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Bacterial infections in irregular and branched confinements pose significant therapeutic challenges. Despite their high antimicrobial efficacy, enzyme-mimicking nanoparticles (nanozymes) face difficulties in achieving localized catalysis at distant infection sites within confined spaces. Incorporating nanozymes into microrobots enables the delivery of catalytic agents to hard-to-reach areas, but poor nanoparticle dispersibility and distribution during fabrication hinder their catalytic performance. To address these challenges, a nanozyme-shelled microrobotic platform is introduced using magnetic microcapsules with collective and adaptive mobility for automated navigation and localized catalysis within complex confinements. Using double emulsions produced from microfluidics as templates, iron oxide and silica nanoparticles are assembled into 100-µm microcapsules, which self-organize into multi-unit, millimeter-size assemblies under rotating magnetic fields. These microcapsules exhibit high peroxidase-like activity, efficiently catalyzing hydrogen peroxide to generate reactive oxygen species (ROS). Notably, microcapsule assemblies display remarkable collective navigation within arched and branched confinements, reaching the targeted apical regions of the tooth canal with high accuracy. Furthermore, these nanozyme-shelled microrobots perform rapid catalysis in situ and effectively kill biofilms on contact via ROS generation, enabling localized antibiofilm action. This study demonstrates a facile method of integrating nanozymes onto a versatile microrobotic platform to address current needs for targeted therapeutic catalysis in complex and confined microenvironments., (© 2024 The Author(s). Advanced Healthcare Materials published by Wiley‐VCH GmbH.)

Cationic biocides play a crucial role in the disinfection of domestic and healthcare surfaces. Due to the rise of bacterial resistance towards common cationic disinfectants like quaternary ammonium compounds (QACs), the development of novel actives is necessary for effective infection prevention and control. Toward this end, a series of 15 chimeric biscationic amphiphilic compounds, bearing both ammonium and phosphonium residues, were prepared to probe the structure and efficacy of mixed cationic ammonium-phosphonium structures. Compounds were obtained in two steps and good yields, with straightforward and chromatography-free purifications. Antibacterial activity evaluation of these compounds against a panel of seven bacterial strains, including two MRSA strains as well as opportunistic pathogen A. baumannii, were encouraging, as low micromolar inhibitory activity was observed for multiple structures. Alkyl chain length on the ammonium group was, as expected, a major determinant of bioactivity. In addition, high therapeutic indexes (up to 125-fold) for triphenyl phosphonium-bearing amphiphiles were observed when comparing antimicrobial activity to mammalian cell lysis activity., (© 2024 Wiley-VCH GmbH.)

New regimes of energy density in energetic materials may be achieved by replacement of oxidizing nitro groups with stronger oxidants such as oxychlorine species. We report the energetic material 1,3-di-tert-butyltetrazolium-5-imidoperchloratomanganese(II) 2, which crystallizes as an oligomeric cubane cluster. Bomb calorimetry on the amorphous, solvent-free phase gives an energy density of at least 40±3 MJ L - , higher than hydrocarbon combustion in air, more than twice that of traditional energetic nitramines, and ≈70 % higher than that of the unmetalated tetrazolium perchlorate salt without metal linkage. The effects of solid-state structure, charge, and lattice energy on the energy of 2 are discussed., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The preparation and characterization of the cocrystalline solid-organic sodium ion electrolyte NaClO 4 (DMF) 3 (DMF=dimethylformamide) is described. The crystal structure of NaClO 4 (DMF) 3 reveals parallel channels of Na + and ClO 4 - ions. Pressed pellets of microcrystalline NaClO 4 (DMF) 3 exhibit a conductivity of 3×10 -4  S cm -1 at room temperature with a low activation barrier to conduction of 25 kJ mol -1 . SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55-65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO 4 (DMF) 3 , permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report a synthetic method to enhance the electrocatalytic activity of birnessite for the oxygen evolution reaction (OER) by intercalating Ni(2+) ions into the interlayer region. Electrocatalytic studies showed that nickel (7.7 atomic %)-intercalated birnessite exhibits an overpotential (η) of 400 mV for OER at an anodic current of 10 mA cm(-2) . This η is significantly lower than the η values for birnessite (η≈700 mV) and the active OER catalyst β-Ni(OH)2 (η≈550 mV). Molecular dynamics simulations suggest that a competition among the interactions between the nickel cation, water, and birnessite promote redox chemistry in the spatially confined interlayer region., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first chemical syntheses of complex, bis-Strychnos alkaloids (-)-sungucine (1), (-)-isosungucine (2), and (-)-strychnogucine B (3) from (-)-strychnine (4) is reported. Key steps included (1) the Polonovski-Potier activation of strychnine N-oxide; (2) a biomimetic Mannich coupling to forge the signature C23-C5' bond that joins two monoterpene indole monomers; and (3) a sequential HBr/NaBH3 CN-mediated reduction to fashion the ethylidene moieties in 1-3. DFT calculations were employed to rationalize the regiochemical course of reactions involving strychnine congeners., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first synthetic manganese tetrazene complexes are described as a redox pair comprising anionic [Mn(N4 Ad2 )2 ](-) (1) and neutral Mn(N4 Ad2 )2 (2) complexes (N4 Ad2 =[Ad-N-N=N-N-Ad](2-) ). Compound 1 is obtained in two forms as lithium salts, one as a cationic Li2 Mn cluster, and one as a Mn-Li 1D ionic polymer. Compound 1 is electronically described as a Mn(III) center with two [N4 Ad2 ](2-) ligands. The one-electron oxidized 2 is crystalized in two morphologies, one as pure 2 and one as an acetonitrile adduct. Despite similar composition, the behavior of 2 differs in the two morphologies. Compound 2-MeCN is relatively air and temperature stable. Crystalline 2, on the other hand, exhibits a compositional, dynamic disorder wherein the tetrazene metallacycle ring-opens into a metal imide/azide complex detectable by X-ray crystallography and FTIR spectroscopy. Electronic structure of 2 was examined by EPR and XPS spectroscopies and DFT calculations, which indicate 2 is best described as a Mn(III) ion with an anion radical delocalized across the two ligands through spin-polarization effects., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Concise biomimetic syntheses of the Strychnos-Strychnos-type bis-indole alkaloids (-)-leucoridine A (1) and C (2) were accomplished through the biomimetic dimerization of (-)-dihydrovalparicine (3). En route to 3, the known alkaloids (+)-geissoschizoline (8) and (-)-dehydrogeissoschizoline (10) were also prepared. DFT calculations were employed to elucidate the mechanism, which favors a stepwise aza-Michael/spirocyclization sequence over the alternate hetero-Diels-Alder cycloaddition reaction., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)