Quaternary ammonium-based coating of textiles is effective against bacteria and viruses with a low risk to human health.

While the global healthcare system is slowly recovering from the COVID-19 pandemic, new multi-drug-resistant pathogens are emerging as the next threat. To tackle these challenges there is a need for safe and sustainable antiviral and antibacterial functionalized materials. Here we develop an 'easy-to-apply' procedure for the surface functionalization of textiles, rendering them antiviral and antibacterial and assessing the performance of these textiles. A metal-free quaternary ammonium-based coating was applied homogeneously and non-covalently to hospital curtains. Abrasion, durability testing, and aging resulted in little change in the performance of the treated textile. Additionally, qualitative and quantitative antibacterial assays on Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumanii revealed excellent antibacterial activity with a CFU reduction of 98-100% within only 4 h of exposure. The treated curtain was aged 6 months before testing. Similarly, the antiviral activity tested according to ISO-18184 with murine hepatitis virus (MHV) showed > 99% viral reduction with the functionalized curtain. Also, the released active compounds of the coating 24 ± 5 µg mL-1 revealed no acute in vitro skin toxicity (IC50: 95 µg mL-1) and skin sensitization. This study emphasizes the potential of safe and sustainable metal-free textile coatings for the rapid antiviral and antibacterial functionalization of textiles.

Kinetics of Guest-Induced Structural Transitions in Metal-Organic-Framework MIL-53(Al)-NH2 Probed by High-Pressure Nuclear Magnetic Resonance.

A nuclear magnetic resonance (NMR) study of a pore opening in amino-functionalized metal-organic framework (MOF) MIL-53(Al) in response to methane pressure variation is presented. Variations of both NMR signal intensities and transversal relaxation rates for methane are found to reveal hysteretic structural transitions in the MOF material, which are smeared out over broad pressure ranges. Experiments with pressure reversals upon an incomplete adsorption/desorption gave deeper insight into the microscopic transition mechanisms. These experiments have unequivocally proven that the non-stepwise pore opening/closing transitions observed in the experiments are governed by a distribution of the opening/closing pressures over different MOF crystallites, for example, due to a distribution of the crystal sizes or shapes. The slow kinetics of the structural transitions measured in the hysteresis regime revealed a complex free energy landscape for the phase transition process.

The Structural and Mechanical Basis for Passive-Hydraulic Pine Cone Actuation.

The opening and closing of pine cones is based on the hygroscopic behavior of the individual seed scales around the cone axis, which bend passively in response to changes in environmental humidity. Although prior studies suggest a bilayer architecture consisting of lower actuating (swellable) sclereid and upper restrictive (non- or lesser swellable) sclerenchymatous fiber tissue layers to be the structural basis of this behavior, the exact mechanism of how humidity changes are translated into global movement are still unclear. Here, the mechanical and hydraulic properties of each structural component of the scale are investigated to get a holistic picture of their functional interplay. Measurements of the wetting behavior, water uptake, and mechanical measurements are used to analyze the influence of hydration on the different tissues of the cone scales. Furthermore, their dimensional changes during actuation are measured by comparative micro-computed tomography (µ-CT) investigations of dry and wet scales, which are corroborated and extended by 3D-digital image correlation-based displacement and strain analyses, biomechanical testing of actuation force, and finite element simulations. Altogether, a model allowing a detailed mechanistic understanding of pine cone actuation is developed, which is a prime concept generator for the development of biomimetic hygromorphic systems.

Taking compact NMR to monitoring real reactions in large-scale chemical industries-General considerations and learnings from a lab-scale test case.

The considerations for use of compact nuclear magnetic resonance in a large-scale industrial environment clearly differ from those in academic and educational settings and even from those in smaller companies. In the first part of this article, these differences will be discussed along with the additional requirements that need to be fulfilled for successful applicability in different use cases. In the second part of the article, outcomes from different research activities aiming to fulfill these requirements will be presented with a focus on an online reaction-monitoring study on a lab-scale nucleophilic chlorination reaction.

Cold-adaptation of a methacrylamide gelatin towards the expansion of the biomaterial toolbox for specialized functionalities in tissue engineering.

Tissue regeneration is witnessing a significant surge in advanced medicine. It requires the interaction of scaffolds with different cell types for efficient tissue formation post-implantation. The presence of tissue subtypes in more complex organs demands the co-existence of different biomaterials showing different hydrolysis rate for specialized cell-dependent remodeling. To expand the available toolbox of biomaterials with sufficient mechanical strength and variable rate of enzymatic degradation, a cold-adapted methacrylamide gelatin was developed from salmon skin. Compared with mammalian methacrylamide gelatin (GelMA), hydrogels derived from salmon GelMA displayed similar mechanical properties than the former. Nevertheless, salmon gelatin and salmon GelMA-derived hydrogels presented characteristics common of cold-adaptation, such as reduced activation energy for collagenase, increased enzymatic hydrolysis turnover of hydrogels, increased interconnected polypeptides molecular mobility and lower physical gelation capability. These properties resulted in increased cell-remodeling rate in vitro and in vivo, proving the potential and biological tolerance of this mechanically adequate cold-adapted biomaterial as alternative scaffold subtypes with improved cell invasion and tissue fusion capacity.

Hygroscopic motions of fossil conifer cones.

Conifer cones represent natural, woody compliant structures which move their scales as passive responses to changes in environmental humidity. Here we report on water-driven opening and closing motions in coalified conifer cones from the Eemian Interglacial (approx. 126,000-113,000 years BP) and from the Middle Miocene (approx. 16.5 to 11.5 million years BP). These cones represent by far the oldest documented evidence of plant parts showing full functionality of such passive hydraulically actuated motion. The functional resilience of these structures is far beyond the biological purpose of seed dispersal and protection and is because of a low level of mineralization of the fossils. Our analysis emphasizes the functional-morphological integrity of these biological compliant mechanisms which, in addition to their biological fascination, are potentially also role models for resilient and maintenance-free biomimetic applications (e.g., adaptive and autonomously moving structures including passive hydraulic actuators).

Water dynamics in different biochar fractions.

Biochar is a carbonaceous porous material deliberately applied to soil to improve its fertility. The mechanisms through which biochar acts on fertility are still poorly understood. The effect of biochar texture size on water dynamics was investigated here in order to provide information to address future research on nutrient mobility towards plant roots as biochar is applied as soil amendment. A poplar biochar has been stainless steel fractionated in three different textured fractions (1.0-2.0 mm, 0.3-1.0 mm and <0.3 mm, respectively). Water-saturated fractions were analyzed by fast field cycling (FFC) NMR relaxometry. Results proved that 3D exchange between bound and bulk water predominantly occurred in the coarsest fraction. However, as porosity decreased, water motion was mainly associated to a restricted 2D diffusion among the surface-site pores and the bulk-site ones. The X-ray µ-CT imaging analyses on the dry fractions revealed the lowest surface/volume ratio for the coarsest fraction, thereby corroborating the 3D water exchange mechanism hypothesized by FFC NMR relaxometry. However, multi-micrometer porosity was evidenced in all the samples. The latter finding suggested that the 3D exchange mechanism cannot even be neglected in the finest fraction as previously excluded only on the basis of NMR relaxometry results. X-ray µ-CT imaging showed heterogeneous distribution of inorganic materials inside all the fractions. The mineral components may contribute to the water relaxation mechanisms by FFC NMR relaxometry. Further studies are needed to understand the role of the inorganic particles on water dynamics.

Non-invasive analysis of swelling in polymer dispersions by means of time-domain(TD)-NMR.

In this contribution, we discuss the potential of low-field time-domain(TD)-NMR to study the swelling of (aqueous) polymer dispersions by a volatile solvent. Due to the sensitivity of transverse relaxation times (T2) to swelling-induced changes in the molecular dynamics of the polymer component, the effects of swelling can be measured without spectral resolution. The measurement is performed on polymer dispersions in native state with solids contents around 50% in a non-invasive way without separating the polymeric phase and the water phase from each other. Using acetone in two polyurethane (PU) dispersions with different hard phase contents, we explore the sensitivity of the method and present a data evaluation strategy based on multicomponent fitting and proton balancing. Furthermore, we report exchange continualization as a further effect that needs to be taken into account for correct interpretation of the data.

Robust spatially resolved pressure measurements using MRI with novel buoyant advection-free preparations of stable microbubbles in polysaccharide gels.

MRI of fluids containing lipid coated microbubbles has been shown to be an effective tool for measuring the local fluid pressure. However, the intrinsically buoyant nature of these microbubbles precludes lengthy measurements due to their vertical migration under gravity and pressure-induced coalescence. A novel preparation is presented which is shown to minimize both these effects for at least 25 min. By using a 2% polysaccharide gel base with a small concentration of glycerol and 1,2-distearoyl-sn-glycero-3-phosphocholine coated gas microbubbles, MR measurements are made for pressures between 0.95 and 1.44 bar. The signal drifts due to migration and amalgamation are shown to be minimized for such an experiment whilst yielding very high NMR sensitivities up to 38% signal change per bar.

Towards quantification of butadiene content in styrene-butadiene block copolymers and their blends with general purpose polystyrene (GPPS) and the relation between mechanical properties and NMR relaxation times.

The properties of styrene-butadiene-styrene (SBS) block copolymers do not only depend on the butadiene content and the degree of polymerisation but also on their chain architecture. In this contribution we present the results of a low-field time domain (TD) NMR study in which the transverse relaxation behaviour of different SBS block copolymers was analysed and correlated with findings from mechanical testing on pure and blended materials and transmission electron microscopy data which provide information on the microphase separation. The results indicate that while a straightforward determination of the butadiene content as in blended materials like ABS is not possible for these materials, the TD-NMR results correlate quite well with the mechanical performance of blends from SBS block copolymers with general purpose polystyrene (GPPS), i.e. industrial grade homopolymer polystyrene. Temperature-dependent experiments on pure and blended materials revealed a slight reduction in the softening temperature of the GPPS fraction in the blends.

Investigations of Li-containing SiCN(O) ceramics via 7Li MAS NMR.

Lithium-containing silicon (oxy)carbonitride ceramics (SiCN(O):Li) were synthesized via precursor-to-ceramic-transformation of Li-containing (poly)silazanes. The precursors were obtained by lithiation of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane with n-butyllithium and by reaction of a commercial poly(organosilazane) VL20 with metallic lithium. The annealing treatment was carried out at temperatures between 200 and 1400 degrees C in argon (DeltaT=200 degrees C) and yielded Li-containing silicon (oxy)carbonitride. X-ray powder diffraction revealed that the resulting SiCN(O):Li ceramics were basically amorphous up to temperatures of 1000 degrees C and formed LiSi(2)N(3), graphite and silicon carbide as crystalline phases at higher temperatures. (7)Li MAS NMR spectroscopy was carried out to investigate the structure of the Li-containing phases and to study the reaction path of metallic Li with polysilazane. Based on the NMR spectra, there is almost no difference found in the chemical shift of the SiCN(O):Li ceramics obtained at different temperatures. Accordingly, Li is assigned to be mainly coordinated to N and O present as contaminant element. Relaxation time measurements showed that the most mobile Li(+) species seems to be present in the product obtained in the pyrolysis temperature range between 600 and 1000 degrees C.

Single-sided and semisingle-sided NMR sensors for highly diffusive samples: application to bottled beverages.

Single-sided NMR sensors such as the NMR-MOUSE have been very successfully implemented for quality control applications in the rubber and polymer industries. More recently, single-sided NMR was also applied in characterization of the fat components in foods. Both industrial polymers and the fat components in food exhibit relatively low self-diffusion coefficients on the order of 5x10(-11) m2/s or lower. The application of conventional single-sided NMR to highly mobile, watery phases in foods and beverages is hampered by the strong magnetic field gradient present in standard single-sided NMR devices. In this contribution, we present both a single-sided NMR sensor with a reduced magnetic field gradient and another ("semisingle-sided") sensor design with an open sample bay using a single-sided RF coil. The latter design allows much better sensitivity without sacrificing the necessary open access needed for measurements on entire food packages such as bottles. As a first application, the sensors were used for determining the oxygen content in bottles with superoxygenated table water.

Oral magnetic resonance imaging contrast agent based on Ilex paraguayensis herbal extract.

In this article we demonstrate the potential of herbal extracts from yerba mate (Ilex paraguayensis) as an oral contrast agent for MRI. At typical drinking concentrations, yerba mate acts as a "biphasic" contrast agent with T1 weighting at short echo times and T2 weighting at echo times greater than about 40 ms. Based on data obtained from X-ray fluorescence elemental analysis, NMR relaxometry, and ESR we identify the relaxation agent in the extract as a low-molecular-weight manganese complex. Yerba mate exhibits an unusually high manganese content that is readily available for hot water extraction. Despite the high elemental manganese levels in I. paraguayensis extract, no manganese-related toxicity of yerba mate has been observed even among heavy yerba mate drinkers, indicating that the manganese in the extract has only a very low bioavailability. Imaging results on staff and patient volunteers demonstrate good contrasting of the GI tract. The relaxation studies of the contrast agent show a sensitivity to pH that is consistent with imaging results from stomach and small bowel.

Proton electron double resonance imaging of free radical distribution in environmental science applications--first results and perspectives.

In this contribution, we explore the potential of proton electron double resonance imaging (PEDRI) in environmental science (hydrogeological) applications. After a discussion of the hydrogeological motivation for studies of free radical transport in environmental matrices, we present results from first experiments that show the principal applicability of the PEDRI technique to sediment samples. Field-cycled (FC) relaxation time contrast is identified as a possible source of artifacts in samples in which strong concentration gradients of the free radical phase are present. Furthermore, an outlook is given on how PEDRI can help in observations of the local interplay among contaminants, water and nonaqueous liquid phases.

Continuous wave MRI diffusion study of water in bentonite clay.

Three-layered clay minerals such as montmorillonite (bentonite) exhibit very short transverse relaxation times. This is especially true for samples with relatively low water contents in the region of 20% to 30%, which is the water content typically used in environmental technology applications (e.g., as a mineral liner material for landfills). The diffusion of water in samples with such short transverse relaxation times can be measured with NMR by observing the moisture gradients or isotope tracer fronts propagating through appropriately prepared samples by means of continuous wave MRI. The first results from such studies on bentonite clays are presented in this paper.

In vivo observation of oxygen-supersaturated water in the human mouth and stomach.

In recent years, a rising number of different table waters supersaturated with oxygen have hit the market with claims of both positive health effects and an increase in athletic performance. A scientific validation of these claims needs additional knowledge on the fate of the oxygen supersaturation in the human digestive tract. Taking advantage of the fact that molecular oxygen is paramagnetic, MRI can be applied to observe the behavior of oxygen-supersaturated water after oral uptake. In this contribution we report results obtained on several healthy volunteers. On the basis of these results we can conclude that oral uptake of oxygen-supersaturated drinking water with a low content in CO(2) leads to a considerable increase in the oxygenation in the lumen of the oral cavity and of the stomach. Comparing the observed contrast changes with those brought about by conventional contrast agents, even the highly oxygen-supersaturated waters still perform rather poorly.

Reduced apparent longitudinal relaxation times in slice-selective experiments in strong magnetic field gradients.

In contrast to transverse nuclear magnetizations, longitudinal spin magnetizations are usually considered as insensitive to magnetic field gradients. While this assumption is valid for homogeneously excited samples, the apparent longitudinal spin relaxation behavior of thin magnetization slices in high magnetic fields is strongly modified by diffusion. In this contribution, we present the results of theoretical and experimental studies on this effect. Furthermore, possible applications and the impact on different types of NMR techniques using strong magnetic field gradients are discussed.

Direct investigation of the fate of NAPL contaminations in a hydrating cement matrix by means of magnetic resonance techniques.

The behavior of nonwatery solvent phases in hydrating cement pastes is of great interest in the context of solidification of wastes containing such phases. In a recent study, the influence of various solvents on the hydration kinetics of cement was studied. In this paper, we present results on the changes in the behavior of the solvent phases themselves during setting of the cement pastes. The methods used in the studies were NMR relaxometry and pulsed field gradient (PFG) NMR diffusometry. To study selectively the behavior of the non-aqueous-phase liquid (NAPL) phases, heavy water was used in the preparation of the cement pastes. The experimental results are in good agreement with the observations from earlier studies concerning the behavior of toluene in hydrating cement. For aliphatic solvents (cyclooctane, n-hexanol), indications for surprisingly large networks of connected droplets in the cement matrices are found.

NMR relaxometry study of cement hydration in the presence of different oxidic fine fraction materials.

NMR relaxometry has been applied to study hydrating cements for about 25 years now. The most important advantage over other experimental approaches is the possibility to conduct non-destructive measurements with a time resolution of minutes. NMR relaxometry data thus can help to identify details in the time course of cement hydration that possibly would be overlooked in other experiments with lower temporal resolution. Time-resolved information on cement hydration kinetics can provide interesting insights into the impact of oxidic additive materials on cement hydration. For PbO, a very strong delay was observed which then was systematically studied. An explanation for this delay is suggested.

Spatial and temporal observations of adsorption and remobilization of heavy metal ions in a sandy aquifer matrix using Magnetic Resonance Imaging.

The exploration of the transport and matrix interactions of heavy metal ions in the subsurface environment under natural conditions is an important field of research in environmental science and technology. Most commonly, column tests are used for a first assessment of the transport behavior. Classical column tests fall short with regard to the spatial and temporal resolution; however, these detailed data are needed for proper upscaling. Hence, providing spatially and temporally resolved data on the distribution of environmentally relevant concentrations of heavy metal ions in a water-wet aquifer matrix poses a major challenge to analytical chemistry. In this contribution, we present the results of Magnetic Resonance Imaging (MRI) studies in which submilligram quantities of heavy metal ions where either fed conventially through the column or locally injected into saturated sand packings. The subsequent transport and mobilization was monitored at a high spatial and temporal resolution. The results from a local injection show that the test design of column tests has not yet come to an end and that column tests under MRI-control may be used as a model system for, e.g., remediation techniques.