Catalysis is vital to industrial chemistry, and the optimization of catalytic reactors attracts considerable resources. It has proven challenging to correlate the active regions in heterogeneous catalyst beds with morphology and to monitor multistep reactions within the bed. We demonstrate techniques, using magnetic resonance imaging and para-hydrogen (p-H2) polarization, that allow direct visualization of gas-phase flow and the density of active catalyst in a packed-bed microreactor, as well as control over the dynamics of the polarized state in space and time to facilitate the study of subsequent reactions. These procedures are suitable for characterizing reactors and reactions in microfluidic devices where low sensitivity of conventional magnetic resonance would otherwise be the limiting factor.
Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals and functional materials as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with –NH2/-NH-alkyl moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using either NH2/NHalkyl-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.
We demonstrate the creation and observation of para-hydrogen-induced polarization in heterogeneous hydrogenation reactions. Wilkinson's catalyst, RhCl(PPh3)3, supported on either modified silica gel or a polymer, is shown to hydrogenate styrene into ethylbenzene and to produce enhanced spin polarizations, observed through NMR, when the reaction was performed with H2 gas enriched in the para spin isomer. Furthermore, gaseous phase para-hydrogenation of propylene to propane with two catalysts, the Wilkinson's catalyst supported on modified silica gel and Rh(cod)(sulfos) (cod = cycloocta-1,5-diene; sulfos = -O3S(C6H4)CH2C(CH2PPh2)3) supported on silica gel, demonstrates heterogeneous catalytic conversion resulting in large spin polarizations. These experiments serve as a direct verification of the mechanism of heterogeneous hydrogenation reactions involving immobilized metal complexes and can be potentially developed into a practical tool for producing catalyst-free fluids with highly polarized nuclear spins for a broad range of hyperpolarized NMR and MRI applications.
Sum frequency generation (SFG) spectroscopy is a powerful tool for probing the orientations of molecules at surfaces and interfaces, but oversimplification in the treatment of the nonresonant (NR) contribution has obscured some fundamental limitations in the analysis of SFG spectra. These difficulties are demonstrated for the case of polystyrene thin films. The NR signal invariably distorts the spectrum and can cause changes in the spectra even in the absence of actual structural changes. The NR signal originates not only from the substrate but from all materials in the system and should not be modeled as having a frequency-independent amplitude. Because of its complicated nature, NR signal must be isolated experimentally in order to obtain meaningful results. Suppression of NR signal, however, causes a different type of distortion, due to apodization of the resonant signal in the time-domain. Experimental methods need to be refined to take these limitations into account and to obtain unique spectral parameters to be used for orientation determination.
Gas‐phase MRI phantom: Magnetic resonance imaging (MRI) in the gas phase was demonstrated using para‐hydrogen‐induced polarization. H2 enriched in the para (antiparallel) spin state and propylene gas were flowed over solid‐supported Wilkinson's catalyst, and the product, propane gas, was collected in an NMR tube. Enhanced signal intensities were observed in the images of phantoms placed inside the NMR tube (see picture).
bThiopeptides are small (12-to 17-amino-acid), heavily modified peptides of bacterial origin. This antibiotic family, with more than 100 known members, is characterized by the presence of sulfur-containing heterocyclic rings and dehydrated residues within a macrocyclic peptide structure. Thiopeptides, including micrococcin P1, have garnered significant attention in recent years for their potent antimicrobial activity against bacteria, fungi, and even protozoa. Micrococcin P1 is known to target the ribosome; however, like those of other thiopeptides, its biosynthesis and mechanisms of self-immunity are poorly characterized. We have discovered an isolate of Staphylococcus epidermidis harboring the genes for thiopeptide production and self-protection on a 24-kb plasmid. Here we report the characterization of this plasmid, identify the antimicrobial peptide that it encodes, and provide evidence of a target replacement-mediated mechanism of self-immunity.
We examine consequences of the non-Boltzmann nature of probability distributions for one-particle kinetic energy, momentum, and velocity for finite systems of classical hard spheres with constant total energy and nonidentical masses. By comparing two cases, reflecting walls (NVE or microcanonical ensemble) and periodic boundaries (NVEPG or molecular dynamics ensemble), we describe three consequences of the center-of-mass constraint in periodic boundary conditions: the equipartition theorem no longer holds for unequal masses, the ratio of the average relative velocity to the average velocity is increased by a factor of [N/(N-1)]1/2, and the ratio of average collision energy to average kinetic energy is increased by a factor of N/(N-1). Simulations in one, two, and three dimensions confirm the analytic results for arbitrary dimension.
Over 85% of all chemical industry products are made using catalysts (1), with the overwhelming majority of these employing heterogeneous catalysts (2) functioning at the gas-solid interface (3). Consequently, optimizing catalytic reactor design attracts much effort. Such optimization relies on heat transfer and fluid dynamics modeling coupled to surface reaction kinetics (4). The complexity of these systems demands many approximations, which can only be tested with experimental observations (5,6) of quantities such as temperature, pressure, concentrations, flow rates, etc. One essential measurement is a map of the spatial variation in temperature throughout the catalyst bed. We present here the first non-invasive maps of gas temperatures in catalyst-filled reactors, including high spatial resolution maps in microreactors enabled by parahydrogen. The thermal maps reveal energy flux patterns whose length scale correlates with the catalyst packing.
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