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    IR-MALDI Mass Spectrometry Imaging with Plasma Post-Ionization of Nonpolar Metabolites
    (Columbus, Ohio : American Chemical Society, 2022) Schneemann, Julian; Schäfer, Karl-Christian; Spengler, Bernhard; Heiles, Sven
    Ambient mass spectrometry imaging (MSI) methods come with the advantage of visualizing biomolecules from tissues with no or minimal sample preparation and operation under atmospheric-pressure conditions. Similar to all other MSI methodologies, however, ambient MSI modalities suffer from a pronounced bias toward either polar or nonpolar analytes due to the underlying desorption and ionization mechanisms of the ion source. In this study, we present the design, construction, testing, and application of an in-capillary dielectric barrier discharge (DBD) module for post-ionization of neutrals desorbed by an ambient infrared matrix-assisted laser desorption/ionization (IR-MALDI) MSI source. We demonstrate that the DBD device enhances signal intensities of nonpolar compounds by up to 104 compared to IR-MALDI without affecting transmission of IR-MALDI ions. This allows performing MSI experiments of mouse tissue and Danaus plexippus caterpillar tissue sections, visualizing the distribution of sterols, fatty acids, monoglycerides, and diglycerides that are not detected in IR-MALDI MSI experiments. The pronounced signal enhancement due to IR-MALDI-DBD compared to IR-MALDI MSI enables mapping of nonpolar analytes with pixel resolutions down to 20 μm in mouse brain tissue and to discern the spatial distribution of sterol lipids characteristic for histological regions of D. plexippus.
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    Indirect reduction of CO2 and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes
    (Cambridge : RSC, 2021) Liu, Xin; Werner, Thomas
    The reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed. © The Royal Society of Chemistry 2021.
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    Comparison of transition metal (Fe, Co, Ni, Cu, and Zn) containing tri-metal layered double hydroxides (LDHs) prepared by urea hydrolysis
    (Cambridge : RSC, 2019) Naseem, Sajid; Gevers, Bianca; Boldt, Regine; Labuschagné, Frederick J. W. J.; Leuteritz, Andreas
    This paper details a successful synthesis and comparison of a range of tri-metal hydrotalcite-like layered double hydroxides (LDHs) using urea hydrolysis. Transition-metal-substituted MgMAl-LDHs were synthesized with M = Fe, Co, Ni, Cu or Zn. 5 mol% and 10 mol% substitutions were performed, where Mg was substituted with Co, Ni, Cu and Zn, and Al with Fe. The successful synthesis of crystalline MgMAl-LDHs was confirmed using X-ray powder diffraction (XRD) analysis. Energy-dispersive X-ray (EDX) spectroscopy was used to identify substituted metals and determine changes in composition. Changes in morphology were studied using scanning electron microscopy (SEM). Thermogravimetric analysis was used to determine the effect of Fe-, Co-, Ni-, Cu- or Zn-substitution on the thermal degradation of the MgMAl-LDH phase. The structure, morphology and thermal behavior of the LDHs were shown to be influenced by the substituted transition metals. The observed thermal stability took the order MgNiAl- > MgFeAl- = MgAl- ≥ MgCoAl- > MgCuAl- > MgZnAl-LDH. The urea hydrolysis method was shown to be a simple preparation method for well-defined crystallite structures with large hexagonal platelets and good distribution of transition metal atoms in the substituted LDHs. © 2019 The Royal Society of Chemistry.