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Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic-organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10-25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.Reactions of lanthanoid metals with tris(pentafluorophenyl)bismuth or pentafluorophenylsilver and two widely disparate formamidines, N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH) and N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH) have been investigated as possible redox transmetallation/protolysis (RTP) syntheses of lanthanoid formamidinates. https://www.selleckchem.com/products/BIBW2992.html Thus, [Ln(DFForm)3(thf)] (Ln = Lu, 1, Yb, 2, Tm, 3, Er, 4, Ho, 5, Dy, 6; thf = tetrahydrofuran), [Ln(DFForm)3(thf)2] (Ln = Tb, 7, Gd, 8, Sm, 9, Nd, 10), and [Yb(DippForm)2(thf)2]·2thf (11) complexes were obtained from an excess of lanthanoid metals, [Bi(C6F5)3]·0.5diox (diox = 1,4-dioxane) and the appropriate formamidine. Reaction of neodymium and [Bi(C6F5)3]·0.5diox with the bulkier DippFormH in thf resulted in C-F activation and formation of [Nd(DippForm)2F(thf)2] (12) and o-HC6F4O(CH2)4N(Dipp)CH[double bond, length as m-dash]N(Dipp) (Dipp = 2,6-di-isopropylphenyl). Although the reaction of erbium and [Bi(C6F5)3]·0.5diox with DippFormH was not complete afteial as an oxidative replacement for diarylmercurials in RTP syntheses of lanthanoid formamidinates but [AgC6F5(py)] does not.Unprecedented metal-metal bonded oxido-carboxylato bridged mixed valence tetraruthenium cluster [(acac)6Ru(μ3-O)2(μ-CH3COO)3] 1 (S = 1/2) (acac = acetylacetonate) with Ru4(μ3-O)2 "butterfly" core has been achieved via the reaction of Ru(acac)2(CH3CN)2 with excess CH3COONa (Ru CH3COONa = 1 15) in refluxing EtOH-H2O (5 1). Structural analysis of 1 ascertained a unique Ru-Ru bonded (Ru2-Ru3 2.5187(6) Å (DFT 2.560 Å)) Ru2(Ru-Ru)(μ3-O)2 butterfly core, unlike the reported other Fe4 or Mn4 derived "butterfly" core. The connectivity of Ru4(μ3-O)2 core in 1 with three Ru2(μ-CH3COO)3 and two each Ru-(acac)2/Ru-acac units resulted in interconnected four RuO6 octahedral entities. The doubly bridged μ3-O2- ions of the nearly planar central metal-metal bonded Ru2O2 core (Ru2-Ru3, "body" or "hinge") linked to the remaining two "wing-tip" Ru atoms (Ru1 and Ru4). Complex 1 with a S = 1/2 spin state displayed paramagnetically shifted 1H NMR over a wide chemical shift range in CDCl3 (δ, 13 to -30 ppm) and a metal based anisotropic EPR (g1 = 2.17, g2 = 2.01, g3 = 1.86; Δg = g1-g3 = 0.31 and 〈g〉 = [1/3(g12 + g22 + g32]1/2 = 2.01) at 100 K in CH3CN-toluene. The metal based one-electron reversible oxidation at 0.49 V and reduction at 0.485 V versus SCE of 1 led to the EPR inactive (even at 4 K) spin-coupled RuIIIRuIIIRuIVRuIV (S = 0) and RuIIIRuIIIRuIIIRuIII (S = 0) electronic configurations for 1+ and 1-, respectively. Mixed valence 1 and 1+ exhibited low-energy near-infrared (NIR) absorption bands at 1350 nm and 1156 nm, respectively, in CH3CN. A combined experimental (UV-vis-NIR and EPR spectroelectrochemistry) and theoretical (DFT) analysis indicated a delocalised mixed valence form of 1 (Ru2(Ru-Ru)(μ3-O)2).Synthesis and characterisation of a dithiadiaza chelator NSNS2A, as well as copper complexes thereof are reported in this paper. Solution structures of copper(i/ii) complexes were calculated using density functional theory (DFT) and validated by both NMR and EPR spectroscopy. DFT calculations revealed a switch in the orientation of tetragonal distortion upon protonation, which might be responsible for poor stability of the Cu(II)NSNS2A complex in aqueous media, whilst the same switch in tetragonal distortion was experimentally observed by changing the solvent. The chelator was radiolabeled with 64Cu and evaluated using PET/MRI in rats. Despite a favorable redox potential to stabilize the cuprous state in vivo, the 64Cu(II)NSNS2A complex showed suboptimal stability compared to its tetraazamacrocyclic analogue, 64Cu(TE2A), with a significant 64Cu uptake in the liver.Magnetic particle/carbon hybrid structures are promising candidates for high performance microwave absorbing materials with light weight and strong absorption. However, it remains a great challenge to balance the permittivity and permeability to realize impedance matching and further improve their absorption bandwidth. Herein, an effective strategy is designed to fabricate sandwich-like Co15Fe85@C/RGO composites. By introducing RGO sheets in the hybrid structures, the electromagnetic parameters, impedance matching and microwave absorption properties of the final materials can be well controlled. The optimized Co15Fe85@C/RGO composite shows an excellent microwave absorption performance, the strongest reflection loss (RL) of the sample is up to -33.38 dB at 10.72 GHz with a matching thickness of 2.5 mm, and the effective bandwidth (RL less then -10 dB) can reach 9.2 GHz (8.64-17.84 GHz). With a single thickness, such a wide absorption band is rarely reported. Their excellent performance can be ascribed to the synergetic effect of the chemical composition and unique sandwich-like structures, which will improve impendence matching and strong microwave attenuation constants of the composites.
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