Generation and Reactivity of a One-Electron-Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn^V(TAML)(N-Mes)]⁻ ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC₆H₄)₃N ]^+.[SbCl₆]⁻ and the resulting Mn^VI species readily undergoes H-atom transfer and nitrene transfer reactions.     

LIOUVILLE RESULTS FOR STABLE SOLUTIONS OF QUASILINEAR EQUATIONS WITH WEIGHTS

This paper is devoted to the quasilinear equation ■where p 2,Ω is a(bounded or unbounded) domain of R~N,w_1,w_2 are nonnegative continuous functions and f is an increasing function. We establish a Liouville type theorem for nontrivial stable solutions of the equation under some mild assumptions on Ω,w_1, w_2 and f, which extends and unifies several results on this topic.     

Three salts from the reactions of cysteamine and cystamine with L‐(+)‐tartaric acid

Reaction between cysteamine (systematic name: 2‐aminoethanethiol, C₂H₇NS) and L‐(+)‐tartaric acid [systematic name: (2R,3R)‐2,3‐dihydroxybutanedioic acid, C₄H₆O₆] results in a mixture of cysteamine tartrate(1−) monohydrate, C₂H₈NS⁺·C₄H₅O₆⁻·H₂O, (I), and cystamine bis[tartrate(1−)] dihydrate, C₄H₁₄N₂S₂²⁺·2C₄H₅O₆⁻·2H₂O, (III). Cystamine [systematic name: 2,2′‐dithiobis(ethylamine), C₄H₁₂N₂S₂], reacts with L‐(+)‐tartaric acid to produce a mixture of cystamine tartrate(2−), C₄H₁₄N₂S₂²⁺·C₄H₄O₆²⁻, (II), and (III). In each crystal structure, the anions are linked by O—H...O hydrogen bonds that run parallel to the a axis. In addition, hydrogen bonding involving protonated amino groups in all three salts, and water molecules in (I) and (III), leads to extensive three‐dimensional hydrogen‐bonding networks. All three salts crystallize in the orthorhombic space group P2₁2₁2₁.     

Purity assessment for avoparcin

Well-characterized pure-substance reference materials for the use as calibrants are essential to establish the metrological traceability of the results of chemical measurements. Normally, the characterization of this type of reference material is conducted through a thorough purity assessment of the compound concerned. For this reason, studies on purity assessment, especially for neat organic compounds, continues as an important part of work being undertaken by metrological institutions around the world. Among others, the need for certified pure reference standards continues to increase for residues analysis in foods, particularly for those compounds which have been banned for food safety reasons, but their residues in foods are still monitored under food surveillance program in many countries. In this respect, avoparcin serves as a very good example where testing laboratories have difficulties in obtaining traceable and comparable results on determination of avoparcin in food matrix samples due, in part, to the unavailability of certified pure-substance reference material as calibrant. In this study, it was attempted to assess the purity of a commercially available test material of avoparcin using the mass balance approach. The objective of this paper is to share the difficulties encountered during the course of purity assessment and how they were addressed. As expected, the most challenging part of work was to identify and estimate the amount of unknown impurities, both organic and inorganic-related ones, given the chemical structure and properties of avoparcin. For instance, avoparcin exists in two forms in the test material, i.e., α- and β-avoparcin, and they were found to be susceptible to hydrolysis under certain conditions.     

A Mesoionic Diselenolene Anion and the Corresponding Radical Dianion

Dichalcogenolenes are archetypal redox non-innocent ligands with numerous applications. Herein, a diselenolene ligand with fundamentally different electronic properties is described. A mesoionic diselenolene was prepared by selenation of a C2-protected imidazolium salt. This ligand is diamagnetic, which is in contrast to the paramagnetic nature of standard dichalcogenolene monoanions. The new ligand is also redox-active, as demonstrated by isolation of a stable diselenolene radical dianion. The unique electronic properties of the new ligand give rise to unusual coordination chemistry. Thus, preparation of a hexacoordinate aluminum tris(diselenolene) complex and a Lewis acidic aluminate complex with two ligand-centered unpaired electrons was achieved.     

Intra- and Inter-molecular Sulf- hydryl Hydrogen Bonding: Facilitating Proton Transfer Events for Determination of pH in Sea Water

This work presents the electrochemical response of a 2-(methylthio)phenol glassy carbon based electrode for a promising voltammetric pH sensor in both buffered and low-buffered solutions. Electropolymerization of the redox species was performed with the resulting polymer presenting a Nernstian response in buffered media, with a sensitivity of 51 mV/pH unit. The effectiveness of the sulfhydryl bond to facilitate proton transfer from the bulk solution to the phenol molecules has been confirmed, providing an accurate pH measurement of 8.28 in sea water media, compared to that measured with a calibrated glass pH probe of 8.30.     

Imaging intrinsic diffusion of bridge-bonded oxygen vacancies on TiO2(110)

We report the first measurements and calculations of the intrinsic mobility of bridge-bonded oxygen (BBO) vacancies on a rutile TiO2(110). The sequences of isothermal (340-420 K) scanning tunneling microscope images show that BBO vacancies migrate along BBO rows. The hopping rate increases exponentially with increasing temperature with an experimental activation energy of 1.15 eV. Density functional theory calculations are in very good agreement giving an energy barrier for hopping of 1.03 eV. Both theory and experiment indicate repulsive interactions between vacancies on a given BBO row.     

Combination of radon and stable isotope analysis as a tool for decision support concerning the remediation of NAPL-contaminated sites

The non-aqueous phase-liquid (NAPL)-contaminated aquifer at a major refinery site in Mexico was investigated. Owing to the depth of the contaminated aquifer section (NAPL source zone) of over 100 m below the surface, the actual aquifer material was not accessible for sampling. Information on the residual NAPL contamination of the aquifer could only be obtained indirectly by analysing groundwater samples from a few wells available at the site. To tackle the problem, an approach alternative to conventional groundwater analysis for dissolved NAPL was chosen. For evaluating the recent contamination and estimating its probable future development, the radioisotope radon-222 and the stable isotopes 13C, 34S and 18O were used as naturally occurring contamination tracers and process indicators. Radon was used as partitioning tracer for the approximate localization and semi-quantitative assessment of the NAPL source zone. The stable isotopes were used as indicators for naturally occurring biodegradation processes, which might potentially be implemented into future remediation schemes.