Polynuclear manganese grids and clusters—A magnetic perspective

High nuclearity paramagnetic, spin-coupled transition metal clusters and grids are fascinating chemists and physicists partly because of their structural beauty, and the challenge of creating them, but also because of their novel physical properties. Magnetic interactions between the spin centers are a primary focus. This review will examine a selection of Mn(II) polynuclear grids and clusters, with nuclearities in the range Mn₄ to Mn₉. Theoretical treatments of the magnetic properties are discussed, and approaches to solving the exchange problem for ‘large’ spin systems related to computational difficulties. A freely available software package (MAGMUN4.1) is presented as a means of dealing simply with spin-coupled clusters in general, and symmetry reduction methods are discussed briefly as a means of dealing with ‘large’ spin systems.     

Diffusion in ethylene–propylene rubber

A study of sorption in a copolymer of ethylene and propylene is presented. Long-time sorption and desorption measurements provided the actual diffusion coefficient in the limit of zero concentration gradient. An analysis of the diffusion–sorption data reinforced the Frisch hypothesis about diffusion in a polymer matrix. The better solvent deforms the microstructure, allowing a more marked dependence of the diffusivity upon concentration.     

Chemical Synthesis of Oligonucleotides Containing N6-Methyladenine Residues in the GATC Site

To investigate by NMR the effects of adenine methylation, a set of oligodeoxynucleotides has been synthesized by phosphotriester or phosphoramidite procedures on silica-gel support. The preparation of fully protected 2′-deoxy-N⁶-methyladenosine 3′-phosphate 4 and (2′-deoxy-N⁶-methyladenosin-3′-O-yl)(methoxy)morpholinophosphine 5 is described. The large-scale chemical synthesis, purification by HPLC, and characterization by MS of these molecules containing N⁶-methyladenine is reported.     

Electron-impact-induced fragmentation of aromatic cyclic diazoketones

The mass spectra of eleven diazoketones have been obtained. High resolution mass measurements of selected ions have shown initial loss of nitrogen followed by loss of carbon monoxide. In many of the spectra, flat-topped metastables were observed.     

Analytical methods used to measure acrylamide concentrations in foods

The state-of-the-art of analysis for acrylamide in food is reviewed. The majority of analytical methods adopts a similar approach: addition of internal standard to the specimen, extraction with water, purification of extract using a solid-phase extraction cartridge, and then determination using either gas chromatography coupled to mass spectroscopy (GC/MS) after bromination, or direct measurement with liquid chromatography coupled to mass spectroscopy (LC/MS). The available methods generally show good agreement and are likely to be accurate. However, improvements in precision (within-laboratory) and repeatability (between-laboratory) are needed by particular data users.     

Halogenation in Fungi: What Do We Know and What Remains to Be Discovered?

In nature, living organisms produce a wide variety of specialized metabolites to perform many biological functions. Among these specialized metabolites, some carry halogen atoms on their structure, which can modify their chemical characteristics. Research into this type of molecule has focused on how organisms incorporate these atoms into specialized metabolites. Several families of enzymes have been described gathering metalloenzymes, flavoproteins, or S-adenosyl-L-methionine (SAM) enzymes that can incorporate these atoms into different types of chemical structures. However, even though the first halogenation enzyme was discovered in a fungus, this clade is still lagging behind other clades such as bacteria, where many enzymes have been discovered. This review will therefore focus on all halogenation enzymes that have been described in fungi and their associated metabolites by searching for proteins available in databases, but also by using all the available fungal genomes. In the second part of the review, the chemical diversity of halogenated molecules found in fungi will be discussed. This will allow the highlighting of halogenation mechanisms that are still unknown today, therefore, highlighting potentially new unknown halogenation enzymes.     

Periodic Mesoporous Organosilica Nanoparticles for CO2 Adsorption at Standard Temperature and Pressure

(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO₂) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth’s temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO₂ present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO₂ adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO₂ adsorption were obtained with 6% bipyridine: 1.045 mmol·g⁻¹ at 298 K and 2.26 mmol·g⁻¹ at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.     

A note on a pioneering work in quantitative spectroscopy: UV bands of the hydroxyl radical

The publication by G.H. Dieke and H.M. Crosswhite (JQSRT 1962;2:97-199) is a classic paper detailing the spectroscopy of the A²Σ⁺←X²Π bands of the hydroxyl radical (OH) in the ultraviolet region. It soon became the basis of astrophysical modeling, most subsequent theoretical and laboratory studies of the OH individual line parameters, and a host of other applications.     

Scattering of time-harmonic elastic waves by an elastic inclusion with quadratic nonlinearity

This paper considers the scattering of a plane, time-harmonic wave by an inclusion with heterogeneous nonlinear elastic properties embedded in an otherwise homogeneous linear elastic solid. When the inclusion and the surrounding matrix are both isotropic, the scattered second harmonic fields are obtained in terms of the Green's function of the surrounding medium. It is found that the second harmonic fields depend on two independent acoustic nonlinearity parameters related to the third order elastic constants. Solutions are also obtained when these two acoustic nonlinearity parameters are given as spatially random functions. An inverse procedure is developed to obtain the statistics of these two random functions from the measured forward and backscattered second harmonic fields.