Effect of Gold Nanoparticles Size on Detection of Methylphosphonic Acid Hydrolysis Product of Nerve Agent

Citrate reduction of gold (III) chloride trihydrate (HAuCl4) is commonly used method to synthesise citrate-capped gold nanoparticles (cit-AuNPs). In this study, the sequence of reagents addition was modified (“inverse” method) to synthesise smaller size of cit-AuNPs than the standard Turkevich method (“direct” method). Ultraviolet-visible spectroscopy (UV-vis) and field emission transmission electron microscopy (FETEM) confirmed the formation of cit-AuNPs. The cit-AuNPs synthesized using “inverse” method are smaller in size (14.0 ± 3.03 nm) with uniform spherical shape compared to “direct” method (23.5 ± 7.52 nm). Smaller particles size of cit-AuNPs provide higher efficiency and sensitivity for detection of methylphosphonic acid (MPA) via colorimetric incorporated with image processing with a linear range from 2.5 to 12.5 mM and a low detection limit of 6.28 mM at shorter detection period (24 to 30 s).

Epigenetic Changes Associated With Exposure to Glyphosate-Based Herbicides in Mammals

Glyphosate is a phosphonomethyl amino acid derivative present in a number of non-selective and systemic herbicides. During the last years the use of glyphosate-based herbicide (GBH) has been increasing exponentially around the world, including Argentina. This fact added to the detection of glyphosate, and its main metabolite, amino methylphosphonic acid (AMPA), in environmental matrices such as soil, sediments, and food, has generated great concern about its risks for humans, animals, and environment. During the last years, there were controversy and intense debate regarding the toxicological effects of these compounds associated with the endocrine system, cancer, reproduction, and development. The mechanisms of action of GBH and their metabolites are still under investigation, although recent findings have shown that they could comprise epigenetic modifications. These are reversible mechanisms linked to tissue-specific silencing of gene expression, genomic imprinting, and tumor growth. Particularly, glyphosate, GBH, and AMPA have been reported to produce changes in global DNA methylation, methylation of specific genes, histone modification, and differential expression of non-coding RNAs in human cells and rodents. Importantly, the epigenome could be heritable and could lead to disease long after the exposure has ended. This mini-review summarizes the epigenetic changes produced by glyphosate, GBHs, and AMPA in humans and rodents and proposes it as a potential mechanism of action through which these chemical compounds could alter body functions.

Two Excited State Collaboration of Heteroleptic Ir(III)-Coumarin Complexes for H2 Evolution Dye-Sensitized Photocatalysts

Interfacial electron injection from a photoexcited surface-immobilized dye to a semiconductor substrate is a key reaction for dye-sensitized photocatalysts. We previously reported that the molecular orientation of heteroleptic Ir(III) photosensitizer on the TiO2 nanoparticle surface was important for efficient interfacial electron injection. In this work, to overcome the weak light absorption ability of heteroleptic Ir(III) photosensitizer and to improve the photoinduced charge-separation efficiency at the dye–semiconductor interface, we synthesized two heteroleptic Ir(III) complexes with different coumarin dyes, [Ir(C6)2(H4CPbpy)]Cl and [Ir(C30)2(H4CPbpy)]Cl [Ir-CX; X = 6 or 30; HC6 = 3-(2-enzothiazolyl)-7-(diethylamino)coumarin, HC30 = 3-(2-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, H4CPbpy = 4,4′-bis(methylphosphonic acid)-2,2′-bipyridine], as the cyclometalated ligands and immobilized them on the surface of Pt-cocatalyst-loaded TiO2 nanoparticles. Ultraviolet-visible absorption and emission spectroscopy revealed that the singlet ligand-centered (1LC) absorption and triplet 3LC emission bands of Ir-C30 occurred at shorter wavelengths than those of Ir-C6, while time-dependent density-functional-theory data suggested that the ligand-to-ligand charge transfer (LLCT) excited states of the two complexes were comparable. The photocatalytic H2 evolution activity of the Ir-C6-sensitized Pt-TiO2 nanoparticles (Ir-C6@Pt-TiO2) under visible light irradiation (λ > 420 nm) was higher than that of Ir-C30@Pt-TiO2. In contrast, their activities were comparable under irradiation with monochromatic light (λ = 450 ± 10 nm), which is absorbed comparably by both Ir-CX complexes. These results suggest that the internal conversion from the higher-lying LC state to the LLCT state effectively occurs in both Ir-CX complexes to trigger electron injection to TiO2.

Phosphonates enantiomers receiving with fungal enzymatic systems

Background Phosphonates derivatives are in the area of interests because of their unique chemical-physical features. These compounds manifest variety of biological interactions within the sensitive living cells, including impact on particular enzymes activities. Biological “cause and effect” interactions are based upon the specific matching between the structures and/or compounds and this is usually the result of proper optical configurations of particular chiral moieties. Presented research is targeted to the phosphonates with the heteroatom incorporated in their side functionalities. Such molecules are described as possible substrates of bioconversion for the first time lately and this field is not fully explored. Results Presented research is targeted to the synthesis of pure hetero-phosphonates enantiomers. The catalytic activity of yeasts and moulds were tested towards two substrates: the thienyl and imidazole phosphonates to resolve their racemic mixtures. Biotransformations conditions differed depending on the outcome, what included changing of following parameters: type of cultivation media, bioprocess duration (24–72 h), additional biocatalyst pre-treatment (24–48 h starvation step triggering the secondary metabolism). (S)-1-amino-1-(3-thienyl)methylphosphonate was produced with the assistance of R. mucilaginosa or A. niger (e.e. up to 98% and yield up to 100%), starting from the 3 mM of substrate racemic mixture. Bioconversion of racemic mixture of 3 mM of (1-amino-1-(4-imidazole)methylphosphonic acid) resulted in the synthesis of S-isomer (up to 95% of e.e.; 100% of yield) with assistance of R. mucilaginosa. 24 h biotransformation was conducted with biomass preincubated under 48-hour starvation conditions. Such stereoselective resolution of the racemic mixtures of substrates undergoes under kinetic control with the conversion of one from the enantiomers. Conclusions Composition of the culturing media and pre-incubation in conditions of nutrient deficiency were significant factors influencing the results of kinetic resolution of racemic mixtures of phosphonic substrates and influencing the economic side of the biocatalysis e.g. by determining the duration of whole biocatalytic process. Graphical abstract

Hydrolysis of Methylphosphonic Anhydride Solid to Methylphosphonic Acid Probed by Raman and Infrared Reflectance Spectroscopies

Much is still unknown about the mechanisms and rates of environmental degradation of organophosphorous pesticides and agents. In this study we focus on the degradation of one organophosphorous compound, namely...

EFFECTS OF LIGNOHUMATE ON THE PHYTOTOXICITY OF PHOSPHORUS-CONTAINING COMPOUNDS (MODEL EXPERIMENTS)

In conditions of chemical pollution, it is relevant to enhance the resistance of plants with substances that have a protective action. The effect of humic substance Lignohumate on the phytotoxic properties of phosphorus-containing compounds methylphosphonic acid (MPA) and sodium pyrophosphate (SPP) was studied in model experiments. Lignohumate was tested at three concentrations (0.1, 0.5, and 1 g/L) on Hordeum distichum L. of the Novichok variety. The test functions were such indicators as the germinating and sprouting ability of seeds, the growth and biomass accumulation of seedlings, and the inhibition effect. Lignohumate in the studied concentrations did not affect germination of the barley seeds, but it stimulated growth of the barley seedlings. In the conditions of MPA pollution (0.01 mol/L), Lignohumate exerted a protective effect on the plants, and the highest concentration of humic preparation (1 g/L) was the most effective. In the experiments with SPP (0.01 mol/L), Lignohumate stimulated germination the barley seeds but it did not reduce the growth inhibitory effect of SPP. The combined exposure to the studied pollutants negatively affected growth and accumulation of biomass by the barley roots. The introduction of Lignohumate weakened the combined effect but could not completely countervail it. The calculation of inhibition effect showed that the phytotoxicity of phosphorus-containing substances reduced in the order MPA (without buffer) - SPP - MPA (with buffer) - MPA+SPP . The introduction of Lignohumate to the growth medium was the most effective in experiments with low-toxic substances.