Organic Phosphorus Mineralization Dominates the Release of Internal Phosphorus in a Macrophyte-Dominated Eutrophication Lake

Macrophyte-dominated eutrophication (MDE) lakes have attracted wide attention due to the high phosphorus (P) loading in sediments that poses a wide spread risk for P release and pollution management. However, because of the superior productivity characteristics, the role of organic P mineralization in sediments in the internal P loading of MDE lake is still under debate. This study investigated the release dynamic of P in the sediments of Lake Caohai, a MDE lake in southwest of China, using a combination of the modified Huffer sequential extraction method, 31P nuclear magnetic resonance spectroscopy (NMR), and composite diffusive gradient in thin films (DGT) technology. Results showed that the apparent P diffusion flux at the sediment-water interface was remarkably high, with a mean value of 0.37 mg m−2 d−1. The phosphate ester organophosphorus components (i.e., Mono-P and Diester-P) continuously deposited and degraded in the sediments maintained the high productivity of the lake, and the mineralization process plays a critical role in the release of internal P. Although the content of inorganic P in sediment is relatively high (accounting for approximately 60% of total P), the reductive mechanism based on P-containing iron oxide/hydroxide has a low contribution to the internal P loading, as was indicated by the low release rate of P-combination iron-manganese (Fe-Mn)/iron-aluminum (Fe-Al) (BD-P and NaOH-P) and the insignificant positive correlations between DGT-labile P and DGT-labile Fe in the sediment cores. Additionally, organic P in sediments could transfer to P-combination Fe-Al/Fe-Mn. However, in severely expropriated environments, the enrichment of P-combination Fe-Al/Fe-Mn in surface sediments inhibited the mineralization of monophosphate to some degree. Taken together, this study emphasized the impact of sediment organic P loading on the release of internal P in lake, highlighting that organic P is also the valuable objects for avoiding eutrophication of MDE lakes.

Allelic variation for alpha-Glucan Water Dikinase is associated with starch phosphate content in tetraploid potato

Key message Association analysis resulted in the identification of specific StGWD alleles causing either an increase or decrease in starch phosphate content which was verified in diploid and tetraploid potato mapping populations. Abstract Potatoes are grown for various purposes like French fries, table potatoes, crisps and for their starch. One of the most important aspects of potato starch is that it contains a high amount of phosphate ester groups which are considered to be important for providing improved functionalization after derivatization processes. Little is known about the variation in phosphate content as such in different potato varieties and thus we studied the genetic diversity for this trait. From other studies it was clear that the phosphate content is controlled by a quantitative trait locus (QTL) underlying the candidate gene α-Glucan Water Dikinase (StGWD) on chromosome 5. We performed direct amplicon sequencing of this gene by Sanger sequencing. Sequences of two StGWD amplicons from a global collection of 398 commercial cultivars and progenitor lines were used to identify 16 different haplotypes. By assigning tag SNPs to these haplotypes, each of the four alleles present in a cultivar could be deduced and linked to a phosphate content. A high value for intra-individual heterozygosity was observed (Ho = 0.765). The average number of different haplotypes per individual (Ai) was 3.1. Pedigree analysis confirmed that the haplotypes are identical-by-descent (IBD) and offered insight in the breeding history of elite potato germplasm. Haplotypes originating from introgression of wild potato accessions carrying resistance genes could be traced. Furthermore, association analysis resulted in the identification of specific StGWD alleles causing either an increase or decrease in starch phosphate content varying from 12 nmol PO4/mg starch to 38 nmol PO4/mg starch. These allele effects were verified in diploid and tetraploid mapping populations and offer possibilities to breed and select for this trait.

Rules of Chemospecificity of Nucleophilc Ring-opening of Dithia-/Oxathia-Phospholane Towards the Selective Synthesis of Nucleoside 5’-O-Pα-Thio/Dithio/Trithio-Phosphate Ester Conjugates

DBU-assisted nucleophilic ring-opening of both uridine-5’-(2-thio-1,3,2-dithia-phospholane), 3, and uridine-(2-thio-1,3,2-oxathia-phospholane), 8, lasted 2 min at RT and resulted in quantitative yields of uridine-5’-phosphoro-di/trithioate esters. Furthermore, it was selective for alcohol and thiol vs. amine nucleophiles. Yet, reaction of mercaptoethanol with 3, was chemo-specific for the oxygen vs. sulfur nucleophile, while for the reaction of mercaptoethanol with 8, the opposite chemo-specificity was observed, probably related to the steric hindrance in the former case. The observed chemospecificity opens facile avenue for the synthesis of nucleoside-5’-O-Pα-thio/dithio/trithio-phosphate ester derivatives

Fire Resistance, Thermal and Anti-Ageing Properties of Transparent Fire-Retardant Coatings Modified with Different Molecular Weights of Polyethylene Glycol Borate

Four kinds of polyethylene glycol borate (PEG-BA) with different molecular weights were grafted into cyclic phosphate ester (PEA) to obtain flexible phosphate esters (PPBs), and then applied in amino resin to obtain a series of transparent intumescent fire-retardant coatings. The comprehensive properties of the transparent coatings containing different molecular weights of PEG-BA were investigated by various analytical instruments. The transparency and mechanical analyses indicate that the presence of PEG-BA slightly decreases the optical transparency of the coatings but improves the flexibility and adhesion classification of the coatings. The results from fire protection and cone calorimeter tests show that low molecular weight of PEG-BA exerts a positive flame-retarded effect in the coatings, while high molecular weight of PEG800-BA behaves against flame-retarded effect. Thermogravimetric and char residue analyses show that the incorporation of low molecular weight of PEG-BA clearly increases the thermal stability and residual weight of the coatings and generates a more compact and stable intumescent char on the surface of the coatings, thus resulting in superior synergistic flame-retarded effect. In particular, MPPB1 coating containing PEG200-BA exerts the best flame-retarded effect and highest residual weight of 36.3% at 700 °C, which has 57.6% reduction in flame spread rate and 23.9% reduction in total heat release compared to those of MPPB0 without PEG-BA. Accelerated ageing test shows that low molecular weight of PEG-BA promotes to enhance the durability of structural stability and fire resistance of the coatings, while PEG800-BA with high molecular weight weakens the ageing resistance. In summary, the fire-resistant and anti-ageing efficiencies of PEG-BA in the coatings depend on its molecular weight, which present the order of PEG200-BA > PEG400-BA > PEG600-BA > PEG800-BA.

Restoring Tumour Selectivity of the Bioreductive Prodrug PR-104 by Developing an Analogue Resistant to Aerobic Metabolism by Human Aldo-Keto Reductase 1C3

PR-104 is a phosphate ester pre-prodrug that is converted in vivo to its cognate alcohol, PR-104A, a latent alkylator which forms potent cytotoxins upon bioreduction. Hypoxia selectivity results from one-electron nitro reduction of PR-104A, in which cytochrome P450 oxidoreductase (POR) plays an important role. However, PR-104A also undergoes ‘off-target’ two-electron reduction by human aldo-keto reductase 1C3 (AKR1C3), resulting in activation in oxygenated tissues. AKR1C3 expression in human myeloid progenitor cells probably accounts for the dose-limiting myelotoxicity of PR-104 documented in clinical trials, resulting in human PR-104A plasma exposure levels 3.4- to 9.6-fold lower than can be achieved in murine models. Structure-based design to eliminate AKR1C3 activation thus represents a strategy for restoring the therapeutic window of this class of agent in humans. Here, we identified SN29176, a PR-104A analogue resistant to human AKR1C3 activation. SN29176 retains hypoxia selectivity in vitro with aerobic/hypoxic IC50 ratios of 9 to 145, remains a substrate for POR and triggers γH2AX induction and cell cycle arrest in a comparable manner to PR-104A. SN35141, the soluble phosphate pre-prodrug of SN29176, exhibited superior hypoxic tumour log cell kill (>4.0) to PR-104 (2.5–3.7) in vivo at doses predicted to be achievable in humans. Orthologues of human AKR1C3 from mouse, rat and dog were incapable of reducing PR-104A, thus identifying an underlying cause for the discrepancy in PR-104 tolerance in pre-clinical models versus humans. In contrast, the macaque AKR1C3 gene orthologue was able to metabolise PR-104A, indicating that this species may be suitable for evaluating the toxicokinetics of PR-104 analogues for clinical development. We confirmed that SN29176 was not a substrate for AKR1C3 orthologues across all four pre-clinical species, demonstrating that this prodrug analogue class is suitable for further development. Based on these findings, a prodrug candidate was subsequently identified for clinical trials.

Glycidol Fatty Acid Ester and 3-Monochloropropane-1,2-Diol Fatty Acid Ester in Commercially Prepared Foods

Glycidyl fatty acid esters (GEs), which are the main pollutant in processed oils, are potential mutagens or carcinogens. 3-Monochloropropane-1,2-diol fatty acid esters (3-MCPDEs) are also well-known food processing contaminants. 3-MCPDEs are believed to be a precursor to GEs in foodstuffs. In vivo, lipase breaks down the phosphate ester of GEs and 3-MCPDEs to produce glycidol and 3-MCPD, respectively, which are genotoxic carcinogens. Thus, it is important to determine human exposure to GEs and 3-MCPDEs through foodstuffs. There are only reports on the amount of GE and 3-MCPDE in cooking oils and cooked foods. The content in multiple types of foods that are actually on the market was not clarified. In this study, 48 commercially prepared foods were analyzed to identify other sources of exposure to GE and 3-MCPDE. All of them contained relatively high amounts of GEs and 3-MCPDEs. The correlation between GEs and 3-MCPDEs in individual foods was examined. There was a correlation between the amounts of GEs and 3-MCPDEs in the food products (r = 0.422, p < 0.005). This is the first report on the content in multiple types of commercially prepared foods that are actually on the market was clarified.

Physicochemical Characterization of an Exopolysaccharide Produced by Lipomyces sp. and Investigation of Rheological and Interfacial Behavior

The present study aimed to evaluate the rheological and interfacial behaviors of a novel microbial exopolysaccharide fermented by L. starkeyi (LSEP). The structure of LSEP was measured by LC-MS, 1H and 13C NMR spectra, and FT-IR. Results showed that the monosaccharide composition of LSEP was D-mannose (8.53%), D-glucose (79.25%), D-galactose (7.15%), and L-arabinose (5.07%); there existed the anomeric proton of α-configuration and the anomeric carbon of α- and β-configuration; there appeared the characteristic absorption peak of the phosphate ester bond. The molecular weight of LSEP was 401.8 kDa. The water holding capacity (WHC, 2.10 g/g) and oil holding capacity (OHC, 12.89 g/g) were also evaluated. The results of rheological properties showed that the aqueous solution of LSEP was a non-Newtonian fluid, exhibiting the shear-thinning characteristics. The adsorption of LSEP can reduce the interfacial tension (11.64 mN/m) well and form an elastic interface layer at the MCT–water interface. Such functional properties make LSEP a good candidate for use as thickener, gelling agent, and emulsifier to form long-term emulsions for food, pharmaceutical, and cosmetic products.