Ambient Catalytic Spinning of Polyethylene Nanofibers.

A novel single-atom Ni(II) catalyst (Ni-OH) is covalently immobilized onto the nano-channels of mesoporous Santa Barbara Amorphous (SBA)-15 particles and isotropic Anodized Aluminum Oxide (AAO) membrane for confined-space ethylene extrusion polymerization. The presence of surface-tethered Ni complexes (Ni@SBA-15 and Ni@AAO) is confirmed by the inductively coupled plasma-optical emission spectrometry (ICP-OES) and X-ray photoelectron spectroscopy (XPS). In the catalytic spinning process, the produced PE materials exhibit very homogeneous fibrous morphology at nanoscale (diameter: ~50 nm). The synthesized PE nanofibers extrude in a highly oriented manner from the nano-reactors at ambient temperature. Remarkably high Mw (1.62×106  g mol-1 ), melting point (124 °C), and crystallinity (41.8 %) are observed among PE samples thanks to the confined-space polymerization. The chain-walking behavior of surface tethered Ni catalysts is greatly limited by the confinement inside the nano-channels, leading to the formation of very low-branched PE materials (13.6/1000 C). Due to fixed supported catalytic topology and room temperature, the filaments are expected to be free of entanglement. This work signifies an important step towards the realization of a continuous mild catalytic-spinning (CATSPIN) process, where the polymer is directly synthesized into fiber shape at negligible chain branching and elegantly avoiding common limitations like thermal degradation or molecular entanglement.

Melanized-Cationic Cellulose Nanofiber Foams for Bioinspired Removal of Cationic Dyes.

In recent years, water pollution has developed into a severe environmental and public health problem due to rapid urbanization and industrialization, especially in some developing countries. Finding solutions to tackle water pollution is urgently required and is of global importance. Currently, a range of water treatment methods are available; however, a water remediation process that is simple, inexpensive, eco-friendly, and effective for the removal of pollutants down to ppm/ppb concentrations has long been sought after. Herein, we describe a novel approach using fungal melanin for developing melanized-cationic cellulose nanofiber (melanized-C-CNF) foams that can successfully remove pollutants in water systems. The foam can be recycled several times while retaining its adsorption/desorption property, indicating high practicability for adsorbing the cationic dye crystal violet. This work highlights the opportunity to combine both the advanced features of sustainable polymers such as cellulose and the unique properties of fungal melanin to manufacture biohybrid composites for water purification.

Metal-Modified Montmorillonite as Plasmonic Microstructure for Direct Protein Detection.

Thanks to its negative surface charge and high swelling behavior, montmorillonite (MMT) has been widely used to design hybrid materials for applications in metal ion adsorption, drug delivery, or antibacterial substrates. The changes in photophysical and photochemical properties observed when fluorophores interact with MMT make these hybrid materials attractive for designing novel optical sensors. Sensor technology is making huge strides forward, achieving high sensitivity and selectivity, but the fabrication of the sensing platform is often time-consuming and requires expensive chemicals and facilities. Here, we synthesized metal-modified MMT particles suitable for the bio-sensing of self-fluorescent biomolecules. The fluorescent enhancement achieved by combining clay minerals and plasmonic effect was exploited to improve the sensitivity of the fluorescence-based detection mechanism. As proof of concept, we showed that the signal of fluorescein isothiocyanate can be harvested by a factor of 60 using silver-modified MMT, while bovine serum albumin was successfully detected at 1.9 µg/mL. Furthermore, we demonstrated the versatility of the proposed hybrid materials by exploiting their plasmonic properties to develop liquid label-free detection systems. Our results on the signal enhancement achieved using metal-modified MMT will allow the development of highly sensitive, easily fabricated, and cost-efficient fluorescent- and plasmonic-based detection methods for biomolecules.

Plasma Processing of Low Vapor Pressure Liquids to Generate Functional Surfaces.

The concept of depositing solid films on low-vapor pressure liquids is introduced and developed into a top-down approach to functionalize surfaces by attaching liquid polyethylene glycol (PEG). Solid-liquid gradients were formed by low-pressure plasma treatment yielding cross-linking and/or deposition of a plasma polymer film subsequently bound to a flexible polydimethylsiloxane (PDMS) backing. The analysis via optical transmission spectroscopy (OTS), optical, confocal laser scanning (CLSM) and scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) as well as by water contact angle (WCA) measurements revealed correlations between optical appearance, chemical composition and surface properties of the resulting water absorbing, covalently bound PEG-functionalized surfaces. Requirements for plasma polymer film deposition on low-vapor pressure liquids and effective surface functionalization are defined. Namely, the thickness of the liquid PEG substrate was a crucial parameter for successful film growth and covalent attachment of PEG. The presented method is a practicable approach for the production of functional surfaces featuring long-lasting strong hydrophilic properties, making them predestined for non-fouling or low-friction applications.

Composition and Stability of Plasma Polymer Films Exhibiting Vertical Chemical Gradients.

Controlling the balance between stability and functional group density in grown plasma polymer films is the key to diverse applications such as drug release, tissue-engineered implants, filtration, contact lenses, microfluidics, electrodes, sensors, etc. Highly functional plasma polymer films typically show a limited stability in air or aqueous environments due to mechanisms like molecular reorganization, oxidation, and hydrolysis. Stabilization is achieved by enhancing cross-linking at the cost of the terminal functional groups such as -OH and -COOH, but also -NH2, etc. To overcome such limitations, a structural and chemical gradient was introduced perpendicular to the surface plane; this vertical gradient structure is composed of a highly cross-linked base layer, gradually changing into a more functional nanoscaled surface termination layer. This was achieved using CO2/C2H4 discharges with decreasing power input and increasing gas ratio during plasma polymer deposition. The aging behavior and stability of such oxygen-functional vertical gradient nanostructures were studied in air and in different aqueous environments (acidic pH 4, neutral pH ≈ 6.2, and basic pH 10). Complementary characterization methods were used, including angle-resolved X-ray photoelectron spectroscopy (ARXPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) as well as water contact angle (WCA) measurements. It was found that in air, the vertical gradient films are stabilized over a period of months. The same gradients also appear to be stable in neutral water over a period of at least 1 week. Changes in the oxygen depth profiles have been observed at pH 4 and pH 10 showing structural and chemical aging effects on different time scales. The use of vertical gradient plasma polymer nanofilms thus represents a novel approach providing enhanced stability, thus opening the possibility for new applications.

Suppression of Hydrophobic Recovery by Plasma Polymer Films with Vertical Chemical Gradients.

Vertical chemical gradients extending over a few nanometers were explored. The gradients are based on plasma-polymerized oxygen-containing ethylene (ppOEt) films. Using plasma conditions with low CO2/C2H4 ratio and high energy input, cross-linked films were deposited as base layer, while increasing CO2 and lowering energy input resulted in less cross-linked yet highly functional films as applied as top layer. Aging studies indicate that, in particular, for very thin gradient structures, the cross-linked subsurface zone effectively hinders reorientation of the surface functional groups, thus restricting hydrophobic recovery and oxidation effects.

Controlling the release from silver electrodes by titanium adlayers for health monitoring.

Beside cancer, cardiovascular disease is the leading cause of deaths worldwide. For medical diagnosis electrocardiography (ECG) is only a powerful predicting tool if the sensed cardiac cycle involves a high signal to noise ratio and reduced artefacts over a long term. The interface of the electrodes to the biological system is therefore improved with a novel textile system. The textile fiber therein is a 100nm silver-coated yarn to improve the signal quality and the reliability of the ECG signals. Long term diagnosis involves a silver release to the applied tissue surface. It is known, that a high silver release can cause a cytotoxic effect on human cells. To prevent cytotoxicity but still enabling good electrical conductivity accompanied by positive antibacterial properties of silver we developed a nanoscaled TiOx adlayer. The biological and electrical properties of these novel electrode systems are investigated and described in the manuscript. FROM THE CLINICAL EDITOR: The detection of cardiovascular disease using electrocardiography (ECG) usually involves the attachment of electrodes on the skin. In this paper, the authors here described a novel textile system using silver-coated yarn, to provide the interface of the electrodes to the biological system. To prevent sustained high silver release that may lead to cytotoxicity, a nanoscaled TiOx adlayer was developed and added to the novel textile electrode.

Absorbing TiO x thin film enabling laser welding of polyurethane membranes and polyamide fibers.

We report on the optical properties of thin titanium suboxide (TiO x ) films for applications in laser transmission welding of polymers. Non-absorbing fibers were coated with TiO x coatings by reactive magnetron sputtering. Plasma process parameters influencing the chemical composition and morphology of the deposited thin films were investigated in order to optimize their absorption properties. Optical absorption spectroscopy showed that the oxygen content of the TiO x coatings is the main parameter influencing the optical absorbance. Overtreatment (high power plasma input) of the fiber surface leads to high surface roughness and loss of mechanical stability of the fiber. The study shows that thin substoichiometric TiO x films enable the welding of very thin polyurethane membranes and polyamide fibers with improved adhesion properties.

Decaborane thiols as building blocks for self-assembled monolayers on metal surfaces.

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B(10)H(13)] 1, [2-(HS)-nido-B(10)H(13)] 2, and [1,2-(HS)(2)-nido-B(10)H(12)] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B(18)H(22)·C(6)H(6) solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B(10)H(13)(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol (1)H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe(2)(PMe(2)Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The XPS-derived stoichiometry is very similar to that for a SAM produced directly from the adsorption of [1-(HS)-7,7-(PMe(2)Ph)(2)-nido-7-PtB(10)H(11)] 4. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be extended to other binary boron hydride clusters.

High-resolution cavity ringdown spectroscopy of the jet-cooled propyl peroxy radical C(3)H(7)O(2).

We have obtained high resolution, partially rotationally resolved, jet-cooled cavity ringdown spectra of the origin band of the A<--X electronic transition of two of the five conformers (G(1)G(2) and G(1)T(2)) of the normal propyl peroxy radical, C(3)H(7)O(2), as well as the G conformer of the iso-propyl peroxy radical isomer. This transition, located in the near infrared, was studied using a narrow band laser source (less than or approximately 250 MHz) and a supersonic slit-jet expansion coupled with an electric discharge allowing us to obtain rotational temperatures of about 15 K. All three spectra have been successfully fitted using an evolutionary algorithm approach with a Hamiltonian including rotational and spin-rotational terms. Excellent agreement with the experimental spectra was obtained by fitting seven molecular parameters in each of the ground and the first excited electronic states as well as the band origin of the electronic transition. These parameters are compared with the results from electronic structure calculations. This analysis confirms unambiguously the previous room-temperature conformer assignments that were based upon quantum chemistry calculations.

Release of graphene-related materials from epoxy-based composites: characterization, quantification and hazard assessment in vitro.

Due to their mechanical strength, thermal stability and electrical conductivity, graphene-related materials (GRMs) have been extensively explored for various applications. Moreover, GRMs have been studied and applied as fillers in polymer composite manufacturing to enhance the polymer performance. With the foreseen growth in GRM production, occupational and consumer exposure is inevitable, thus raising concerns for potential health risks. Therefore, this study aims (1) to characterize aerosol particles released after mechanical abrasion on GRM-reinforced epoxy composites, (2) to quantify the amounts of protruding and free-standing GRMs in the abraded particles and (3) to assess the potential effects of the pristine GRMs as well as the abraded particles on human macrophages differentiated from the THP-1 cell line in vitro. GRMs used in this study included graphene nanoplatelets (GNPs), graphene oxide (GO), and reduced graphene oxide (rGO). All types of pristine GRMs tested induced a dose-dependent increase in reactive oxygen species formation, but a decrease in cell viability was only detected for large GNPs at high concentrations (20 and 40 µg mL-1). The particle modes measured using a scanning mobility particle sizer (SMPS) were 300-400 nm and using an aerodynamic particle sizer (APS) were between 2-3 µm, indicating the release of respirable particles. A significant fraction (51% to 92%) of the GRMs embedded in the epoxy composites was released in the form of free-standing or protruding GRMs in the abraded particles. The abraded particles did not induce any acute cytotoxic effects.

High-resolution cavity ringdown spectroscopy of the jet-cooled ethyl peroxy radical C2H5O2.

We have recorded high resolution, partially rotationally resolved, jet-cooled cavity ringdown spectra of the origin band of the A-X electronic transition of both the G and T conformers of the perproteo and perdeutero isotopologues of the ethyl peroxy radical, C(2)H(5)O(2). This transition, located in the near infrared, was studied using a narrow band laser source (< or approximately 250 MHz) and a supersonic slit-jet expansion coupled with an electric discharge allowing us to obtain rotational temperatures of about 15 K. All four spectra have been successfully simulated using an evolutionary algorithm approach with a Hamiltonian including rotational and spin-rotational terms. Excellent agreement with the experimental spectra was obtained by fitting seven molecular parameters in each ground and the first excited electronic states as well as the band origin of the electronic transition. This analysis unambiguously confirms the assignment of the lower frequency origin band to the G conformer and the higher frequency one to the T conformer.

Extending the Range of Controlling Protein Adsorption via Subsurface Architecture.

Recently, it has been shown that water, confined in a plasma polymer subsurface chemical gradient, nanometers below the surface, significantly reduced the amount of adsorbed protein bovine serum albumin (BSA). Relating to this effect, we proposed the hypothesis that oriented water molecules within the subsurface gradient generate a long-range dipolar field, which interacts with dipolar proteins such as BSA near the surface region. This study extends the above used in situ multistep plasma deposition process to introduce plasma oxidation modifications of the subsurface architecture with the aim to further control the effect on protein adsorption. Neutron reflectivity measurements reveal that the oxidation time increases the amount of matrix-confined water. There is, however, an optimal oxidation time to obtain minimal protein adsorption, which suggests that a minimal distance between confined water molecules plays an important role. Altogether we can extend the range of controlling the adsorbed protein mass by the introduction of this additional plasma oxidation step.

Scalable Biosynthesis of Melanin by the Basidiomycete Armillaria cepistipes.

Natural melanin features many interesting properties, including the ability to shield electromagnetic radiation, the ability to act as scavenger for radical and reactive oxygen species and the capacity to chelate different metal ions. For these reasons, melanin is becoming increasingly relevant for the development of functional materials with potential applications in cosmetics, drug delivery, and water purification. However, the extraction and purification of melanin from conventional sources (e.g., sepia ink, hair, and wool) is inefficient and not easily scalable, hence diverting its technological applications. Some fungal species, especially wood-decay basidiomycetes, can be regarded as promising sources of melanin. In the present study, we screened different fungi in regard to their melanin-biosynthesis abilities using l-tyrosine as a precursor, and we found that an Armillaria cepistipes strain (Empa 655) produced the highest yield of melanin (27.98 g L-1). Physicochemical characterization of the obtained fungal melanin revealed a typical eumelanin structure. The method for the biosynthesis of fungal melanin we propose is efficient, scalable, and sustainable and has the potential to provide support for further technological exploitation.

Observation of the A-x electronic transition of the isomers and conformers of pentyl peroxy radical using cavity ringdown spectroscopy.

Cavity ringdown spectra of the A-X electronic transition of all eight isomers of the pentyl peroxy radical are reported. Using the corresponding assignments from previously studied smaller alkyl peroxy radicals, assignments of origin bands are made for the pentyl peroxy isomers including some conformer-specific assignments for bands of a given isomer. Ab initio calculations also were performed to aid in the spectral assignments for neopentyl, t-butyl, and t-pentyl peroxies. In addition to the origins, vibrational bands have also been assigned for some species. Using the analyzed spectra, the relative reactivity of the primary, secondary, and tertiary hydrogen atoms in isopentane could be determined semiquantitatively.

Plasma polymer film designs through the eyes of ToF-SIMS.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used for the detailed chemical characterization of complex organic materials. Of particular interest in biointerface materials, it provides the accurate molecular information on their surface, a prerequisite for the understanding of subsequent interaction with biomaterials. Plasma polymer films are promising biointerface materials, as tuning the deposition parameters allows the control over film stability and density of surface functional groups. However, the optimization of these film properties not only requires a detailed characterization of the film chemistry, but also that of the deposition mechanisms. Here, ToF-SIMS is used within its different operation modes to investigate those on several plasma polymer film designs. The detailed information on surface molecular chemistry, interface conformation, vertical and lateral chemical and cross-linking gradients is gathered and linked to the underlying deposition mechanisms. In combination with other techniques, the interpretation and understanding of the final functional property of the films in terms of protein adsorption and site-specific binding is achieved.

Extraction of Biofilms From Ureteral Stents for Quantification and Cultivation-Dependent and -Independent Analyses.

Ureteral stenting is a common surgical procedure, which is associated with a high morbidity and economic burden, but the knowledge on the link between biofilms on these stents, morbidity, and the impact of the involved microbiota is still limited. This is partially due to a lack of methods that allow for a controlled extraction of the biofilms from stents. Development of an appropriate in vitro model to assess prevention of biofilm formation by antimicrobial coatings and biomaterials requires a profound understanding of the biofilm composition, including the involved microbiota. This work describes an analytical pipeline for the extraction of native biofilms from ureteral stents for both cultivation-dependent and -independent analysis, involving a novel mechanical abrasion method of passing stent samples through a tapered pinhole. The efficiency of this novel method was evaluated by quantifying the removed biofilm mass, numbers of cultivable bacteria, calcium content, and microscopic stent analysis after biofilm removal using 30 clinical stent samples. Furthermore, the extraction of in vitro formed Escherichia coli biofilms was evaluated by universal 16S quantitative PCR, a cultivation-independent method to demonstrate efficient biofilm removal by the new approach. The novel method enables effective contamination-free extraction of the biofilms formed on ureteral stents and their subsequent quantification, and it represents a useful tool for comprehensive examinations of biofilms on ureteral stents.

Rapid Assay to Assess Bacterial Adhesion on Textiles.

Textiles are frequently colonized by microorganisms leading to undesired consequences like hygienic problems. Biocidal coatings often raise environmental and health concerns, thus sustainable, biocide-free coatings are of interest. To develop novel anti-adhesive textile coatings, a rapid, reliable, and quantitative high-throughput method to study microbial attachment to fabrics is required, however currently not available. Here, a fast and reliable 96-well plate-based screening method is developed. The quantification of bacterial adhesion is based on nucleic acid staining by SYTO9, with Pseudomonas aeruginosa and Staphylococcus aureus as the model microorganisms. Subsequently, 38 commercially available and novel coatings were evaluated for their anti-bacterial adhesion properties. A poly(l-lysine)-g-poly(ethylene glycol) coating on polyester textile substratum revealed an 80% reduction of bacterial adhesion. Both the coating itself and the anti-adhesive property were stable after 20 washing cycles, confirmed by X-ray analysis. The assay provides an efficient tool to rapidly screen for non-biocidal coatings reducing bacterial attachment.

Affinity-Driven Immobilization of Proteins to Hematite Nanoparticles.

Functional nanoparticles are valuable materials for energy production, bioelectronics, and diagnostic devices. The combination of biomolecules with nanosized material produces a new hybrid material with properties that can exceed the ones of the single components. Hematite is a widely available material that has found application in various sectors such as in sensing and solar energy production. We report a single-step immobilization process based on affinity and achieved by genetically engineering the protein of interest to carry a hematite-binding peptide. Fabricated hematite nanoparticles were then investigated for the immobilization of the two biomolecules C-phycocyanin (CPC) and laccase from Bacillus pumilus (LACC) under mild conditions. Genetic engineering of biomolecules with a hematite-affinity peptide led to a higher extent of protein immobilization and enhanced the catalytic activity of the enzyme.

Ultrathin, flexible, and transparent polymer multilayer composites for the protection of silver surfaces.

Silver coatings at the nanoscale became of high interest for the integration of electronic functionalities on all kinds of objects for daily use. In these thin coatings, corrosion is a big problem as it destroys these thin layers and leads to a loss of conductivity due to missing bulk material. For protection of thin silver coatings against H(2)S induced corrosion, we developed nanocoatings based on the covalent layer-by-layer technique. We prepared composites by subsequent deposition of polyamines like polyethylenimine (PEI) or polyallylamine (PAAm) and polyanhydrides like poly(maleic anhydride-alt-methyl vinyl ether) (Gantrez) or poly(styrene-co-maleic anhydride) (PSMA). For the tuning of the hydrophobicity, the layers were terminated by reaction with palmitoylic acid derivatives. Reflectivity measurements, contact angle measurements, and AFM measurements were made to investigate how the coatings affect the surface properties. All coatings show a lower reflectivity below 450 nm compared to pure silver, depending on the number of layers deposited. The addition of a palmitoylic derivative to the surface increases the hydrophobicity, but only in case of the Gantrez-PVAm-composite, this approach leads to real hydrophobicity, reaching contact angles above 90°. AFM measurements show a decrease of the roughness of the polymer coated surfaces compared to the pure metal surfaces. Corrosion tests in a H(2)S atmosphere show a good protective effect of the palmitoyl-terminated composites. Martindale abrasion tests on coated textiles reveal a good stability of the prepared polymer composites.