The redox chemistry of sulfenic acids

A persistent triptycenyl sulfenic acid is used as a model for cysteine-derived and other biologically relevant sulfenic acids in experiments which define their redox chemistry. EPR spectroscopy reveals that sulfinyl radicals are persistent and unreactive toward O(2), allowing the O-H bonding dissociation enthalpy (BDE) of the sulfenic acid to be readily determined by equilibration with TEMPO as 71.9 kcal/mol. The E° (RSO?/RSO(-)) and pK(a) of this sulfenic acid are also reported.     

Evidence for shape coexistence at medium spin in Rb

Four previously known rotational bands in ⁷⁶Rb have been extended to moderate spins using the Gammasphere and Microball γ ray and charged particle detector arrays and the ⁴⁰Ca(⁴⁰Ca, 3pn) reaction at a beam energy of 165 MeV. The properties of two of the negative-parity bands can only readily be interpreted in terms of the highly successful Cranked Nilsson-Strutinsky model calculations if they have the same configuration in terms of the number of g9/2 particles, but they result from different nuclear shapes (one near-oblate and the other near-prolate). These data appear to constitute a unique example of shape coexisting structures at medium spins.     

Expanding Lipidome Coverage Using LC-MS/MS Data-Dependent Acquisition with Automated Exclusion List Generation

Untargeted omics analyses aim to comprehensively characterize biomolecules within a biological system. Changes in the presence or quantity of these biomolecules can indicate important biological perturbations, such as those caused by disease. With current technological advancements, the entire genome can now be sequenced; however, in the burgeoning fields of lipidomics, only a subset of lipids can be identified. The recent emergence of high resolution tandem mass spectrometry (HR-MS/MS), in combination with ultra-high performance liquid chromatography, has resulted in an increased coverage of the lipidome. Nevertheless, identifications from MS/MS are generally limited by the number of precursors that can be selected for fragmentation during chromatographic elution. Therefore, we developed the software IE-Omics to automate iterative exclusion (IE), where selected precursors using data-dependent topN analyses are excluded in sequential injections. In each sequential injection, unique precursors are fragmented until HR-MS/MS spectra of all ions above a user-defined intensity threshold are acquired. IE-Omics was applied to lipidomic analyses in Red Cross plasma and substantia nigra tissue. Coverage of the lipidome was drastically improved using IE. When applying IE-Omics to Red Cross plasma and substantia nigra lipid extracts in positive ion mode, 69% and 40% more molecular identifications were obtained, respectively. In addition, applying IE-Omics to a lipidomics workflow increased the coverage of trace species, including odd-chained and short-chained diacylglycerides and oxidized lipid species. By increasing the coverage of the lipidome, applying IE to a lipidomics workflow increases the probability of finding biomarkers and provides additional information for determining etiology of disease.

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Graphical Abstract ?

     

Modeling oil droplets in plateau borders

It is widely known that oil droplets can decrease the stability of aqueous films and foams. While less widely recognized, it has also been observed that oil droplets can, under certain circumstances, increase the stability of foams, especially if they are caught in the Plateau borders. In this paper, how the oil droplet deforms and is, in turn, deformed by the Plateau border is modeled using Surface Evolver. The two dimensionless parameters that affect these shapes are the size of the oil droplet relative to the Plateau border and the ratio of the oil-water interfacial tension to the air-water interfacial tension. The calculated pressures in all the phases were used to obtain the pressure exerted on the oil-water-air pseudoemulsion film, which allows the factors that influence the stability of these droplets in the Plateau border to be investigated. The final section of the paper demonstrates that the presence of an oil droplet in a Plateau border can have a major influence on the drainage of the aqueous phase along the Plateau border. This retardation of the flow would result in the oil droplets in the Plateau borders increasing the stability of foams in which they are found.     

Considerations for quantification of lipids in nerve tissue using matrix-assisted laser desorption/ionization mass spectrometric imaging

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometric imaging is a technique that provides the ability to identify and characterize endogenous and exogenous compounds spatially within tissue with relatively little sample preparation. While it is a proven methodology for qualitative analysis, little has been reported for its utility in quantitative measurements. In the current work, inherent challenges in MALDI quantification are addressed. Signal response is monitored over successive analyses of a single tissue section to minimize error due to variability in the laser, matrix application, and sample inhomogeneity. Methods for the application of an internal standard to tissue sections are evaluated and used to quantify endogenous lipids in nerve tissue. A precision of 5% or less standard error was achieved, illustrating that MALDI imaging offers a reliable means of in situ quantification for microgram-sized samples and requires minimal sample preparation.     

Characterization and dynamics of substituted ruthenacyclobutanes relevant to the olefin cross-metathesis reaction

The reaction of the phosphonium alkylidene [(H(2)IMes)RuCl(2)=CHP(Cy)(3))](+) BF(4)(-) with propene, 1-butene, and 1-hexene at -45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α'-disubstituted (both cis and trans) ruthenacycles. On an NMR time scale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR time scale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H(2)IMes)Cl(2)Ru(CHRCH(2)CH(2)) (R = CH(3), CH(2)CH(3), (CH(2))(3)CH(3)). EXSY NMR experiments at -87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analogue. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H(2)IMes)Cl(2)Ru(CH(2)CH(2)CH(2)) was observed in up to 98% yield via NMR at -40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics toward olefin metathesis catalyst and reaction design are described.     

Introduction to Physics in Modern Medicine, 2nd edn., by Suzanne Amador Kane

The inexorable miniaturisation of technologies, the relentless drive to improve efficiency and the enticing prospect of boosting performance through quantum effects are all compelling reasons to investigate microscopic machines. Thermal absorption machines are a particularly interesting class of device that operate autonomously and use only heat flows to perform a useful task. In the quantum regime, this provides a natural setting in which to quantify the thermodynamic cost of various operations such as cooling, timekeeping or entanglement generation. This article presents a pedagogical introduction to the physics of quantum absorption machines, covering refrigerators, engines and clocks in detail.