Search

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed for the synthesis of α-quaternary (Z)-trisubstituted allylic amino acids under mild conditions. This methodology features broad substrate compatibilities in yields of up to 87% and up to 94% ee. A facile scale-up and straightforward conversion to 1,2,3,5-tetrasubstituted pyrrole and 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies the synthetic utility of this method. [ABSTRACT FROM AUTHOR]

With industrial development and eventual commercial use, environmental chemicals through accidental spills and effluents appear more frequently in aquatic ecosystems and may produce an enormous effect on water, soil, wildlife and human health. Therefore, aquatic toxicity becomes an increasingly important endpoint in the evaluation of the environmental impact of chemicals. In this study, based on ECOTOX database, a large data set containing 824 diverse compounds with experimental 48 h EC50 values on crustaceans was compiled. A series of in silico models were then developed using six machine learning methods combined with seven types of molecular fingerprints. Performance of these models was measured by an external validation set, involving 246 molecules. The best model proposed is MACCS fingerprint and SVM algorithm with high accuracy of 0.87 for external validation set. Additionally, we proposed five structural alerts identified by information gain and substructure frequency analysis for mechanistic interpretation. The models and structural alerts can provide critical information and useful tools for a priori evaluation of chemical aquatic toxicity in environmental hazard assessment. [ABSTRACT FROM AUTHOR]

To explore the oxidation effects and mechanisms for the oxidation of alkanes by H2O2 in a Fenton system catalyzed by two types of iron bound to soil organic matter (Fe-SOM) in crude oil-contaminated soil, an oxidation experiment was performed in active Fe-SOM and Fe-SOM systems. The results showed that the TPH removal ability of active Fe-SOM (average 0.36 g TPH/g Fe-SOM) was 2.25-fold higher than the corresponding value of Fe-SOM. Active Fe-SOM contained both –NH2 and –OH functional groups, and had a higher content of iron with high binding energy, while Fe-SOM only contained –NH2 groups. Thus, a large yield of hydroxyl radicals (·OH) was generated (8.92 a.u.) by active Fe-SOM catalyzing the decomposition of H2O2, while the corresponding yield of ·OH in the Fe-SOM system was only 4.81 a.u. In addition, the removal efficiency of C17–C23 (70%) was comparable to that of C24–C30 (69%), not restricted by the hydrophobicity of different alkanes. The alkane removal by active Fe-SOM was higher than that by Fe-SOM, although the content of Fe-SOM was double that of active Fe-SOM. In summary, the active Fe-SOM formed in the soil sample containing humic acid-like and hydrophobic acid derivates could catalyze H2O2 decomposition to improve the removal efficiency of crude oil in contaminated soil. [ABSTRACT FROM AUTHOR]

We use Brownian dynamics (BD) simulations to investigate the formation and structural characteristics of the complex between a spherical polyelectrolyte brush (SPB) and oppositely charged surfactants. Increasing the amount of added surfactants leads to a collapsed conformation of the SPB and the number of adsorbed surfactants exhibits a linear dependence. Nevertheless, the surfactant uptake into the SPB does not increase with further addition of surfactants. It is found that the surfactant length has a strong influence on the SPB conformation and the adsorption properties of surfactant. Upon changing the surfactant length from 3 to 11, the SPB undergoes a swelling-deswelling-reswelling conformational transition. The brush deswelling is due to the increase in the surfactant uptake. The increasing size of adsorbed aggregates is a main reason for reswelling of the SPB. A non-linear relationship between the brush thickness and the grafting density is observed. Especially at intermediate grafting densities, increasing the number of grafted chains has a weak effect on the brush thickness. We also find that a completely collapsed brush conformation occurs at high surfactant/SPB charge ratios or large surfactant lengths, while the brush layer is in a partly collapsed or extended state at an intermediate charge ratio and surfactant length. [ABSTRACT FROM AUTHOR]

To explore the oxidation effects and mechanisms for the oxidation of alkanes by H2O2 in a Fenton system catalyzed by two types of iron bound to soil organic matter (Fe-SOM) in crude oil-contaminated soil, an oxidation experiment was performed in active Fe-SOM and Fe-SOM systems. The results showed that the TPH removal ability of active Fe-SOM (average 0.36 g TPH/g Fe-SOM) was 2.25-fold higher than the corresponding value of Fe-SOM. Active Fe-SOM contained both -NH2 and -OH functional groups, and had a higher content of iron with high binding energy, while Fe-SOM only contained -NH2 groups. Thus, a large yield of hydroxyl radicals (·OH) was generated (8.92 a.u.) by active Fe-SOM catalyzing the decomposition of H2O2, while the corresponding yield of ·OH in the Fe-SOM system was only 4.81 a.u. In addition, the removal efficiency of C17-C23 (70%) was comparable to that of C24-C30 (69%), not restricted by the hydrophobicity of different alkanes. The alkane removal by active Fe-SOM was higher than that by Fe-SOM, although the content of Fe-SOM was double that of active Fe-SOM. In summary, the active Fe-SOM formed in the soil sample containing humic acid-like and hydrophobic acid derivates could catalyze H2O2 decomposition to improve the removal efficiency of crude oil in contaminated soil.