Oxidatively-induced C(sp3)-C(sp3) bond formation at a tucked-in iron(iii) complex.

Carbon-carbon (C-C) bond formation is a cornerstone of synthetic chemistry, relying on routes such as transition-metal mediated cross-coupling for the introduction of new carbon-based functionality. For {[M] n+-C} (M = metal) structural units, studies that offer well-defined relationships between metal oxidation state, hydrocarbon strain, and {[M] n+-C} bond thermochemistry are thus informative, providing a means to reliably access new product classes. Here, we show that one-electron oxidation of the iron tucked-in complex [(η6-C5Me4[double bond, length as m-dash]CH2)Fe(dnppe)] (dnppe = 1,2-bis(di-n-propylphosphino)ethane) results in C(sp3)-C(sp3) bond formation giving unique {Fe2} dimers. Freeze-quenched CW X-band EPR spectroscopy allowed for spectroscopic identification of the reactive [(η6-C5Me4[double bond, length as m-dash]CH2)Fe(dnppe)]+ intermediate. Density functional theory (DFT) calculations reveal a primarily Fe-centered radical and a weak {[Fe]-C} bond (BDE[Fe]-C = 24.5 kcal mol-1, c.f. BDEC-C(ethane) = 90 kcal mol-1). For comparison, a structurally analogous Fe(iii) methyl complex was prepared, [Cp*Fe(dnppe)(CH3)]+ (Cp* = C5Me5 -), where C(sp3)-C(sp3) coupling was not observed, consistent with a larger calculated BDE[Fe]-C value of 47.8 kcal mol-1. These data are analogized to the simple hydrocarbons ethane and cyclopropane, where a strain-induced BDEC-C decrease of 33 kcal mol-1 is witnessed on cyclization.

Giant auxetic behavior in remote-plasma synthesized few-layer tungsten semicarbide.

Auxetic crystals exhibiting highly positive lateral expansivity when stretched are an experimentally elusive class of two-dimensional (2D) materials with tremendous potential, for example in the direct transduction of electric signals and the compensation of thermal expansion at the nanoscale. 2D tungsten semi-carbide (W2C) was theoretically predicted to exhibit giant auxetic behavior, but has yet to be synthesized, as the corresponding full carbide (WC) is energetically favored under thermodynamic equilibrium synthesis processes such as furnace-based chemical vapor deposition. Here, we report on an ad hoc designed dual-zone remote plasma deposition system specially conceived to grow tungsten carbides out of thermodynamic equilibrium with well-tuned ratios of W and C precursors. We report on the specific conditions under which this system allowed for the synthesis of flakes of few-layer tungsten semicarbide (FL-W2C) which are 2D in nature due to retained periodicity at the mesoscopic level in a Stranski-Krastanov growth process. Under applied strain, FL-W2C 2D crystals exhibit the strongest auxetic behavior observed to date. This result suggests that the theoretically predicted high negative Poisson's ratio of single-layer W2C, also extends to thicker FL-W2C flakes that are retaining the periodicity of the 2D crystal at the mesoscopic level.

A methodological primer of extracellular vesicles isolation and characterization via different techniques.

We present four different protocols of varying complexity for the isolation of cell culture-derived extracellular vesicles (EVs)/exosome-enriched fractions with the objective of providing researchers with easily conducted methods that can be adapted for many different uses in various laboratory settings and locations. These protocols are primarily based on polymer precipitation, filtration and/or ultracentrifugation, as well as size-exclusion chromatography (SEC) and include: (i) polyethylene glycol and sodium chloride supplementation of the conditioned medium followed by low-speed centrifugation; (ii) ultracentrifugation of conditioned medium; (iii) filtration of conditioned media through a 100-kDa exclusion filter; and (iv) isolation using a standard commercial kit. These techniques can be followed by further purification by ultracentrifugation, sucrose density gradient centrifugation, or SEC if needed and the equipment is available. HEK293 and SH-SY5Y cell cultures were used to generate conditioned medium containing exosomes. This medium was then depleted of cells and debris, filtered through a 0.2-µM filter, and supplemented with protease and RNAse inhibitors prior to exosomal isolation. The purified EVs can be used immediately or stably stored at 4°C (up to a week for imaging or using intact EVS downstream) or at -80°C for extended periods and then used for biochemical study. Our aim is not to compare these methodologies but to present them with descriptors so that researchers can choose the "best method" for their work under their individual conditions.