Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy

Manganese oxide (MnO_x) electrocatalysts are examined herein by in situ soft X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L‐edge XAS data with previous mechanistic studies indicates Mn^IV is the highest oxidation state involved in the catalytic mechanism. MnO_x is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn?O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K‐edge provide complementary evidence for such a transition. This step is crucial for the formation of O₂ from water.     

Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

Trifluoromethoxy (OCF₃) and difluoromethoxy (OCF₂H) groups are fluorinated structural motifs that exhibit unique physicochemical characteristics. Incorporation of these substituents into organic molecules is a highly desirable approach used in medicinal chemistry and drug discovery processes to alter the properties of a parent compound. Recently, tri‐ and difluoromethyl ethers have received increasing attention and several innovative strategies to access these valuable functional groups have been developed. The focus of this Minireview is the use of visible‐light photoredox catalysis in the synthesis of tri‐ and difluoromethyl ethers. Recent photocatalytic strategies for the formation of O?CF₃, C?OCF_3, O?CF₂H, and C?OCF₂H bonds as well as other transformations leading to the construction of OR_F groups are discussed herein.     

Differential pulse voltammetry in analysis of disinfectants — 2-mercaptobenzothiazole, 4-chloro-3-methylphenol, triclosan, chloramine-T

The aim of this work was to study the possibility of simultaneous voltammetric determination of some disinfectants used as components in cosmetic products. The examined compounds were: triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), chloramine-T (N-chloro-p-toluenesulfonamide sodium salt), 4-chloro-3-methylphenol and 2-mercaptobenzothiazole. Measurements were performed using glassy carbon electrode immersed in Britton-Robinson buffers which acted as supporting electrolytes. The dependence of oxidation and reduction potentials on pH was examined using cyclic voltammetry. Britton-Robinson buffer of pH 9.9 was chosen for further studies to ensure the best separation of compounds. The resultant oxidation potentials indicate the possibility to simultaneously determine some of the disinfectants.. Oxidation reactions of mixtures containing two compounds (4-chloro-3-methylphenol and chloramine-T, 2-mercaptobenzothiazole and 4-chloro-3-methylphenol, 2-mercaptobenzothiazole and triclosan) were recorded as differential pulse voltammograms.     

Dynamic Light Scattering and NMR Studies of Napin

We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of ¹H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated.     

5,5‐Di­methoxy‐2‐phenoxy‐1,3,2‐dioxaphosphorinane 2‐oxide

In the title compound, C₁₁H₁₅O₆P, the six‐membered dioxa­phospho­rinane ring of the cyclic phosphate triester exists in a distorted chair conformation, with the phenoxy group in an axial position. The phenyl ring and both methoxy groups are in a trans–gauche orientation with respect to the 1,3,2‐di­oxa­phospho­rinane ring. In the phosphate group, a significant deformation from the ideal tetrahedral shape is observed. The crystal structure is stabilized by a three‐dimensional network of C—H⋯O interactions.     

Comparison of the effectiveness of epoxy cure accelerators using a fluorescent molecular probe

A simple optical method for quantitative comparison of the effectiveness of epoxy cure accelerators, used for speeding up the crosslinking process of epoxy resins with cyclic anhydrides, is described. Fluorescent molecular probes and a miniature fiber optic spectrometer have been applied for measurement of the cure kinetics of a model epoxy resin/anhydride composition in the presence of various cure accelerators. A quantitative index of accelerator performance has been determined for several of the most common accelerators.     

Synthesis and evaluation of the catalytic properties of semicarbazides derived from N-triphenylmethyl-aziridine-2-carbohydrazides

A straightforward synthesis of a series of new catalysts derived from N-triphenylmethyl-aziridine-2-carbohydrazides is described. The new compounds have been tested for the enantioselective addition of diethyl- and phenylethynylzinc to aryl and alkyl aldehydes, which afforded the corresponding chiral alcohols in high chemical yields (up to 92%) and with excellent ee’s of approximately 90%.     

Detection of drug active ingredients by chemometric processing of solid-state NMR spectrometry data -- the case of acetaminophen

This paper presents a preliminary study in building discriminant models from solid-state NMR spectrometry data to detect the presence of acetaminophen in over-the-counter pharmaceutical formulations. The dataset, containing 11 spectra of pure substances and 21 spectra of various formulations, was processed by partial least squares discriminant analysis (PLS-DA). The model found coped with the discrimination, and its quality parameters were acceptable. It was found that standard normal variate preprocessing had almost no influence on unsupervised investigation of the dataset. The influence of variable selection with the uninformative variable elimination by PLS method was studied, reducing the dataset from 7601 variables to around 300 informative variables, but not improving the model performance. The results showed the possibility to construct well-working PLS-DA models from such small datasets without a full experimental design.     

Use of direct immersion solid-phase microextraction on polyacrylate and polydimethylsiloxane stationary phases for simultaneous determination of the neutral and basic pharmaceuticals in wastewater

Direct immersion solid-phase microextraction has been optimized and applied to the simultaneous determination of the neutral and basic pharmaceuticals: caffeine, carbamazepine, clomipramine, chlorprothixene and clotrimazole at low concentrations in municipal wastewater. Two absorption type stationary phases: polydimethylsiloxane (PDMS) and polyacrylate (PA) have been found to be most effective for extraction of target analytes. The separation and detection were carried out by gas chromatograph coupled with mass spectrometer working in the selected ion monitoring mode. The method was validated for linearity, detection and quantitation limits, selectivity and precision. The average correlation coefficient of the calibration curves was 0.9933. The LOD values in influent and effluent wastewater were in the range of 10–145 ng L^?1 and 4–111 ng L^?1, respectively, which were a bit higher than those in the deionized water due to matrix effect. The high values of distribution coefficient (K _fs ) in PDMS/water and PA/water systems (log K _fs between 3.05 and 4.23) indicates the very high applicability of these stationary phases for determination of carbamazepine, clomipramine, chlorprothixene and clotrimazole in water samples.

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Catalytic Oxidative Cyclocondensation of o‐Aminophenols to 2‐Amino‐3H‐phenoxazin‐3‐ones

The catalytic oxidative cyclocondensation of the o‐aminophenols 1a–f was investigated. The oxidants used were air/laccase, H₂O₂/horseradish peroxidase, H₂O₂/ebselen (3), and TBHP/diphenyl diselenide 4. The products obtained were 2‐amino‐3H‐phenoxazin‐3‐one—questiomycin A, its derivative 2b, and cinnabarinic acid and actinocin (2c,d). Substrates with methyl groups at 4 and 5 positions of benzene ring were converted to different dihydrophenoxazinones 2g,h. Compounds having chlorine atoms at the same positions underwent oxidation to planar phenoxa-zinones 2e,f with elimination of one hydrochloride molecule.