A Chemiluminescent Probe for HNO Quantification and Real‐Time Monitoring in Living Cells

Azanone (HNO) is a reactive nitrogen species with pronounced biological activity and high therapeutic potential for cardiovascular dysfunction. A critical barrier to understanding the biology of HNO and furthering clinical development is the quantification and real‐time monitoring of its delivery in living systems. Herein, we describe the design and synthesis of the first chemiluminescent probe for HNO, HNOCL‐1 , which can detect HNO generated from concentrations of Angeli's salt as low as 138 nm with high selectivity based on the reaction with a phosphine group to form a self‐cleavable azaylide intermediate. We have capitalized on this high sensitivity to develop a generalizable kinetics‐based approach, which provides real‐time quantitative measurements of HNO concentration at the picomolar level. HNOCL‐1 can monitor dynamics of HNO delivery in living cells and tissues, demonstrating the versatility of this method for tracking HNO in living systems.     

Bidentate Boron Lewis Acids: Selectivity in Host–Guest Complex Formation

Bidentate boron Lewis acids based on 1,8‐diethynylanthracene were synthesised in two steps by initial stannylation of the terminal alkynes and subsequent tin–boron exchange with different chloroboranes. The reactions were very selective, and the target compounds were obtained in high purity and good to excellent yields. Complexation experiments of 1,8‐bis[(diphenylboranyl)ethynyl]anthracene with nitrogen bases (pyridine, pyrimidine, TMEDA) afforded three stable adducts, which were structurally characterised by X‐ray diffraction. Competition experiments demonstrated the selective exchange of guests, and quantum‐chemical calculations provided information on their energetics. NMR experiments at low temperature gave insight into the dynamic behaviour of the TMEDA adduct.     

The Influence of β-Ammonium Substitution on the Reaction Kinetics of Aminooxy Condensations with Aldehydes and Ketones

The click-chemistry capture of volatile aldehydes and ketones by ammonium aminooxy compounds has proven to be an efficient means of analyzing the carbonyl subset in complex mixtures, such as exhaled breath or environmental air. In this work, we examine the carbonyl condensation reaction kinetics of three aminooxy compounds with varying β-ammonium ion substitution using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). We determined the activation energies for the reactions of the aminooxy compounds ATM, ADMH and AMAH with a panel of ketones and aldehydes that included acrolein and crotonaldehyde. The measurements indicate that the activation energies for the oximation reactions are quite low, less than 75 kJ mol⁻¹. ADMH is observed to react the fastest with the carbonyls studied. We postulate this result may be attributed to the ADMH ammonium proton effecting a Brønsted-Lowry acid-catalyzed elimination of water during the rate-determining step of oxime ether formation. A theoretical study of oxime ether formation is presented to explain the enhanced reactivity of ADMH relative to the tetraalkylammonium analog ATM.     

Magnetoresistance and spin-transfer torque in magnetic tunnel junctions

We comment on both recent progress and lingering puzzles related to research on magnetic tunnel junctions (MTJs). MTJs are already being used in applications such as magnetic-field sensors in the read heads of disk drives, and they may also be the first device geometry in which spin-torque effects are applied to manipulate magnetic dynamics, in order to make non-volatile magnetic random access memory. However, there remain many unanswered questions about such basic properties as the magnetoresistance of MTJs, how their properties change as a function of tunnel-barrier thickness and applied bias, and what are the magnitude and direction of the spin-transfer-torque vector induced by a tunnel current.     

Assessment of material uncertainties in solid foams based on local homogenization procedures

The present study is concerned with a numerical prediction and assessment of uncertainties in the macroscopic material properties of solid foams. The material properties are determined by means of a homogenization analysis considering a large scale representative volume element. The microstructure for the representative volume element is determined randomly using a Voronoï tesselation in Laguerre geometry with prescribed cell size distribution. For assessment of the scatter in the effective material response, the homogenization scheme is applied to subsets of the large scale representative volume element. By this means, an interrelation between the local microstructural characteristics and the local mesoscopic material response is established. In a first approach, the individual cells of the foam microstructure are employed as testing volume elements. As an alternative, a moving window technique is applied. The sets of homogenization results obtained by both approaches are evaluated by stochastic methods. For the local effective properties, a distinct scatter is observed. The results in both cases reveal that the local porosity is the most important influence parameter. For the microstructures investigated, only weak local correlations of the effective stiffnesses with a rapid spatial decay of the correlation is observed.     

Carbon-13 and nitrogen-15 nuclear magnetic resonance of physostigmine (eserine)

The ¹⁵N and ¹³C nmr spectra of physostigmine are discussed along with complete assignment of the signals. This alkaloid ¹⁵ N nmr spectrum is notable because it contains nitrogens in three different environments.