A plausible mechanism is described based on intramolecular hydrogen bonding in the gas phase, which creates a small difference of proton affinities between the epimers. More importantly, this mechanism allows the explanation of the different ionization efficiencies of the epimers based on kinetic control of the ionization process, where ionization initially takes place at the hydroxyl group with subsequent proton transfer to a basic carbon atom. The barrier for this transfer differs between the epimers and is in direct competition with H2O elimination from the protonated hydroxyl group. The “hidden” site of high gas phase basicity was revealed through computational calculations and appears to be inaccessible via direct protonation.In this work, we demonstrate a facile synthesis of UiO-66-NH2 metal-organic framework (MOF)/oxidized single-walled carbon nanotubes (ox-SWCNTs) composite at room temperature. Acetic acid (HAc) was used as a modulator to manipulate the morphology of the MOF in these composites. With a zirconium oxide cluster (Zr) to 2-aminoteraphthalate linker (ATA) 11.42 ratio and acetic acid modulator, we achieved predominately heterogeneous MOF growth on the sidewalls of CNTs. Understanding the growth mechanism of these composites was facilitated by conducting DFT calculations to investigate the interactions between ox-SWCNTs and the MOF precursors. The synthesized composites combine both microporosity of the MOF and electrical conductivity of the SWCNTs. Gas sensing tests demonstrated higher response for UiO-66-NH2/ox-SWCNT hybrid toward dry air saturated with dimethyl methylphosphonate (DMMP) vapor compared to oxidized single-walled carbon nanotubes (ox-SWCNTs) alone.Amide hydrogen-deuterium exchange (HDX) has long been used to determine regional flexibility and binding sites in proteins; however, the data are too sparse for full structural characterization. Experiments that measure HDX rates, such as HDX-NMR, have far higher throughput compared to structure determination via X-ray crystallography, cryo-EM, or a full suite of NMR experiments. Data from HDX-NMR experiments encode information on the protein structure, making HDX a prime candidate to be supplemented by computational algorithms for protein structure prediction. We have developed a methodology to incorporate HDX-NMR data into ab initio protein structure prediction using the Rosetta software framework to predict structures based on experimental agreement. To demonstrate the efficacy of our algorithm, we examined 38 proteins with HDX-NMR data available, comparing the predicted model with and without the incorporation of HDX data into scoring. Methotrexate order The root-mean-square deviation (rmsd, a measure of the average atomic distance between superimposed models) of the predicted model improved by 1.42 Å on average after incorporating the HDX-NMR data into scoring. The average rmsd improvement for the proteins where the selected model rmsd changed after incorporating HDX data was 3.63 Å, including one improvement of more than 11 Å and seven proteins improving by greater than 4 Å, with 12/15 proteins improving overall. Additionally, for independent verification, two proteins that were not part of the original benchmark were scored including HDX data, with a dramatic improvement of the selected model rmsd of nearly 9 Å for one of the proteins. Moreover, we have developed a confidence metric allowing us to successfully identify near-native models in the absence of a native structure. Improvement in model selection with a strong confidence measure demonstrates that protein structure prediction with HDX-NMR is a powerful tool which can be performed with minimal additional computational strain and expense.Ultraviolet matrix-assisted laser desorption ionization mass spectrometry imaging (UV-MALDI-MSI) is a powerful tool to visualize bacterial metabolites in microbial colonies and in biofilms. However, a challenge for the method is the efficient extraction of analytes from deeper within the bacterial colonies and from the cytoplasm of individual cells during the matrix coating step. Here, we used a pulsed infrared (IR) laser of 2.94 μm wavelength to disrupt and ablate bacterial cells without a prior coating with a MALDI matrix. Instead, tissue water or, in some experiments, in addition a small amount of glycerol was exploited for the deposition of the IR laser energy and for supporting the ionization of the analytes. Compared to water, glycerol exhibits a lower vapor pressure, which prolonged the available measurement time window within an MSI experiment. Mass spectra were acquired with a hybrid Synapt G2-S HDMS instrument at a pixel size of 120 μm. A frequency-quadrupled q-switched NdYAG laser with 266 nm wavel2 approach for the highest analytical sensitivity, we characterized the expansion dynamics of the particle plume as generated by the IR laser. Here, we recorded the total ion count and the intensities of selected signals registered from P. aeruginosa samples as a function of the interlaser delay and buffer gas pressure in the ion source. The data revealed that the IR-MALDI-2 ion signals are primarily generated from slow particles having mean velocities of ∼10 m/s. Interestingly, two different pressure/delay time regimes of the optimized ionization efficiency for phospholipids and smaller metabolites, respectively, were revealed, a result pointing to yet-unknown convoluted reaction cascades. The described IR-MALDI-2 method could be a helpful new tool for a microbial mass spectrometry imaging of small molecules requiring little sample preparation.The discovery of pyramidal inversion has continued to impact modern organic and organometallic chemistry. Sequential alkylation reactions of an N-heterocyclic carbene (NHC) ligated dicarbondiphosphide 1 with RI (R = Me, Et, or iBu) and ZnMe2 give rise to the highly stereoselective synthesis of cis-1,3-diphosphetanes 3. cis-3 is conformationally favorable at room temperature, whereas inversion to trans-3 is observed at 110 °C. One-electron oxidation of cis-3 with Fc+(BArF) (Fc = [Fe(C5H5)2]; BArF = [B(3,5-(CF3)2C6H3)4)]-) leads to the stereoselective formation of trans-1,3-diphosphetane radical cation salts 3•+(BArF), which can be reversibly transformed to cis-3 upon one-electron reduction. Salts 3•+(BArF) represent the first examples of 1,3-diphosphetane radical cations. These results provide a potential application of planar four-membered heterocycle-based building blocks for electrically fueled molecular switches.