustainable cellulose-based products.

The use of cellulose aerogels as antibacterial materials has been investigated by applying a contact-active layer-by-layer modification to the aerogel surface. Studying the adsorption of multilayers of polyvinylamine (PVAm) and polyacrylic acid to aerogels comprising crosslinked cellulose nanofibrils and monitoring the subsequent bacterial adhesion revealed that up to 26 mg PVAm g aerogel⁻¹ was adsorbed without noticeably affecting the aerogel structure. The antibacterial effect was tested by measuring the reduction of viable bacteria in solution when the aerogels were present. The results show that >99.9% of the bacteria adhered to the surface of the aerogels. Microscopy further showed adherence of bacteria to the surfaces of the modified aerogels. These results indicate that it is possible to create materials with three-dimensional cellulose structures that adsorb bacteria with very high efficiency utilizing the high specific surface area of the aerogels in combination with their open structure.

Cellulose nanofibril (CNF) materials have been widely studied in recent years and are suggested for a wide range of applications, e.g., medical and hygiene products. One property not very well studied is the interaction between bacteria and these materials and how this can be controlled. The current work studies how bacteria adhere to different CNF materials modified with polyelectrolyte multilayers. The tested materials were TEMPO-oxidized to have different surface charges, periodate-oxidized to vary the water interaction and hot-pressed to alter the surface structure. Then, multilayers were constructed using polyvinylamine (PVAm) and polyacrylic acid. Both the material surface charge and water interaction affect the amount of polymer adsorbed to the surfaces. Increasing the surface charge decreases the adsorption after the first PVAm layer, possibly due to conformational changes. Periodate-oxidized and crosslinked films have low initial polymer adsorptions; the decreased swelling prevents polymer diffusion into the CNF micropore structure. Microscopic analysis after incubating the samples with bacterial suspensions show that only the materials with the lowest surface charge enable bacteria to adhere to the surface because, when adsorbing up to 5 layers PVAm/PAA, the increased anionic surface charge appears to decrease the net surface charge. Both the amounts of PVAm and PAA influence the net surface charge and thus the bacterial adhesion. The structure generated by the hot-pressing of the films also strongly increases the number of bacteria adhering to the surfaces. These results indicate that the bacterial adhesion to CNF materials can be tailored using polyelectrolyte multilayers on different CNF substrates.

In recent years, antibacterial surfaces have been a subject of increased interest. Especiallyinteresting are non-leaching, contact-active surfaces that physically disrupts the bacterialcell using immobilised cationic polymers. Thus the risks of bacterial resistance and discharge of hazardous biocides is minimised. The assembly of such surfaces is elaborate andusually involves organic solvents. Here, polyelectrolyte multilayers (PEM) are proposed as an effective surface modification method, with an overall goal of producing antibacterial cellulose fibres. The PEM process is based on physical adsorption of oppositely charged polymers in aqueous solutions. Multilayers were formed with the bactericidal polymer polyvinylamine (PVAm) and polyacrylic acid. PVAm compounds with hydrophobic modificationswere applied as well, as they possess increased antibacterial activity in solution.

In this work, the multilayer formation was studied on model surfaces of silicone oxide and glass in order to obtain fundamental knowledge of the polymer system. QCM-D and reflectometry, which detect total mass including bound water and polymer mass only, respectively, were used to analyse the layer formation. Salt-concentrations were varied at 1, 10 or 100 mM NaCl. A stepwise multilayer formation with exponential-like polymer adsorption but with decreasing water content for each layer was seen at all salt concentrations.A higher salt concentration resulted in an increased adsorbed mass. No significant differences in adsorption between the modified and unmodified PVAm could be detected. AFM imaging applied to multilayers having nine layers showed large surface aggregates under high salt conditions for the C6-modified PVAm. Dynamic light scattering showed that the polymer occurred as single molecules in solution; hence it was concluded that theaggregation is surface-associated.

The multilayers were then tested for bacterial growth inhibition. The relative bacterial inhibition was time-dependent, as the surface was saturated with bacteria over time. After two hours, a maximal inhibition of 99 % could be observed for the multilayers. After eight hours, a moderate inhibition of less than 40 % was detected. Using multilayers affected the results positively compared to single layers. After three layers, though, no further reductionwas seen. Viability staining of the surface-adhered bacteria revealed that the adhered bacteria had intact membranes. Therefore, the microbiological properties of the multilayers can at this point be described more as growth-inhibiting by bacterial adhesion effectsthan as biocidal. However, this work has shown the importance of combining surface characterisation and microbial testing to understand the bacteria-surface interaction.

Contact-active antibacterial surfaces with irreversibly attached antibacterial com-pounds are a sustainable alternative to traditional biocides. No chemicals are released into nature and the antibacterial mechanism reduces the risk of the evolution of re-sistant bacteria. However, the preparation of such surfaces is far from sustainable, as organic solvents and harsh reaction conditions commonly are required. An alter-native option is to use polyelectrolyte multilayers (PEM), based on physical ad-sorption, which can be performed in water-based solutions at room temperature. Although contact-active antibacterial PEMs have been reported previously, this is the first study of renewable cellulosic wood fibres.

The build-up of cationic polymer polyvinylamine (PVAm) and anionic polyacrylic acid (PAA) multilayers on model surfaces was studied to optimise adsorption. The amount of adsorbed polyelectrolytes was continuously growing with increasing number of layers, but remained dense and flat as the number of layers increased. The largest adsorption was obtained at a high salt concentration, which shielded the repulsion between the polymers.

Model surfaces were also used to evaluate the influence of the polymer and number of layers on the antibacterial properties. Multilayers on model surfaces showed a low bacteriostatic effect, with up to approximately 40 % inhibition for 3 layers of un-modified PVAm/PAA. In contrast, when the same multilayers were applied on cel-lulosic fibres, bacterial-growth inhibition of > 99.9% was obtained. Hydrophobically modified PVAm did not yield better results, despite being superior in solution. An increase in fibre charge by fibre oxidation led to the largest amount of adsorbed pol-ymer and the best antibacterial properties, an effect that lasted for weeks. Electron microscopy study of bacteria on the fibres showed that the bacteria interacted more on a highly charged surface and that the morphology of the bacterial cell could be affected. The effect was suggested to be due to electrostatic interaction with the pos-itively charged modified fibres. The promising results offer the possibilities of a new generation of antibacterial surfaces based on a renewable resource.

The structure and adsorption behaviors of two types of hydrophobically modified polyvinylamines (PVAm) containing substituents of hexyl and octyl chains were compared to a native polyvinylamine sample. The conformation of dissolved polyvinylamines was studied in aqueous salt solutions using dynamic light scattering. Modified PVAm showed hydrodynamic diameters similar to native PVAm, which indicated that all PVAm polymers were present as single molecules in solution. The adsorption of the polyvinylamines, both native and hydrophobically modified, from aqueous solution onto negatively charged silica surfaces was studied in situ by reflectometry and quartz crystal microgravimetry with dissipation. Polyelectrolyte multilayers; (PEM) with up to nine individual layers were formed together with poly(acrylic acid). Obtained PEM structures were rigid and showed high adsorbed amounts combined with low dissipation, with similar results for both the modified and unmodified PVAm. This suggests that electrostatics dominated the PEM formation. At lower salt concentrations, the hydrophobically modified PVAm produced multilayers with low water contents, indicating that secondary interactions induced by the hydrophobic constituents can also have a significant influence on the properties of the formed layers. The surface structure of PEMs with nine individual layers was imaged in dry state using atomic force microscopy in a dynamic mode. Modified PVAm was found to induce a different structure of the PEM at 100 mM, with larger aggregates compared to those of native PVAm. From these results, it is proposed that modified PVAm can induce aggregation within the PEM, whereas PVAm remains as single molecules in solution.

Contact-active antibacterial surfaces are a novel tool in the antibacterial battle. The preparation of such surfaces usually involves harsh reaction conditions and organic solvents. A more sustainable alternative would involve physical adsorption of water-soluble polyelectrolytes using a renewable substrate. Here, highly charged cationic polyvinylamines (PVAm), with or without hydrophobic modifications, have been adsorbed onto the naturally anionic cellulosic wood-fibres. To increase the amount of PVAm, polyelectrolyte multilayers were prepared using polyacrylic acid as the anionic polyelectrolyte. The modified fibres were characterised for PVAm content, water retention and antibacterial properties. The use of multilayers increased the total polymer content without notably reducing the water swelling. The fibres were shown to have excellent bioactive properties and reduced waterborne Escherichia coli and Bacillus subtilis by more than 99.9 %, which is a generally accepted definition of an antibacterial material. A large reduction in bacterial growth was observed upon addition of nutrients, although minor growth was detected after 24 h. The results further show that one adsorbed polymer layer was sufficient to obtain a contact-active surface, which makes the PVAm multilayer system seemingly unique. No polymer leaching from any of the samples was detected, indicating that the fibres work via a contact-active antibacterial mechanism. The results show the feasibility of constructing a sustainable antibacterial material using a renewable substrate and water-based solutions in the material construction process.

There is a need for new, antibacterial cellulose-based materials. Antibacterial cellulosic fibers with irreversibly attached polyvinylamine (PVAm) and polyacrylic acid (PAA) in multilayers were developed based on a water-based physical adsorption process. The antibacterial substance is thus prevented from leaching, in contrast to materials containing, for example, silver. It was shown on fibers from different sources that the antibacterial effect against both Escherichia coli and Bacillus subtilis can be tailored. The efficiency correlated with the initial fiber charge, which in turn correlated with the amount of adsorbed PVAm. In the case of highly charged fibers, the antibacterial efficacy was more than 99.9%. A sustainable antibacterial material can be obtained in a simple way based on a water-based process.

New methods are needed to fight antibiotic-resistant bacteria. One alternative that has been proposed is non-leaching, permanently antibacterial surfaces. In this study, we test multilayers formed with antibacterial cationic polyvinylamine (PVAm) and polyacrylic acid (PAA) in a growth-inhibition assay. Both hydrophobically modified and native PVAm were investigated. Multilayers did reduce the bacterial growth, as compared to single layers. However, the sampling time in the assay was critical, as the treated surface area is a capacity-limiting factor. After 2 h incubation, a maximal growth inhibition of more than 99% was achieved with multilayers. In contrast, after 8 h we observed a maximal growth-inhibition of 40%. At longer incubation times, the surface becomes saturated, which explains the observed time-dependent effectiveness. The polymers giving multilayers with the strongest growth-inhibiting properties were native PVAm and PVAm modified with C(8), which also were the polymers with highest charge density. We therefore conclude that this effect is mainly an electrostatically driven process. Viability staining using a fluorescent stain showed a high viability rate of the adhered bacteria. The multilayers are therefore more bacteriostatic than antibacterial.

The world is in desperate need of new methods for controlling microbial growth. Antibacterial surfaces, with antibacterial polymers irreversible attached, is a promising alternative. By targeting the bacterial membrane, the risk of evolving resistant bacteria is reduced. The attachment of the polymers prevents unwanted leaching and keeps a high, active surface concentration. The making of such surfaces does however involve harsh reaction conditions and is thus unsuitable for use in large scale. Using the polyelectrolyte multilayer (PEM) technique we here electrostatically adsorb cationic antibacterial polymers. This takes place in aqueous solutions and in room temperature, making it an appealing alternative. Previous studies performed in our group have focused on model surfaces to get fundamental knowledge about the multilayer properties. Here the PEMs are applied on cellulosic pulp and tested for antibacterial properties against E. coli and B. subtilis. The obtained material was found to be antibacterial against both bacterial strains. These antibacterial fibers, produced in a safe, sustainable process, will give opportunities for new products and new applications.

Contact-active antibacterial materials with irreversibly attached antibacterial agents have been developed as an environmentally friendly alternative to traditional biocide treatments. Of particular interest are materials fabricated through the physical adsorption of charged polymers. This simple method allows for the use of water-based processes and materials originating from renewable sources, e.g., cellulosic fibres. Furthermore, by varying the process parameters, such as ionic strength, it is possible to tune the properties of the adsorbed polymer layer. However, the underlying antibacterial mechanism remains obscure, and this hinders the rational design of antibacterial multilayers. To gain further insight into the antibacterial mechanisms of physically adsorbed multilayers of polyvinylamine and polyacrylic acid, the surface charge of cellulose fibres was increased via radical oxidation. This oxidation increased the amount of polymer that was adsorbed and resulted in increased antibacterial efficacy against both Escherichia coli and Bacillus subtilis compared with polymer-modified unoxidised fibres. Electron microscopy analysis of the E. coli adhered to the fibres revealed that the multilayer treatment resulted in elongated bacteria with deformed cell walls. This work demonstrates the importance of electrostatic interaction to the antibacterial effect of polymer-modified fibres.

 Portable purifi cation systems are easy ways to obtain clean drinking water when there is no large-scale water treatment available. In this study, the potential to purify water using bacteria adsorbing cellulosic fi bers, functionalized with polyelectrolytes according to the layer-by-layer method, is investigated. The adsorbed polyelectrolytes create a positive charge on the fi ber surface that physically attracts and bonds with bacteria. Three types of cellulosic materials have been modifi ed and tested for the bacterial removal capacity in water. The time, material-water ratio and bacterial concentration dependence, as well as the bacterial removal capacity in water from natural sources, have been evaluated. Freely dispersed bacteria adsorbing cellulosic fi bers can remove greater than 99.9% of Escherichia coli  from nonturbid water, with the most notable reduction occurring within the fi rst hour. A fi ltering approach using modifi ed cellulosic fi bers is desirable for purifi cation of natural water. An initial fi ltration test showed that polyelectrolyte multilayer modifi ed cellulosic fi bers can remove greater than 99% of bacteria from natural water. The bacteria adsorbing cellulosic fi bers do not leach any biocides, and it is an environmentally sustainable and cheap option for disposable water purification devices.

Water filtration is a popular way to remove particles and microorganisms from drinking water but is generally based on size exclusion of the particles. Bacteria can be modeled as small particles with a diameter of 1-2 µm, which is usually too small to be excluded by paper filters. In this article, commercial available paper filters have been surface modified by polyelectrolyte multilayer adsorption to create a positively charged filter that can trap the negatively charged bacteria through electrostatic interactions. The polyelectrolyte modified filters bind the bacteria to there surface and will thereby remove bacteria from the water instead of inactivated them through addition of biocides. The modified filters can remove more than 99.9 % of bacteria in water, depending on filter design, and has successfully been compared to a commercial cellulose water filter, based on the release of silver to inactivate bacteria. This cheap and easy modification of filter paper has potential to create disposable water purification filters that could be used in emergency situations to prevent outbreak of lethal diarrheal diseases.

Filtration is a common way to obtain pure drinking water by removing particles and microorganisms based on size exclusion. Cellulose-based filters are affordable and biobased option for the removal of particles but bacteria are usually too small to be removed by size exclusion alone. In this article, the surfaces of cellulose fibres in two types of commercial paper filters have been given a positive net charge to trap bacteria through electrostatic interactions without releasing any biocides. The fibres were modified with the cationic polyelectrolyte polyvinylamine polymer in single layers (1 L) or in multilayers together with the anionic polyelectrolyte polyacrylic acid (3 L or 5 L) using a water-based process at room temperature. Filtration tests show that all filters, using both types of filter papers and a number of layers, can physically remove more than 99.9% of E. coli from water and that the 3 L modified filters can remove more than 97% of cultivatable bacteria from natural water samples. The bacterial reduction increased with increasing number of filter sheets used for the filtration and the majority of the bacteria were trapped in the top sheets of the filter. The results show the potential for creating water purification filters from bio-based everyday consumable products with a simple modification process. The filters could be used in the future for point-of-use water purification that may be able to save lives without releasing bactericides.

Portable purification systems are easy ways to obtain clean drinking water when there is no large-scale water treatment available. In this study, the potential to purify water using bacteria adsorbing cellulose functionalized with polyelectrolytes, according to the Layer-by-Layer method, is investigated. The adsorbed polyelectrolytes create a positive charge on the cellulose surface that physically attracts and bonds with bacteria. Three types of cellulose material have been modified and tested for the bacterial removal capacity in water. The time, material-water ratio and bacterial concentration dependence, as well as the bacterial removal capacity in water from natural sources, have been evaluated. Freely dispersed bacteria adsorbing cellulose can remove greater than 99.9% of Escherichia coli from non-turbid water, with the most notable reduction occurring within the first hour. For turbid water, a filtering approach using modified cellulose fibers is desirable. This bacteria adsorbing cellulose does not leach any biocides, and it is an environmentally sustainable and cheap option for disposable water purification devices.