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Significantly higher quantities were observed in untoasted wood compared to medium or highly toasted wood. These findings provide new insights into the molecular origin of taste changes due to oak aging.The assembly of heterometallic complexes capable of activating dioxygen is synthetically challenging. Tacedinaline Here, we report two different approaches for the preparation of heterometallic superoxide complexes [PhL2CrIII-η1-O2][MX]2 (PhL = -OPh2SiOSiPh2O-, MX+ = [CoCl]+, [ZnBr]+, [ZnCl]+) starting from the CrII precursor complex [PhL2CrII]Li2(THF)4. The first strategy proceeds via the exchange of Li+ by [MX]+ through the addition of MX2 to [PhL2CrII]Li2(THF)4 before the reaction with dioxygen, whereas in the second approach a salt metathesis reaction is undertaken after O2 activation by adding MX2 to [PhL2CrIII-η1-O2]Li2(THF)4. The first strategy is not applicable in the case of redox-active metal ions, such as Fe2+ or Co2+, as it leads to the oxidation of the central chromium ion, as exemplified with the isolation of [PhL2CrIIICl][CoCl]2(THF)3. However, it provided access to the hetero-bimetallic complexes [PhL2CrIII-η1-O2][MX]2 ([MX]+ = [ZnBr]+, [ZnCl]+) with redox-inactive flanking metals incorporated. The second strategy can be applied not only for redox-inactive but also for redox-active metal ions and led to the formation of chromium(III) superoxide complexes [PhL2CrIII-η1-O2][MX]2 (MX+ = [ZnCl]+, [ZnBr]+, [CoCl]+). The results of stability and reactivity studies (employing TEMPO-H and phenols as substrates) as well as a comparison with the alkali metal series (M+ = Li+, Na+, K+) confirmed that although the stability is dependent on the Lewis acidity of the counterions M and the number of solvent molecules coordinated to those, the reactivity is strongly dependent on the accessibility of the superoxide moiety. Consequently, replacement of Li+ by XZn+ in the superoxides leads to more stable complexes, which at the same time behave more reactive toward O-H groups. Hence, the approaches presented here broaden the scope of accessible heterometallic O2 activating compounds and provide the basis for further tuning of the reactivity of [RL2CrIII-η1-O2]M2 complexes.The synthesis of polymeric materials that simultaneously possess multiple excellent mechanical properties and high-efficient self-healability at room temperature is always a huge challenge. Here, we report the synthesis of a transparent polyurea material that can self-heal at room temperature with the aid of water and, meanwhile, has multiple remarkable mechanical performances, including super-high strength, excellent toughness, and large stretchability. Thanks to the synergistic enhancement of both dynamic imine bonds and hierarchical hydrogen bonds within the networks, the resulting polyureas have a world-record tensile strength of 41.2 MPa when compared with other polyurethanes that can self-heal at room temperature and, at the same time, a large breaking strain of 823.0% and a superior toughness of 127.2 MJ/m3. Besides the influence of imine bonds, the mechanical properties of the polyureas are also strongly related to the density and strength of the hierarchical hydrogen bonds within the polyurea networks, and these two factors could be finely controlled by adjusting the mass ratio of the soft segments with different chain lengths and the types of diisocyanates used for polyurea synthesis, respectively. More importantly, the highly dynamic characteristic of both imine bonds and hierarchical hydrogen bonds within the polyureas endows the materials with repeated water-enabled room-temperature self-healing capacity with a high healing efficiency of 92.2%. Moreover, the polyureas can also be recycled or remolded under mild conditions by the hot-pressing or dissolution/casting process. The synthesized polyureas also show great potential in damping applications with a loss factor larger than 0.3 over the temperature range from 12 to 75 °C. It is believed that polyureas with super-high and well-tunable mechanical properties and high-efficient room-temperature self-healing ability have great potential to substitute traditional irreparable polymers in diverse practical applications.Icosahedral virus-like particles (VLPs) derived from bacteriophages Qβ and PP7 encapsulating small-ultrared fluorescent protein (smURFP) were produced using a versatile supramolecular capsid disassemble-reassemble approach. The generated fluorescent VLPs display identical structural properties to their nonfluorescent analogs. Encapsulated smURFP shows indistinguishable photochemical properties to its unencapsulated counterpart, exhibits outstanding stability toward pH, and produces bright in vitro images following phagocytosis by macrophages. In vivo imaging allows the biodistribution to be imaged at different time points. Ex vivo imaging of intravenously administered encapsulated smURFP reveals a localization in the liver and kidneys after 2 h blood circulation and substantial elimination after 16 h of imaging, highlighting the potential application of these constructs as noninvasive in vivo imaging agents.We have previously reported the crystal structures of endothelin-1 (ET-1)-bound, ligand-free, and antagonist bosentan-bound forms of the thermostabilized ET type B receptor (ETB). Although other agonist-bound structures of ETB have been determined, the interactions for high-affinity binding and ETB receptor activation, as well as the roles of rearrangement of the hydrogen-bond network surrounding the ligand in G protein activation, remain elusive. ET-1, a 21-amino acid residue peptide, plays fundamental roles in basal vascular tone, sodium balance, cell proliferation, and stress-responsive regulation. We studied the interactions between the ET-1(8-21) peptide and ETB in the ligand binding and activation of ETB using a series of Ala-substituted ET-1(8-21) analogues and the mutated ETB. We found that while D8, L17, D18, I20, and W21 were responsible for high-affinity binding and potent G protein activation, Y13 and F14 in the helical region of ET-1 are prerequisites for the full activation of ETB via interactions near the extracellular side.

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