Johannes Leisen

Highly Tunable Molecular Sieving and Adsorption Properties of Mixed-Linker Zeolitic Imidazolate Frameworks

Nanoporous zeolitic imidazolate frameworks (ZIFs) form structural topologies equivalent to zeolites. ZIFs containing only one type of imidazole linker show separation capability for limited molecular pairs. We show that the effective pore size, hydrophilicity, and organophilicity of ZIFs can be continuously and drastically tuned using mixed-linker ZIFs containing two types of linkers, allowing their use as a more general molecular separation platform. We illustrate this remarkable behavior by adsorption and diffusion measurements of hydrocarbons, alcohols, and water in mixed-linker ZIF-8(x)-90(100-x) materials with a large range of crystal sizes (338 nm to 120 μm), using volumetric, gravimetric, and PFG-NMR methods. NMR, powder FT-Raman, and micro-Raman spectroscopy unambiguously confirm the mixed-linker nature of individual ZIF crystals. Variation of the mixed-linker composition parameter (x) allows continuous control of n-butane, i-butane, butanol, and isobutanol diffusivities over 2-3 orders of magnitude and control of water and alcohol adsorption especially at low activities.

Direct synthesis of single-walled aminoaluminosilicate nanotubes with enhanced molecular adsorption selectivity

Internal functionalization of single-walled nanotubes is an attractive, yet difficult challenge in nanotube materials chemistry. Here we report single-walled metal oxide nanotubes with covalently bonded primary amine moieties on their inner wall, synthesized through a one-step approach. Conclusive molecular-level structural information on the amine-functionalized nanotubes is obtained through multiple solid-state techniques. The amine-functionalized nanotubes maintain a high carbon dioxide adsorption capacity while significantly suppressing the adsorption of methane and nitrogen, thereby leading to a large enhancement in adsorption selectivity over unfunctionalized nanotubes (up to four-fold for carbon dioxide/methane and ten-fold for carbon dioxide/nitrogen). The successful synthesis of single-walled nanotubes with functional, covalently-bound organic moieties may open up possibilities for new nanotube-based applications that are currently inaccessible to carbon nanotubes and other related materials.

Quantitative magnetic resonance imaging of fluid distribution and movement in textiles

Magnetic resonance imaging (MRI) is used to characterize fluid distribution and movement in textiles. The standard spin-echo sequence commonly used in the medical field is not suitable for quantitative imaging of moisture profiles in textiles because the echo time duration allows too much time for signal loss. The signal attenuation is greater for low moisture content and less pronounced for polypropylene than it is for cotton and other materials with higher surface concentrations of water-binding functional groups. A single-point imaging (SPI) sequence, also called constant-time imaging, provides quantitative profile images on industrially relevant timescales. This is demonstrated by measuring profiles of water in wet unbacked nylon cut-pile carpet during a drying process. A comprehensive introduction to MRI is provided with special consideration of water, textiles, and the relevant chemical and physical influences on the MRI time signal and resulting image.

Biomarkers of whale shark health: a metabolomic approach.

In a search for biomarkers of health in whale sharks and as exploration of metabolomics as a modern tool for understanding animal physiology, the metabolite composition of serum in six whale sharks (Rhincodon typus) from an aquarium collection was explored using 1H nuclear magnetic resonance (NMR) spectroscopy and direct analysis in real time (DART) mass spectrometry (MS). Principal components analysis (PCA) of spectral data showed that individual animals could be resolved based on the metabolite composition of their serum and that two unhealthy individuals could be discriminated from the remaining healthy animals. The major difference between healthy and unhealthy individuals was the concentration of homarine, here reported for the first time in an elasmobranch, which was present at substantially lower concentrations in unhealthy whale sharks, suggesting that this metabolite may be a useful biomarker of health status in this species. The function(s) of homarine in sharks remain uncertain but it likely plays a significant role as an osmolyte. The presence of trimethylamine oxide (TMAO), another well-known protective osmolyte of elasmobranchs, at 0.1–0.3 mol L−1 was also confirmed using both NMR and MS. Twenty-three additional potential biomarkers were identified based on significant differences in the frequency of their occurrence between samples from healthy and unhealthy animals, as detected by DART MS. Overall, NMR and MS provided complementary data that showed that metabolomics is a useful approach for biomarker prospecting in poorly studied species like elasmobranchs.

A model of through-air drying of tufted textile materials

Abstract A transient two-dimensional mathematical model is developed to simulate the through-air drying process for tufted textile materials. The heat and mass transfer in a cylindrical porous medium and the air flowing around it are analyzed separately. First, thermal and mass circuits are used to analyze the simultaneous heat and mass transfer within the porous medium. Then, the equations of the conservation of mass and energy are written for the drying medium. The resulting system of three non-linear differential equations is numerically solved by an implicit finite difference method. The numerical solutions are compared with experimental drying results obtained using magnetic resonance imaging (MRI) and a laboratory through-air dryer (LTAD).

Structure Elucidation of Mixed-Linker Zeolitic Imidazolate Frameworks by Solid-State 1H CRAMPS NMR Spectroscopy and Computational Modeling

Mixed-linker zeolitic imidazolate frameworks (ZIFs) are nanoporous materials that exhibit continuous and controllable tunability of properties like effective pore size, hydrophobicity, and organophilicity. The structure of mixed-linker ZIFs has been studied on macroscopic scales using gravimetric and spectroscopic techniques. However, it has so far not been possible to obtain information on unit-cell-level linker distribution, an understanding of which is key to predicting and controlling their adsorption and diffusion properties. We demonstrate the use of (1)H combined rotation and multiple pulse spectroscopy (CRAMPS) NMR spin exchange measurements in combination with computational modeling to elucidate potential structures of mixed-linker ZIFs, particularly the ZIF 8-90 series. All of the compositions studied have structures that have linkers mixed at a unit-cell-level as opposed to separated or highly clustered phases within the same crystal. Direct experimental observations of linker mixing were accomplished by measuring the proton spin exchange behavior between functional groups on the linkers. The data were then fitted to a kinetic spin exchange model using proton positions from candidate mixed-linker ZIF structures that were generated computationally using the short-range order (SRO) parameter as a measure of the ordering, clustering, or randomization of the linkers. The present method offers the advantages of sensitivity without requiring isotope enrichment, a straightforward NMR pulse sequence, and an analysis framework that allows one to relate spin diffusion behavior to proposed atomic positions. We find that structures close to equimolar composition of the two linkers show a greater tendency for linker clustering than what would be predicted based on random models. Using computational modeling we have also shown how the window-type distribution in experimentally synthesized mixed-linker ZIF-8-90 materials varies as a function of their composition. The structural information thus obtained can be further used for predicting, screening, or understanding the tunable adsorption and diffusion behavior of mixed-linker ZIFs, for which the knowledge of linker distributions in the framework is expected to be important.

Control of Microfluidic Flow in Amphiphilic Fabrics

Woven textile fabrics were designed and constructed from hydrophilic and hydrophobic spun yarns to give planar substrates containing amphiphilic microchannels with defined orientations and locations. Polypropylene fibers were spun to give hydrophobic yarns, and the hydrophilic yarns were spun from a poly(ethylene terephthalate) copolyester. Water wicking rates into the fabrics were measured by video microscopy from single drops, relevant for point-of-care microfluidic diagnostic devices, and from reservoirs. intra-yarn microchannels in the hydrophilic polyester yarns were shown to selectively transport aqueous fluids, with the flow path governed by the placement of the hydrophilic yarns in the fabric. By comparing fluid transport in fabric constructions with systematic variations in the numbers of adjacent parallel and orthogonal hydrophilic yarns, it was found that inter-yarn microchannels significantly increased wicking rates. Simultaneous wicking of an aqueous and hydrocarbon fluid into the hydrophilic and hydrophobic microchannels of an amphiphilic fabric was successfully demonstrated. The high degree of interfacial contact and micrometer-scale diffusion lengths of such coflowing immiscible fluid streams inside amphiphilic fabrics suggest potential applications as highly scalable and affordable microcontactors for liquid-liquid extractions.

IN-PLANE MOISTURE TRANSPORT IN PAPER DETECTED BY MAGNETIC RESONANCE IMAGING

Magnetic resonance imaging was used to visualize in-plane moisture transport in laboratory-made handsheets, heavy paperboard, and polyethylene-coated paperboard. Beginning with wet samples sealed on both surfaces, the moisture content was reduced through evaporation from the outside edges. The diffusion of moisture to the outside edges, i.e., in the plane of the sheets, was found to be isotropic with respect to the sample machine and cross directions. Isotropic in-plane moisture diffusion was observed for samples exhibiting a relatively high degree of fiber orientation, and under conditions of forced convection with air flow rates up to 10 L/min past the outside edges.

Aminosilanes Grafted to Basic Alumina as CO2 Adsorbents—Role of Grafting Conditions on CO2 Adsorption Properties

Solid oxide-supported amine sorbents for CO2 capture are amongst the most rapidly developing classes of sorbent materials for CO2 capture. Herein, basic γ supports are used as hosts for amine sites through the grafting of 3-aminopropyltrimethoxysilane to the alumina surface under a variety of conditions, yielding the expected surface-grafted alkylamine groups, as demonstrated by FTIR spectroscopy and (29)Si and (13)C cross-polarization magic-angle spinning (CPMAS NMR) spectroscopy. Grafting amine sites on the surface in the presence of water leads to a high density of amine sites on the surface whereas simultaneously creating a unique type of aluminum species on the surface, as demonstrated by both 1D and 2D (27)Al MAS NMR spectroscopy. The thus prepared sorbents result in higher CO2 adsorption capacities and amine efficiencies compared to sorbents prepared in the absence of water or similar amine loading sorbents prepared using silica supports. In situ FTIR spectra of the sorbents exposed to CO2 at various pressures show no distinct difference in the nature of the adsorbed CO2 species on alumina- versus silica-supported amines, whereas water adsorption isotherms show that the improved performance of the amine-grafted alumina support is not a consequence of retained water on the more hydrophobic aminoalumina materials. The findings demonstrate that amine-grafted, basic alumina materials can be tuned to be more efficient than the corresponding silica-supported materials at comparable amine loadings, further demonstrating that the properties of amine sites can be tuned by controlling or adjusting the support surface properties.

Understanding DABCO Nanorotor Dynamics in Isostructural Metal-Organic Frameworks

Flexible framework dynamics present in the subset of metal-organic frameworks known as soft porous crystals give rise to interesting structural properties that are unique to this class of materials. In this work, we use experiments and molecular simulation to understand the highly dynamic nanorotor behavior of the 1,4-diazabicyclo[2.2.2]octane (DABCO) ligand in the pillared Zn-DMOF and Zn-DMOF-TM (TM = tetramethyl) structures. While DABCO is known to be displaced in the presence of water in the parent Zn-DMOF structure, the Zn-DMOF-TM variation is highly stable even after adsorbing significant amounts of water vapor. The dynamics of DABCO in the presence of water guest molecules is therefore also explored in the Zn-DMOF-TM structure via in situ NMR and IR experiments. This analysis shows that the rotational motion of the DABCO linkers is dependent on water content, but not a likely source of water instability because the dynamics are fast and largely unaffected by the presence of methyl functional groups.