Immobilization of Bi2WO6 on Polymer Membranes for Photocatalytic Removal of Micropollutants from Water - A Stable and Visible Light Active Alternative.

In this work, bismuth tungstate Bi2WO6 is immobilized on polymer membranes to photocatalytically remove micropollutants from water as an alternative to titanium dioxide TiO2. A synthesis method for Bi2WO6 preparation and its immobilization on a polymer membrane is developed. Bi2WO6 is characterized using X-ray diffraction and UV-vis reflectance spectroscopy, while the membrane undergoes analysis through scanning electron microscopy, X-ray photoelectron spectroscopy, and degradation experiments. The density of states calculations for TiO2 and Bi2WO6, along with PVDF reactions with potential reactive species, are investigated by density functional theory. The generation of hydroxyl radicals OH• is investigated via the reaction of coumarin to umbelliferone via fluorescence probe detection and electron paramagnetic resonance. Increasing reactant concentration enhances Bi2WO6 crystallinity. Under UV light at pH 7 and 11, the Bi2WO6 membrane completely degrades propranolol in 3 and 1 h, respectively, remaining stable and reusable for over 10 cycles (30 h). Active under visible light with a bandgap of 2.91 eV, the Bi2WO6 membrane demonstrates superior stability compared to a TiO2 membrane during a 7-day exposure to UV light as Bi2WO6 does not generate OH• radicals. The Bi2WO6 membrane is an alternative for water pollutant degradation due to its visible light activity and long-term stability.

Enhanced EDC removal from water through electron beam-mediated adsorber particle integration in microfiltration membranes.

The existence of endocrine disrupting chemicals (EDCs) in water and wastewater gives rise to significant environmental concerns. Conventional treatment approaches demonstrate limited capacity for EDC removal. Thus, incorporation of advanced separation procedures becomes essential to enhance the efficiency of EDC removal. In this work, adsorber composite microfiltration polyethersulfone membranes embedded with divinyl benzene polymer particles were created. These membranes were designed for effectively removing a variety of EDCs from water. The adsorber particles were synthesized using precipitation polymerization. Subsequently, they were integrated into the membrane scaffold through a phase inversion process. The technique of electron beam irradiation was applied for the covalent immobilization of particles within the membrane scaffold. Standard characterization procedures were carried out (i.e., water permeance, contact angle, X-ray photoelectron spectroscopy and scanning electron microscopy) to gain a deep understanding of the synthesized membrane properties. Dynamic adsorption experiments demonstrated the excellent capability of the synthesized composite membranes to effectively remove EDCs from water. Particularly, among the various target molecules examined, testosterone stands out with the most remarkable enhancement, presenting an adsorption loading of 220 mg m-2. This is an impressive 26-fold increase in the adsorption when compared to the performance of the pristine membrane. Similarly, androst-4-ene-3,17-dione exhibited an 18-fold improvement in adsorption capacity in comparison to the pristine membrane. The composite membranes also exhibited significant adsorption capacities for other key compounds, including 17ß-estradiol, equilin, and bisphenol-A. With the implementation of an effective regeneration procedure, the composite membranes were put to use for adsorption over three consecutive cycles without any decline in their adsorption capacity.

Fluorescence Lifetime Control of Nitrogen Vacancy Centers in Nanodiamonds for Long-Term Information Storage.

Today's huge amount of data generation and transfer induced an urgent requirement for long-term data storage. Here, we demonstrate and discuss a concept for long-term storage using NV centers inside nanodiamonds. The approach is based upon the radiation-induced generation of additional vacancies (so-called GR1 states), which quench the initial NV centers, resulting in a reduced overall fluorescence lifetime of the NV center. Using the tailored fluorescence lifetime of the NV center to code the information, we demonstrate a "beyond binary" data storage density per bit. We also demonstrate that this process is reversible by heating the sample or the spot of information. This proof of principle shows that our technique may be a promising alternative data storage technology, especially in terms of long-term storage, due to the high stability of the involved color centers. In addition to the proof-of-principle demonstration using macroscopic samples, we suggest and discuss the usage of focused electron beams to write information in nanodiamond materials, to read it out with focused low-intensity light, and to erase it on the macro-, micro-, or nanoscale.

Reagent-Free Immobilization of Industrial Lipases to Develop Lipolytic Membranes with Self-Cleaning Surfaces.

Biocatalytic membrane reactors combine the highly efficient biotransformation capability of enzymes with the selective filtration performance of membrane filters. Common strategies to immobilize enzymes on polymeric membranes are based on chemical coupling reactions. Still, they are associated with drawbacks such as long reaction times, high costs, and the use of potentially toxic or hazardous reagents. In this study, a reagent-free immobilization method based on electron beam irradiation was investigated, which allows much faster, cleaner, and cheaper fabrication of enzyme membrane reactors. Two industrial lipase enzymes were coupled onto a polyvinylidene fluoride (PVDF) flat sheet membrane to create self-cleaning surfaces. The response surface methodology (RSM) in the design-of-experiments approach was applied to investigate the effects of three numerical factors on enzyme activity, yielding a maximum activity of 823 ± 118 U m-2 (enzyme concentration: 8.4 g L-1, impregnation time: 5 min, irradiation dose: 80 kGy). The lipolytic membranes were used in fouling tests with olive oil (1 g L-1 in 2 mM sodium dodecyl sulfate), resulting in 100% regeneration of filtration performance after 3 h of self-cleaning in an aqueous buffer (pH 8, 37 °C). Reusability with three consecutive cycles demonstrates regeneration of 95%. Comprehensive membrane characterization was performed by determining enzyme kinetic parameters, permeance monitoring, X-ray photoelectron spectroscopy, FTIR spectroscopy, scanning electron microscopy, and zeta potential, as well as water contact angle measurements.

Radiation-Induced Graft Immobilization (RIGI): Covalent Binding of Non-Vinyl Compounds on Polymer Membranes.

Radiation-induced graft immobilization (RIGI) is a novel method for the covalent binding of substances on polymeric materials without the use of additional chemicals. In contrast to the well-known radiation-induced graft polymerization (RIGP), RIGI can use non-vinyl compounds such as small and large functional molecules, hydrophilic polymers, or even enzymes. In a one-step electron-beam-based process, immobilization can be performed in a clean, fast, and continuous operation mode, as required for industrial applications. This study proposes a reaction mechanism using polyvinylidene fluoride (PVDF) and two small model molecules, glycine and taurine, in aqueous solution. Covalent coupling of single molecules is achieved by radical recombination and alkene addition reactions, with water radiolysis playing a crucial role in the formation of reactive solute species. Hydroxyl radicals contribute mainly to the immobilization, while solvated electrons and hydrogen radicals play a minor role. Release of fluoride is mainly induced by direct ionization of the polymer and supported by water. Hydrophobic chains attached to cations appear to enhance the covalent attachment of solutes to the polymer surface. Computational work is complemented by experimental studies, including X-ray photoelectron spectroscopy (XPS) and fluoride high-performance ion chromatography (HPIC).

Estradiol Removal by Adsorptive Coating of a Microfiltration Membrane.

This work demonstrates the enhancement of the adsorption properties of polyethersulfone (PES) microfiltration membranes for 17ß-estradiol (E2) from water. This compound represents a highly potent endocrine-disrupting chemical (EDC). The PES membranes were modified with a hydrophilic coating functionalized by amide groups. The modification was performed by the interfacial reaction between hexamethylenediamine (HMD) or piperazine (PIP) as the amine monomer and trimesoyl chloride (TMC) or adipoyl chloride (ADC) as the acid monomer on the surface of the membrane using electron beam irradiation. The modified membranes and the untreated PES membrane were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), water permeance measurements, water contact angle measurements, and adsorption experiments. Furthermore, the effects of simultaneous changes in four modification parameters: amine monomer types (HMD or PIP), acid monomer types (TMC or ADC), irradiation dosage (150 or 200 kGy), and the addition of toluene as a swelling agent, on the E2 adsorption capacity were investigated. The results showed that the adsorption capacities of modified PES membranes toward E2 are >60%, while the unmodified PES membrane had an adsorption capacity up to 30% for E2 under similar experimental conditions, i.e., an enhancement of a factor of 2. Next to the superior adsorption properties, the modified PES membranes maintain high water permeability and no pore blockage was observed. The highlighted results pave the way to develop efficient low-cost, stable, and high-performance adsorber membranes.

Highly Efficient One-Step Protein Immobilization on Polymer Membranes Supported by Response Surface Methodology.

Immobilization of proteins by covalent coupling to polymeric materials offers numerous excellent advantages for various applications, however, it is usually limited by coupling strategies, which are often too expensive or complex. In this study, an electron-beam-based process for covalent coupling of the model protein bovine serum albumin (BSA) onto polyvinylidene fluoride (PVDF) flat sheet membranes was investigated. Immobilization can be performed in a clean, fast, and continuous mode of operation without any additional chemicals involved. Using the Design of Experiments (DoE) approach, nine process factors were investigated for their influence on graft yield and homogeneity. The parameters could be reduced to only four highly significant factors: BSA concentration, impregnation method, impregnation time, and electron beam irradiation dose. Subsequently, optimization of the process was performed using the Response Surface Methodology (RSM). A one-step method was developed, resulting in a high BSA grafting yield of 955 mg m-2 and a relative standard deviation of 3.6%. High efficiency was demonstrated by reusing the impregnation solution five times consecutively without reducing the final BSA grafting yield. Comprehensive characterization was conducted by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and measurements of zeta potential, contact angle and surface free energy, as well as filtration performance. In addition, mechanical properties and morphology were examined using mercury porosimetry, tensile testing, and scanning electron microscopy (SEM).

Reduction of Biofouling of a Microfiltration Membrane Using Amide Functionalities-Hydrophilization without Changes in Morphology.

A major goal of membrane science is the improvement of the membrane performance and the reduction of fouling effects, which occur during most aqueous filtration applications. Increasing the surface hydrophilicity can improve the membrane performance (in case of aqueous media) and decelerates membrane fouling. In this study, a PES microfiltration membrane (14,600 L m-2 h-1 bar-1) was hydrophilized using a hydrophilic surface coating based on amide functionalities, converting the hydrophobic membrane surface (water contact angle, WCA: ~90°) into an extremely hydrophilic one (WCA: ~30°). The amide layer was created by first immobilizing piperazine to the membrane surface via electron beam irradiation. Subsequently, a reaction with 1,3,5-benzenetricarbonyl trichloride (TMC) was applied to generate an amide structure. The presented approach resulted in a hydrophilic membrane surface, while maintaining permeance of the membrane without pore blocking. All membranes were investigated regarding their permeance, porosity, average pore size, morphology (SEM), chemical composition (XPS), and wettability. Soxhlet extraction was carried out to demonstrate the stability of the applied coating. The improvement of the modified membranes was demonstrated using dead-end filtration of algae solutions. After three fouling cycles, about 60% of the initial permeance remain for the modified membranes, while only ~25% remain for the reference.

Growth, Polymorphism, and Spatially Controlled Surface Immobilization of Biotinylated Variants of IAPP21-27 Fibrils.

The islet amyloid polypeptide (IAPP) is a regulatory peptide that can aggregate into fibrillar structures associated with type 2 diabetes. In this study, the IAPP21-27 segment was modified with a biotin linker at the N-terminus (Btn-GNNFGAIL) to immobilize peptide fibrils on streptavidin-coated surfaces. Key residues for fibril formation of the N-terminal biotinylated IAPP21-27 segment were identified by using an alanine scanning approach combined with molecular dynamics simulations, thioflavin T fluorescence measurements, and scanning electron microscopy. Significant contributions of phenylalanine (F23), leucine (L27), and isoleucine (I26) for the fibrillation of the short peptide segment were identified. The fibril morphologies of the peptide variants differed depending on their primary sequence, ranging from flexible and semiflexible to stiff and crystal-like structures. These insights could advance the design of new functional hybrid bionanomaterials and fibril-engineered surface coatings using short peptide segments. To validate this concept, the biotinylated fibrils were immobilized on streptavidin-coated surfaces under spatial control.

Electron beam functionalized photodynamic polyethersulfone membranes - photophysical characterization and antimicrobial activity.

Polymer membranes are powerful filtration tools in medicine and water treatment. Their efficiency and operational lifetime is limited by biofouling caused by microorganisms. This study describes the development of photodynamical active antimicrobial polymer membranes in a one-pot functionalization step using a well-known photosensitizer (PS). Commercially available polyethersulfone (PES) membranes for microfiltration were doped with the polycationic PS TMPyP using electron beam irradiation. These membranes were characterized in terms of binding stability and quantification of the PS and membrane morphology. Furthermore, the photodynamic ability was verified by time resolved singlet oxygen luminescence scans and successfully tested against the Gram-negative bacterium E. coli under low dose white light illumination resulting in the reduction in cell survival of 6 log10 units. Finally, in preliminarily experiments the photodynamic action against the Gram-positive bacteria M. luteus and the Gram-negative P. fluorescence and the mold C. cladosporioides was demonstrated. These promising results show the high photodynamic potential of electron beam functionalization of PES membranes with TMPyP. It preserves the photodynamic abilities of the immobilized PS resulting in efficient photodynamic inactivation of bacteria and mold on the membrane surface. The uprising worldwide spread of antibiotic resistant bacteria makes the development of new antibacterial strategies an inevitable challenge. The photodynamic inactivation of bacteria and its adaptation for antimicrobial surfaces, e.g. filtration membranes for water treatment, displays many advantages in terms of a wide application range, low mutagenic potential and environmental compatibility.

Charge Separating Microfiltration Membrane with pH-Dependent Selectivity.

Membrane filters are designed for selective separation of components from a mixture. While separation by size might be the most common approach, other characteristics like charge can also be used for separation as presented in this study. Here, a polyether sulfone membrane was modified to create a zwitterionic surface. Depending on the pH value of the surrounding solution the membrane surface will be either negatively or positively charged. Thus, the charged state can be easily adjusted even by small changes of the pH value of the solution. Charged polystyrene beads were used as model reagent to investigate the pH dependent selectivity of the membrane. It was found that electrostatic forces are dominating the interactions between polystyrene beads and membrane surface during the filtration. This enables a complete control of the membrane's selectivity according to the electrostatic interactions. Furthermore, differently charged beads marked with fluorescent dyes were used to investigate the selectivity of mixtures of charged components. These different components were successfully separated according to their charged state proving the selectivity of the invented membrane.

Degradation of polystyrene and selected analogues by biological Fenton chemistry approaches: Opportunities and limitations.

Conventional synthetic polymers typically are highly resistant to microbial degradation, which is beneficial for their intended purpose but highly detrimental when such polymers get lost into the environment. Polystyrene is one of the most widespread of such polymers, but knowledge about its biological degradability is scarce. In this study, we investigated the ability of the polymer-degrading brown-rot fungus Gloeophyllum trabeum to attack polystyrene via Fenton chemistry driven by the redox-cycling of quinones. Indications of superficial oxidation were observed, but the overall effects on the polymer were weak. To assess factors constraining biodegradation of polystyrene, the small water-soluble model compounds ethylbenzene and isopropylbenzene (cumene) were also subjected to biodegradation by G. trabeum. Likewise, ethylbenzene sulfonate, cumene sulfonate and the dimer 1,3-diphenylbutane sulfonate were used as model compounds for comparison with polystyrene sulfonate, which G. trabeum can substantially depolymerise. All model compounds but cumene were degraded by G. trabeum and yielded a large variety of oxidised metabolites, suggesting that both the very poor bioavailability of polystyrene and its inert basic structure play important roles constraining biodegradability via biologically driven Fenton chemistry.

Bio-Inspired Polymer Membrane Surface Cleaning.

To generate polyethersulfone membranes with a biocatalytically active surface, pancreatin was covalently immobilized. Pancreatin is a mixture of digestive enzymes such as protease, lipase, and amylase. The resulting membranes exhibit self-cleaning properties after "switching on" the respective enzyme by adjusting pH and temperature. Thus, the membrane surface can actively degrade a fouling layer on its surface and regain initial permeability. Fouling tests with solutions of protein, oil, and mixtures of both, were performed, and the membrane's ability to self-clean the fouled surface was characterized. Membrane characterization was conducted by investigation of the immobilized enzyme concentration, enzyme activity, water permeation flux, fouling tests, porosimetry, X-ray photoelectron spectroscopy, and scanning electron microscopy.

Peptide-Mediated Specific Immobilization of Catalytically Active Cytochrome P450 BM3 Variant.

Cytochrome P450 BM3 (CYP102A1) from Bacillus megaterium is an interesting target for biotechnological applications, because of its vast substrate variety combined with high P450 monooxygenase activity. The low stability in vitro could be overcome by immobilization on surfaces. Here we describe a novel method for immobilization on metal surfaces by using selectively binding peptides. A P450 BM3 triple mutant (3M-P450BM3: A74G, F87V, L188Q) was purified as protein thioester and ligated to indium tin oxide or gold binding peptides (BP) named HighSP-BP and Cys-BP, respectively. The ligation products were characterized by Western Blot and tryptic digestion combined with mass spectrometry, and displayed high affinity binding on the depicted surfaces. Next, we could demonstrate by benzyloxyresorufin O-dealkylation assay (BROD assay) that the activity of immobilized ligation products is higher than for the soluble form. The study provides a new tool for selective modification and immobilization of P450 variants.

High quality reduced graphene oxide flakes by fast kinetically controlled and clean indirect UV-induced radical reduction.

This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the GO is not excited directly. While the direct photoexcitation of aqueous GO (when GO is the only light-absorbing component) takes several hours of reaction time at ambient temperature (4 h) leading only to a partial GO reduction, the addition of small amounts of isopropanol and acetone (2% and 1%) leads to a dramatically shortened reaction time by more than two orders of magnitude (2 min) and a very efficient and soft reduction of graphene oxide. This method avoids the formation of non-volatile species and in turn contamination of the produced rGO and it is based on the highly efficient generation of reducing carbon centered isopropanol radicals via the reaction of triplet acetone with isopropanol. While the direct photolysis of GO dispersions easily leads to degradation of the carbon lattice of GO and thus to a relatively low electric conductivity of the films of flakes, our indirect photoreduction of GO instead largely avoids the formation of defects, keeping the carbon lattice intact. Mechanisms of the direct and indirect photoreduction of GO have been elucidated and compared. Raman spectroscopy, XPS and conductivity measurements prove the efficiency of the indirect photoreduction in comparison with the state-of-the-art reduction method for GO (hydriodic acid/trifluoroacetic acid). The rapid reduction times and water solvent containing only small amounts of isopropanol and acetone may allow easy process up-scaling for technical applications and low-energy consumption.

Membrane Functionalization with Hyperbranched Polymers.

Polymer membranes have been modified with hyperbranched polymers with the aim to generate a high density of hydrophilic functional groups at the membrane surface. For this purpose hyperbranched polymers containing amino, alcohol, and carboxylic acid end groups were used for membrane modification, respectively. Thus, surface potential and charges were changed significantly to result in attractive or repulsive interactions towards three different proteins (albumin, lysozyme, myoglobin) that were used to indicate membrane fouling properties. Our studies demonstrated that hydrophilization alone is not effective for avoiding membrane fouling when charged proteins are present. In contrast, electrostatic repulsion seems to be a general key factor.

Methods for visualising active microbial benzene degraders in in situ microcosms.

Natural attenuation maybe a cost-efficient option for bioremediation of contaminated sites but requires knowledge about the activity of degrading microbes under in situ conditions. In order to link microbial activity to the spatial distribution of contaminant degraders, we combined the recently improved in situ microcosm approach, so-called 'direct-push bacterial trap' (DP-BACTRAP), with nano-scale secondary ion mass spectrometry (NanoSIMS) analysis on samples from contaminated constructed wetlands. This approach is based on initially sterile microcosms amended with (13)C-labelled benzene as a source of carbon and energy for microorganisms. The microcosms were introduced directly in the constructed wetland, where they were colonised by indigenous microorganisms from the sediment. After incubation in the field, the samples were analysed by NanoSIMS, scanning electron microscopy (SEM) and fluorescence microscopy in order to visualise (13)C-labelled microbial biomass on undisturbed samples from the microcosms. With the approach developed, we successfully visualised benzene-degrading microbes on solid materials with high surface area by means of NanoSIMS. Moreover, we could demonstrate the feasibility of NanoSIMS analysis of unembedded porous media with a highly complex topography, which was frequently reasoned to not lead to sufficient results.

Mechanistic aspects of the radiation-chemical reduction of graphene oxide to graphene-like materials.

PURPOSE: The aim of the work was to investigate mechanistic details of the preparation of graphene-like materials (GLM) via reduction of graphene oxide (GO) in aqueous dispersions by electron beam (EB) generated reducing free radicals. MATERIALS AND METHODS: A 10 MeV linear accelerator was employed to irradiate aqueous GO dispersions at ambient temperatures. The kinetics of GO reduction was followed using UV-Vis spectroscopy. The resulting GLM were characterized by X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), Raman spectroscopy and conductivity measurements. RESULTS: The reduction of GO could be afforded with high efficiency within minutes at room temperature via the reaction of GO with reducing radicals generated by EB irradiation. The detailed investigation of the reduction mechanism allowed a selection of the best reducing free radicals in terms of both their efficiency and environmental impact of their precursors and final products. CONCLUSIONS: The EB-treatment of aqueous GO dispersions is a highly efficient, environmentally friendly, cost-effective and easily up-scalable method for the preparation of GLM. The efficiency of the new reduction approach is comparable with the best existing methods.

Biocompatible polysaccharide-based cryogels.

This study focuses on the development of novel biocompatible macroporous cryogels by electron-beam assisted free-radical crosslinking reaction of polymerizable dextran and hyaluronan derivatives. As a main advantage this straightforward approach provides highly pure materials of high porosity without using additional crosslinkers or initiators. The cryogels were characterized with regard to their morphology and their basic properties including thermal and mechanical characteristics, and swellability. It was found that the applied irradiation dose and the chemical composition strongly influence the material properties of the resulting cryogels. Preliminary cytotoxicity tests illustrate the excellent in vitro-cytocompatibility of the fabricated cryogels making them especially attractive as matrices in tissue regeneration procedures.

Amino-functionalized monolithic spin-type columns for high-throughput lectin affinity chromatography of glycoproteins.

Hydrophilic poly(ethylene glycol)-based monoliths were synthesized in the spin-tip format for high-throughput applications via pulsed electron beam irradiation. Monoliths with a homogeneous porous structure and a total porosity of 69% were obtained. The cross-linked polymeric structure was further mechanically stabilized via the incorporation of silica nanoparticles. Amino-functionalization of the monoliths was accomplished by a straightforward, water-based, one-step approach that entailed the electron-beam irradiation-induced grafting of poly(allylamine). The amine functionalized spin columns showed very low unspecific protein adsorption and were successfully applied as adsorbents in lectin affinity chromatography for the purification of ovalbumin. The novel columns also outperformed a commercially available system.