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Understanding and describing the dynamics of proteins is one of the major challenges in biology. Here, we use multifield variable-temperature NMR longitudinal relaxation (R1) measurements to determine the hierarchical activation energies of motions of four different proteins two small globular proteins (GB1 and the SH3 domain of α-spectrin), an intrinsically disordered protein (the C-terminus of the nucleoprotein of the Sendai virus, Sendai Ntail), and an outer membrane protein (OmpG). The activation energies map the motions occurring in the side chains, in the backbone, and in the hydration shells of the proteins. We were able to identify similarities and differences in the average motions of the proteins. We find that the NMR relaxation properties of the four proteins do share similar features. The data characterizing average backbone motions are found to be very similar, the same for methyl group rotations, and similar activation energies are measured. The main observed difference occurs for the intrinsically disordered Sendai Ntail, where we observe much lower energy of activation for motions of protons associated with the protein-solvent interface as compared to the others. We also observe variability between the proteins regarding side chain 15N relaxation of lysine residues, with a higher activation energy observed in OmpG. This hints at strong interactions with negatively charged lipids in the bilayer and provides a possible mechanistic clue for the "positive-inside" rule for helical membrane proteins. Overall, these observations refine the understanding of the similarities and differences between hierarchical dynamics in proteins.Zintl phases with nominal 9-4-9 formulas are very interesting for their potential applications as thermoelectric materials. However, the formation of such phases usually requires divalent transition metals, for example, Zn, Mn, and Cd, which are covalently bonded to the pnictogen atoms. In this report, for the first time, two Mg-containing compounds with such structures as Sr9Mg4.45(1)Bi9 and Sr9Mg4.42(1)Sb9 were synthesized and their structures were determined by the single-crystal X-ray diffraction method. Both title compounds crystallize in the orthorhombic space group Pnma and are isostructural with Ca9Mn4.41(1)Sb9, which features complex polyanion structures compared to the classical 9-4-9 phases. For Sr9Mg4.45(1)Bi9, its low thermal conductivity, combined with its high electrical conductivity and moderate Seebeck coefficient, leads to a decent figure of merit of 0.57 at 773 K, which obviously prevails in the unoptimized 9-4-9 phases. The discovery of such Mg-containing 9-4-9 phases is very significant, as the discovery not only enriches the structure map of the well-known 9-4-9 family but also provides very valuable thermoelectric candidates surely deserving of more in-depth investigation.We report a reactive flux technique using the common reagent P2S5 and metal precursors developed to circumvent the synthetic bottleneck for producing high-quality single- and mixed-metal two-dimensional (2D) thiophosphate materials. For the monometallic compound, M2P2S6 (M = Ni, Fe, and Mn), phase-pure materials were quickly synthesized and annealed at 650 °C for 1 h. Crystals of dimensions of several millimeters were grown for some of the metal thiophosphates using optimized heating profiles. The homogeneity of the bimetallic thiophosphates MM'P2S6 (M, M' = Ni, Fe, and Mn) was elucidated using energy-dispersive X-ray spectroscopy and Rietveld refinement. The quality of the selected materials was characterized by transmission electron microscopy and atomic force microscopy measurements. We report two novel bimetallic thiophosphates, MnCoP2S6 and FeCoP2S6. The Ni2P2S6 and MnNiP2S6 flux reactions were monitored in situ using variable-temperature powder X-ray diffraction to understand the formation reaction pathways. The phases were directly formed in a single step at approximately 375 °C. The work functions of the semiconducting materials were determined and ranged from 5.28 to 5.72 eV.Superelastic aerogels with excellent electrical conductivity, reversible compressibility, and high durability hold great potential for varied emerging applications, ranging from wearable electronics to multifunctional scaffolds. In the present work, superelastic MXene/reduced graphene oxide (rGO) aerogels are fabricated by mixing MXene and GO flakes, followed by a multistep reduction of GO, freeze-casting, and finally an annealing process. By optimizing both the composition and reducing conditions, the resultant aerogel shows a reversible compressive strain of 95%, surpassing all current reported values. The conducting MXene/rGO network provides fast electron transfer and stable structural integrity under compression/release cycles. When assembled into compressible supercapacitors, 97.2% of the capacitance was retained after 1000 compression/release cycles. Moreover, the high conductivity and porous structure also enabled the fabrication of a piezoresistive sensor with high sensitivity (0.28 kPa-1), wide detection range (up to 66.98 kPa), and ultralow detection limit (∼60 Pa). click here It is envisaged that the superelasticity of MXene/rGO aerogels offers a versatile platform for utilizing MXene-based materials in a wide array of applications including wearable electronics, electromagnetic interference shielding, and flexible energy storage devices.It has been over half a century since the last class of antibiotics active against the most problematic Gram-negative bacteria was approved by the Food and Drug Administration (FDA). The major challenge with developing antibiotics to treat these infections is not drug-target engagement but rather the inability of most small molecules to traverse the Gram-negative membranes, be retained, and accumulate within the cell. Despite an abundance of lead compounds, limited understanding of the physicochemical properties needed for compound accumulation (or avoidance of efflux) in Gram-negative bacteria has precluded a generalizable approach for developing Gram-negative antibiotics. Indeed, in many instances, despite years of intensive derivatization efforts and the synthesis of hundreds of compounds aimed at building in Gram-negative activity, little or no progress has been made in expanding the spectrum of activity for many Gram-positive-only antibiotics. In this Account, we describe the discovery and successful applications of a promising strategy for enhancing the accumulation of Gram-positive-only antibiotics as a means of imbuing compounds with broad-spectrum activity.
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