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The longitudinal and transverse nuclear magnetic resonance relaxivity dispersion (NMRD) of 1 H in water induced by the paramagnetic relaxation enhancement (PRE) of dissolved lanthanide ions (Ln 3+ ) can become very strong. Longitudinal and transverse 1 H NMRD for Gd 3+ , Dy 3+ , Er 3+ and Ho 3+ were measured from 20 MHz/0.47 T to 1382 MHz/32.5 T, which extended previous studies by a factor of more than two in the frequency range. For the NMRD above 800 MHz, we used a resistive magnet, which exhibits reduced field homogeneity and stability in comparison to superconducting and permanent NMR magnets. These drawbacks were addressed by dedicated NMRD methods. In a comparison of NMRD measurements between 800 MHz and 950 MHz performed in both superconducting and resistive magnets, it was found that the longitudinal relaxivities were almost identical. However, the magnetic field fluctuations of the resistive magnet strongly perturbed the transverse relaxation. The longitudinal NMRDs are consistent with previous work up to 600 MHz. The transverse NMRD nearly scales with the longitudinal one with a factor close to one. The data can be interpreted within a PRE model that comprises the dipolar hyperfine interactions between the 1 H and the paramagnetic ions, as well as a Curie spin contribution that is dominant at high magnetic fields for Dy 3+ , Er 3+ and Ho 3+ . Our findings provide a solid methodological basis and valuable quantitative insights for future high-frequency NMRD studies, enhancing the measurement accuracy and applicability of PRE models for paramagnetic ions in aqueous solutions.

Quality control in a production plant shows its maximum potential in the form of inline measurements. Defects and imperfections can be detected early and directly, and waste and costs can be reduced. Nuclear Magnetic Resonance offers a wide range of applications but requires dedicated adaptation to the respective process and material conditions. A V-shaped low-field NMR sensor was developed for non-invasive inline measurements on anode slurries in a battery production plant. In battery production, inline monitoring of the quality of anode slurries is demanded, offering the possibility of predictive control of the following process steps. Methods of low-field NMR to determine flow properties were adapted to the desired application. Further, magnetic resonance imaging measurements were made to determine the flow properties of model substances and anode slurries, thus providing verification. The sensor measurements show the ability to measure the flow behavior of, amongst other fluids, anode slurries in a form suitable for inline quality control in a battery production plant.

To reduce unwanted fat bloom in the manufacturing and storage of chocolates, detailed knowledge of the chemical composition and molecular mobility of the oils and fats contained is required. Although the formation of fat bloom on chocolate products has been studied for many decades with regard to its prevention and reduction, questions on the molecular level still remain to be answered. Chocolate products with nut-based fillings are especially prone to undesirable fat bloom. The chemical composition of fat bloom is thought to be dominated by the triacylglycerides of the chocolate matrix, which migrate to the chocolate's surface and recrystallize there. Migration of oils from the fillings into the chocolate as driving force for fat bloom formation is an additional factor in the discussion. In this work, the migration was studied and confirmed by MRI, while the chemical composition of the fat bloom was measured by NMR spectroscopy and HPLC-MS, revealing the most important triacylglycerides in the fat bloom. The combination of HPLC-MS with NMR spectroscopy at 800 MHz allows for detailed chemical structure determination. A rapid routine was developed combining the two modalities, which was then applied to investigate the aging, the impact of chocolate composition, and the influence of hazelnut fillings processing parameters, such as the degree of roasting and grinding of the nuts or the mixing time, on fat bloom formation.

Inline analytics in industrial processes reduce operating costs and production rejection. Dedicated sensors enable inline process monitoring and control tailored to the application of interest. Nuclear Magnetic Resonance is a well-known analytical technique but needs adapting for low-cost, reliable and robust process monitoring. A V-shaped low-field NMR sensor was developed for inline process monitoring and allows non-destructive and non-invasive measurements of materials, for example in a pipe. In this paper, the industrial application is specifically devoted to the quality control of anode slurries in battery production. The characterization of anode slurries was performed with the sensor to determine chemical composition and detect gas inclusions. Additionally, flow properties play an important role in continuous production processes. Therefore, the in- and outflow effects were investigated with the V-shaped NMR sensor as a basis for the future determination of slurry flow fields.

Process monitoring and control require dedicated and reliable measures which reflect the status of the process under investigation. Although nuclear magnetic resonance is known to be a versatile analytical technique, it is only seldomly found in process monitoring. Single-sided nuclear magnetic resonance is one well known approach for being applied in process monitoring. The dedicated V-sensor is a recent approach that allows the inline investigation of materials in a pipe non-destructively and non-invasively. An open geometry of the radiofrequency unit is realized using a tailored coil, enabling the sensor to be applied for manifold mobile applications in in-line process monitoring. Stationary liquids were measured, and their properties were integrally quantified as the basis for successful process monitoring. The sensor, in its inline version, is presented along with its characteristics. An exemplary field of application is battery production in terms of anode slurries; thus, the first results on graphite slurries will demonstrate the added value of the sensor in process monitoring.

A time-dependent understanding of swelling characteristics and external stimuli behavior is crucial for the development and understanding of functional hydrogels. Magnetic resonance imaging (MRI) offers the opportunity to study three-dimensional (3D) soft materials nondestructively. This technique is already widely used as an image-based medical diagnostic tool and is applied here to evaluate complex structures of a hydrogel-a double network of chemically crosslinked casein enhanced with alginate-fabricated by 3D printing. When hydrogel disks immersed in four different liquid systems were analyzed, the material exhibited distinct system-dependent behavior characterized by rheological and mechanical measurements. Further material functionalization was achieved by macroscopic structuring of the hydrogel as an auxetic material based on a re-entrant honeycomb structure. MRI offers the advantage of monitoring overall changes in the area of the analyzed specimen and internal structural changes simultaneously. To assess the behavior of this complex structure, a series of short MRI measurements, each lasting 1.7 min, captured liquid diffusion and thus structural swelling behavior. A clear dependence of external and internal structural changes as a function of liquid properties causing these changes was observed. In conclusion, this approach might pave the way for prospective applications to monitor liquid diffusion into (e.g., vascularization) and swelling behavior of functional hydrogels.

Charge transport, diffusion properties, and glassy dynamics of blends of imidazolium-based ionic liquid (IL) and the corresponding polymer (polyIL) were examined by Pulsed-Field-Gradient Nuclear Magnetic Resonance (PFG-NMR) and rheology coupled with broadband dielectric spectroscopy (rheo-BDS). We found that the mechanical storage modulus (G') increases with an increasing amount of polyIL and G' is a factor of 10,000 higher for the polyIL compared to the monomer (GIL'= 7.5 Pa at 100 rad s -1 and 298 K). Furthermore, the ionic conductivity (σ0) of the IL is a factor 1000 higher than its value for the polymerized monomer with 3.4×10-4 S cm -1 at 298 K. Additionally, we found the Haven Ratio (HR) obtained through PFG-NMR and BDS measurements to be constant around a value of 1.4 for the IL and blends with 30 wt% and 70 wt% polyIL. These results show that blending of the components does not have a strong impact on the charge transport compared to the charge transport in the pure IL at room temperature, but blending results in substantial modifications of the mechanical properties. Furthermore, it is highlighted that the increase in σ0 might be attributed to the addition of a more mobile phase, which also possibly reduces ion-ion correlations in the polyIL.

As virtual reality (VR) has drastically evolved over the past few years, the field of applications of VR flourished way beyond the gaming industry. While commercial VR solutions might be available, there is a need to develop a workflow for specific applications. Bioprinting represents such an example. Here, complex 3D data is generated and needs to be visualized in the context of quality control. We demonstrate that the transfer to a commercially available VR software is possible by introducing an optimized workflow. In the present work, we developed a workflow for the visualization of the critical quality attribute (cQA) cell distribution in bioprinted (extrusion-based) samples in VR. The cQA cell distribution is directly influenced by the pre-processing step mixing of cell material in the bioink. Magnetic Resonance Imaging (MRI) was used as an analytical tool to generate spatially resolved 2.5 and 3D data of the bioprinted objects. A sample with poor quality in respect of the cQA cell distribution was identified as its inhomogeneous cell distribution could be displayed spatially resolved in VR. The described workflow facilitates the usage of VR as a tool for quality inspection in the field of bioprinting and represents a powerful tool for visualization of complex 3D MRI data., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Gretzinger, Schmieg, Guthausen and Hubbuch.)

The current trend for ultra-high-field magnetic resonance imaging (MRI) technologies opens up new routes in clinical diagnostic imaging as well as in material imaging applications. MRI selectivity is further improved by using contrast agents (CAs), which enhance the image contrast and improve specificity by the paramagnetic relaxation enhancement (PRE) mechanism. Generally, the efficacy of a CA at a given magnetic field is measured by its longitudinal and transverse relaxivities r 1 and r 2 , i.e., the longitudinal and transverse relaxation rates T 1 -1 and T 2 -1 normalized to CA concentration. However, even though basic NMR sensitivity and resolution become better in stronger fields, r 1 of classic CA generally decreases, which often causes a reduction of the image contrast. In this regard, there is a growing interest in the development of new contrast agents that would be suitable to work at higher magnetic fields. One of the strategies to increase imaging contrast at high magnetic field is to inspect other paramagnetic ions than the commonly used Gd(III)-based CAs. For lanthanides, the magnetic moment can be higher than that of the isotropic Gd(III) ion. In addition, the symmetry of electronic ground state influences the PRE properties of a compound apart from diverse correlation times. In this work, PRE of water 1 H has been investigated over a wide range of magnetic fields for aqueous solutions of the lanthanide containing polyoxometalates [Dy III (H 2 O) 4 GeW 11 O 39 ] 5- ( Dy-W 11 ), [Er III (H 2 O) 3 GeW 11 O 39 ] 5- ( Er-W 11 ) and [{Er III (H 2 O)(CH 3 COO)(P 2 W 17 O 61 )} 2 ] 16- ( Er 2 -W 34 ) over a wide range of frequencies from 20 MHz to 1.4 GHz. Their relaxivities r 1 and r 2 increase with increasing applied fields. These results indicate that the three chosen POM systems are potential candidates for contrast agents, especially at high magnetic fields.

The removal or degradation of particulate organic matter is a crucial part in biological wastewater treatment. This is even more valid with respect to aerobic granular sludge and the impact of particulate organic matter on the formation and stability of the entire granulation process. Before the organic part of the particulate matter can be hydrolyzed and finally degraded by the microorganism, the particles have to be transported towards and retained within the granulated biomass. The understanding of these processes is currently very limited. Thus, the present study aimed at visualizing the transport of particulate organic matter into and through an aerobic granular sludge bed. Magnetic Resonance Imaging (MRI) was successfully applied to resolve the different fractions of a granular sludge bed over time and space. Quantification and merging of 3D data sets allowed for a clear determination of the particle distribution within the granular sludge bed. Dextran coated super paramagnetic iron oxide nanoparticles (SPIONs, d p  =  38 ± 10 nm) served as model particles for colloidal particles. Microcrystalline cellulose particles ( d p  = 1-20 μm) tagged with paramagnetic iron oxide were applied as a reference for toilet paper, which is a major fraction of particulate matter in domestic wastewater. The results were supplemented by the use of real wastewater particles with a size fraction between 28 and 100 μm. Colloidal SPIONs distributed evenly over the granular sludge bed penetrating the granules up to 300 μm. Rinsing the granular sludge bed proved their immobilization. Microcrystalline cellulose and real wastewater particles in the micrometer range accumulated in the void space between settled granules. An almost full retention of the wastewater particles was observed within the first 20 mm of the granular sludge bed. Moreover, the formation of particle layers indicates that most of the micrometer-sized particles are not attached to the biomass and remain mobile. Consequently, these particles are released into the bulk phase when the granulated sludge bed is resuspended., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2020 The Author(s).)

Milk protein fractionation by microfiltration membranes is an established but still growing field in dairy technology. Even under cross-flow conditions, this filtration process is impaired by the formation of a deposit by the retained protein fraction, mainly casein micelles. Due to deposition formation and consequently increased overall filtration resistance, the mass flow of the smaller whey protein fraction declines within the first few minutes of filtration. Currently, there are only a handful of analytical techniques available for the direct observation of deposit formation with opaque feed media and membranes. Here, we report on the ongoing development of a non-invasive and non-destructive method based on magnetic resonance imaging (MRI), and its application to characterise deposit layer formation during milk protein fractionation in ceramic hollow fibre membranes as a function of filtration pressure and temperature, temporally and spatially resolved. In addition, the chemical composition of the deposit was analysed by reversed phase high pressure liquid chromatography (RP-HPLC). We correlate the structural information gained by in-situ MRI with the protein amount and composition of the deposit layer obtained by RP-HPLC. We show that the combination of in-situ MRI and chemical analysis by RP-HPLC has the potential to allow for a better scientific understanding of the pressure and temperature dependence of deposit layer formation.

With the aim to synthesize soluble cluster molecules, the silver salt of (4-( tert -butyl)phenyl)methanethiol [AgSCH 2 C 6 H 4 t Bu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag 115 S 34 (SCH 2 C 6 H 4 t Bu) 47 (dpph) 6 ] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31 P/ 109 Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution.

Hypothesis: The accuracy of the inner water droplet size determination of W/O/W emulsions upon water diffusion measurement by diffusion NMR was evaluated. The resulting droplet size data were compared to the results acquired from the diffusion measurement of a highly water soluble marker compound with low permeability in the oil layer of a W/O/W emulsion, which provide a closer representation of the actual droplet size. Differences in droplet size data obtained from water and the marker were ascribed to extra-droplet water diffusion., Experiments: The diffusion data of the tetramethylammonium cation marker were measured using high-resolution pulsed field gradient NMR, whereas the water diffusion was measured using both low-resolution and high-resolution NMR. Different data analysis procedures were evaluated to correct for the effect of extra-droplet water diffusion on the accuracy of water droplet size analysis., Findings: Using the water diffusion data, the use of a low measurement temperature and diffusion delay Δ could reduce the droplet size overestimation resulting from extra-droplet water diffusion, but this undesirable effect was inevitable. Detailed analysis of the diffusion data revealed that the extra-droplet diffusion effect was due to an exchange between the inner water phase and the oil phase, rather than by exchange between the internal and external aqueous phase. A promising data analysis procedure for retrieving reliable size data consisted of the application of Einstein's diffusion law to the experimentally determined diffusion distances. This simple procedure allowed determining the inner water droplet size of W/O/W emulsions upon measurement of water diffusion by low-resolution NMR at or even above room temperature., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Magnetic Resonance Imaging is a powerful tool for the investigation of a biofilms' physical structure determining mass transport behavior which is of major importance in biofilm research. The entire biofilm is imaged in situ non-invasively and non-destructively on a meso-scale. In this study, different contrast agents were applied to study the biofilm's properties with the focus on mass transport, which is achieved by varying the contrast agents with respect to their NMR and interaction properties. The spatio-temporal tracking of these cluster, molecular and particulate contrast agents in biofilms was achieved by T1-, T2-weighted and proton density images during short (20h) and long (14 d) term exposures. The best biofilm surface visualization was observed when applying a new high spin coordination cluster (Fe10Gd10) showing a high affinity to the biofilm's surface and a fast immobilization within minutes. Contrarily, the small molecular contrast agents show no immobilization and fully penetrated into the biofilm. A concentration equilibrium was observed which was confirmed in back diffusion experiments. Interactions between larger nanoparticulate contrast agents and the biofilm required hours to achieve immobilization. Thus, the penetration depth into the biofilm is predominantly size-dependent. Here, it is shown that biofilm surface interactions can be observed in situ and spatio-temporarily resolved. The reported methodology demonstrates a new means to explore mass transfer of various substances in biofilms., Statement of Significance: In biofilm research, the investigation of the biofilms' physical structure is of high relevance for the understanding of mass transport processes. However, commonly used imaging techniques for biofilm imaging such as CLSM or electron microscopy rarely visualize the real biofilm due to their invasiveness and destructiveness. Magnetic Resonance Imaging (MRI) represents the ideal tool to image the biofilm in situ, non-invasively and non-destructively with a spatial resolution of several 10μm. To gain specific structural and functional information, a variety of MRI contrast agents (molecular and particulate) was applied with different properties for the first time. Results elucidate the interactions between the biofilms' surface and the contrast agents and open a new field for biotechnological applications by functional contrast enhancement., (Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

The application of engineered nanoparticles (ENP) such as iron-based ENP in environmental systems or in the human body inevitably raises the question of their mobility. This also includes aspects of product optimization and assessment of their environmental fate. Therefore, the key aim was to investigate the mobility of iron-based ENP in water-saturated porous media. Laboratory-scale transport experiments were conducted using columns packed with quartz sand as model solid phase. Different superparamagnetic iron oxide nanoparticles (SPION) were selected to study the influence of primary particle size (d(P)=20 nm and 80 nm) and surface functionalization (plain, -COOH and -NH2 groups) on particle mobility. In particular, the influence of natural organic matter (NOM) on the transport and retention behaviour of SPION was investigated. In our approach, a combination of conventional breakthrough curve (BTC) analysis and magnetic resonance imaging (MRI) to non-invasively and non-destructively visualize the SPION inside the column was applied. Particle surface properties (surface functionalization and resulting zeta potential) had a major influence while their primary particle size turned out to be less relevant. In particular, the mobility of SPION was significantly increased in the presence of NOM due to the sorption of NOM onto the particle surface resulting in a more negative zeta potential. MRI provided detailed spatially resolved information complementary to the quantitative BTC results. The approach can be transferred to other porous systems and contributes to a better understanding of particle transport in environmental porous media and porous media in technical applications., (Copyright © 2015 Elsevier B.V. All rights reserved.)