Selective Functionalisation of 5-Methylcytosine by Organic Photoredox Catalysis

The epigenetic modification 5-methylcytosine plays a vital role in development, cell specific gene expression and disease states. The selective chemical modification of the 5-methylcytosine methyl group is challenging. Currently, no such chemistry exists. Direct functionalisation of 5-methylcytosine would improve the detection and study of this epigenetic feature. We report a xanthone-photosensitised process that introduces a 4-pyridine modification at a C(sp³)−H bond in the methyl group of 5-methylcytosine. We propose a reaction mechanism for this type of reaction based on density functional calculations and apply transition state analysis to rationalise differences in observed reaction efficiencies between cyanopyridine derivatives. The reaction is initiated by single electron oxidation of 5-methylcytosine followed by deprotonation to generate the methyl group radical. Cross coupling of the methyl radical with 4-cyanopyridine installs a 4-pyridine label at 5-methylcytosine. We demonstrate use of the pyridination reaction to enrich 5-methylcytosine-containing ribonucleic acid.     

Catalytically active gold on ordered titania supports

Almost two decades have passed since supported Au nanoparticles were found to be active for CO oxidation. This discovery inspired extensive research addressing the origin of the unique properties of supported Au nanoparticles, the design and synthesis of potentially technical Au catalysts, and the extension of Au catalysis to other reactions. This tutorial review summarises the current understanding of the origin of the unique properties of titania-supported Au catalysts for carbon monoxide oxidation. The key issues of catalysis by nanostructured Au, effects of oxide support and active site/structure, especially those provided from model studies are discussed in detail. The successful synthesis of a highly catalytically active gold bilayer may lead to the design and synthesis of practically active Au nanofilm catalysts.     

Comment on 'aggregation-induced phosphorescent emission (AIPE) of iridium(III) complexes': origin of the enhanced phosphorescence

An investigation of the photophysics of Ir(iii) complexes with controlled ligand structures and our quantum chemical calculations attest that the most probable explanation for the reported 'aggregation-induced phosphorescent emission', which was originally claimed to be related to an intermolecular excimer, is restricted intramolecular motion.     

Preparation of highly photosensitizing liposomes with fullerene-doped lipid bilayer using dispersion-controllable molecular exchange reactions

Fullerene-containing liposomes with high photosensitization ability were prepared. Disaggregated fullerenes were efficiently injected into the bilayer of liposomes by a phototriggered molecular exchange reaction. These liposomes showed far higher photoreactivity than liposomes thermally produced by heating and microwave irradiation. This result indicates that control of self-aggregation of fullerene leads to a high quantum yield for the photoreaction because of the suppression of self-quenching of photoexcited fullerenes.     

One-dimensional simulation of lanthanide isotachophoresis using COMSOL

Electrokinetic separations can be used to quickly separate rare earth metals to determine their forensic signature. In this work, we simulate the concentration and separation of trivalent lanthanide cations by isotachophoresis. A one-dimensional simulation is developed using COMSOL v4.0a, a commercial finite element simulator, to represent the isotachophoretic separation of three lanthanides: lanthanum, terbium, and lutetium. The binding ligand chosen for complexation with the lanthanides is α-hydroxyisobutyric acid (HIBA) and the buffer system includes acetate, which also complexes with the lanthanides. The complexes formed between the three lanthanides, HIBA, and acetate are all considered in the simulation. We observe that the presence of only lanthanide:HIBA complexes in a buffer system with 10 mM HIBA causes the slowest lanthanide peak (lutetium) to split from the other analytes. The addition of lanthanide:acetate complexes into the simulation of the same buffer system eliminates this splitting. Decreasing the concentration of HIBA in the buffer to 7 mM causes the analyte stack to migrate faster through the capillary.     

Inquiry Learning of High School Students Through a Problem‐Based Environmental Health Science Curriculum

The purpose of this study was to examine the degree to which high school students improved their inquiry capabilities in relation to scientific literacy through their experience of a problem‐based environmental health science curriculum. The two inquiry capabilities studied were scientific questioning and approaches to inquiry into their own questions. A total of 129 high school students taught by two teachers in one school wrote responses to environmental health issues at the beginning and at the end of a 10‐week long inquiry curriculum. An additional group of 46 students of one of the two teachers learned an alternative curriculum and participated as a comparison group. The students using the inquiry curriculum performed significantly better than those using the alternative curriculum in posing active inquiry questions and generating hypothesis‐driven approaches to inquiry into their questions. The inquiry curriculum students also improved significantly from the pretest to the posttest in both measures of inquiry capacity. Among the students who were less prepared for inquiry in the beginning, 68% improved inquiry‐questioning capability, while among the students who were more prepared for inquiry, 36% improved in generating hypotheses‐driven approaches. Implications for curriculum design and implementation were provided along with further research suggestions.     

Scanning transmission X-ray microscopic analysis of purified melanosomes of the mouse iris

Melanosomes are specialized intracellular membrane bound organelles that produce and store melanin pigment. The composition of melanin and distribution of melanosomes determine the color of many mammalian tissues, including the hair, skin, and iris. However, the presence of melanosomes within a tissue carries potentially detrimental risks related to the cytotoxic indole–quinone intermediates produced during melanin synthesis. In order to study melanosomal molecules, including melanin and melanin-related intermediates, we have refined methods allowing spectromicroscopic analysis of purified melanosomes using scanning transmission X-ray microscopy. Here, we present for the first time absorption data for melanosomes at the carbon absorption edge ranging from 284 to 290 eV. High-resolution images of melanosomes at discrete energies demonstrate that fully melanized mature melanosomes are internally non-homogeneous, suggesting the presence of an organized internal sub-structure. Spectra of purified melanosomes are complex, partially described by a predominating absorption band at 288.4 eV with additional contributions from several minor bands. Differences in these spectra were detectable between samples from two strains of inbred mice known to harbor genetically determined melanosomal differences, DBA/2J and C57BL/6J, and are likely to represent signatures arising from biologically relevant and tractable phenomena.     

A grasp-knapsack hybrid for a nurse-scheduling problem

This paper is concerned with the application of a GRASP approach to a nurse-scheduling problem in which the objective is to optimise a set of preferences subject to a set of binding constraints. The balance between feasibility and optimality is a key issue. This is addressed by using a knapsack model to ensure that the solutions produced by the construction heuristic are easy to repair. Several construction heuristics and neighbourhoods are compared empirically. The best combination is further enhanced by a diversification strategy and a dynamic evaluation criterion. Tests show that it outperforms previously published approaches and finds optimal solutions quickly and consistently.     

Cellularity of cyclotomic Birman–Wenzl–Murakami algebras

We show that cyclotomic BMW algebras are cellular algebras.