Identification tree based on fragmentation rules for structure elucidation of organophosphorus esters by electrospray mass spectrometry

Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non‐volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI‐MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MSⁿ) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision‐induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an ‘identification tree’ based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the ‘identification tree’. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. Copyright © 2013 John Wiley & Sons, Ltd.     

Is Genetic Engineering a Route to Enhance Microalgae-Mediated Bioremediation of Heavy Metal-Containing Effluents?

Contamination of the biosphere by heavy metals has been rising, due to accelerated anthropogenic activities, and is nowadays, a matter of serious global concern. Removal of such inorganic pollutants from aquatic environments via biological processes has earned great popularity, for its cost-effectiveness and high efficiency, compared to conventional physicochemical methods. Among candidate organisms, microalgae offer several competitive advantages; phycoremediation has even been claimed as the next generation of wastewater treatment technologies. Furthermore, integration of microalgae-mediated wastewater treatment and bioenergy production adds favorably to the economic feasibility of the former process—with energy security coming along with environmental sustainability. However, poor biomass productivity under abiotic stress conditions has hindered the large-scale deployment of microalgae. Recent advances encompassing molecular tools for genome editing, together with the advent of multiomics technologies and computational approaches, have permitted the design of tailor-made microalgal cell factories, which encompass multiple beneficial traits, while circumventing those associated with the bioaccumulation of unfavorable chemicals. Previous studies unfolded several routes through which genetic engineering-mediated improvements appear feasible (encompassing sequestration/uptake capacity and specificity for heavy metals); they can be categorized as metal transportation, chelation, or biotransformation, with regulation of metal- and oxidative stress response, as well as cell surface engineering playing a crucial role therein. This review covers the state-of-the-art metal stress mitigation mechanisms prevalent in microalgae, and discusses putative and tested metabolic engineering approaches, aimed at further improvement of those biological processes. Finally, current research gaps and future prospects arising from use of transgenic microalgae for heavy metal phycoremediation are reviewed.     

Model-independent constraints on spin observables

We discuss model-independent constraints on spin observables in exclusive and inclusive reactions, with special attention to the case of photoproduction.     

Current trends in the computational modelling of polyoxometalates

Computational chemistry applied to the study of polyoxometalates has achieved its maturity in the last years. During two decades, important advances have been made using theoretical tools in the comprehension and interpretation of many relevant issues. In the present mini-review, we want to stress that different techniques have been incorporated to the routine of computation: from the very first Hartree?CFock LCAO-SCF calculation on the decavanadate anion, followed by numerous density functional theory?Cbased studies on increasingly complex systems, also applying correlated ab initio techniques for magnetism and, more recently, using molecular dynamics to analyse properties in liquid media, the information provided by computational chemistry gets more and more relevant.     

DFT Mechanistic Study on Diene Metathesis Catalyzed by Ru‐Based Grubbs–Hoveyda‐Type Carbenes: The Key Role of π‐Electron Density Delocalization in the Hoveyda Ligand

The catalytic activity and catalyst recovery of two heterogenized ruthenium‐based precatalysts ( H and NO₂(4) ) in diene ring‐closing metathesis have been studied by means of density functional calculations at the B3LYP level of theory. For comparison and rationalization of the key factors that lead to higher activities and higher catalyst recoveries, four other Grubbs–Hoveyda complexes have also been investigated. The full catalytic cycle (catalyst formation, propagation, and precatalyst regeneration) has been considered. DFT calculations suggest that either for the homogeneous and heterogenized systems the activity of the catalysts mainly depends on the ability of the precursor to generate the propagating carbene. This ability does not correlate with the traditionally identified key factor, the Ru???O interaction strength. In contrast, precatalysts with lower alkoxy‐dissociation energy barriers and lower stabilities compared with the propagating carbene also present larger C1? C2 bond length (i.e., lower π character of the C? C bond that exists between the metal–carbene (Ru?C) and the phenyl ring of the Hoveyda ligand). Catalyst recovery, regardless of whether a release–return mechanism occurs or not, is also mainly determined by the π delocalization. Therefore, future Grubbs–Hoveyda‐type catalyst development should be based on fine‐tuning the π‐electron density of the phenyl moiety, with the subsequent effect on the metalloaromaticity of the ruthenafurane ring, rather than considering the modification of the Ru???O interaction.     

Analytical approach for CRLH-based antennas design

This paper presents an analytical model for CRLH (Composite Right-Left Handed) antennas preliminary design. The objective of this work is to develop a tool to estimate quickly the scattering and radiating characteristics of these CRLH-based structures. The analytical model provides thus a set of parameters which roughly fulfill desired requirements. Afterwards, the antenna designer can refine the CRLH-based antenna performances with full 3D electromagnetic simulation software.     

Hidrogeochemical study in South Amazon region using Photoacoustic Spectroscopy

In this study we demonstrate the usefulness of the Photoacoustic Spectroscopy (PAS) in the investigation of water collected from a natural site located within the Amazon region, Brazil, during the wet to dry seasons transition (May/2006). The water samples were collected from different stages along a hydrologic pathway including precipitation water (Prec), groundwater (GW), through flow water (TF), overland flow water (OF), and stream flow water (SW). The observed photoacoustic spectral features, in the 0.3 to 1.0 μm wavelength region, fall within three distinct bands (C, S, and L). We found band-C, band-S and band-L occurring in the spectral range of 0.30 to 0.40 μm, 0.40 to 0.45 μm and 0.45 to 1.0 μm regions, respectively. The photoacoustic features shift peak positions and change intensities for all samples investigated, thus supporting the proposal of PAS as a useful technique to investigate water samples from natural environments.