Iodine-promoted amide formation via oxidative cleavage of indoles: novel quinazoline-4(3H)-one and tryptanthrin syntheses.

A highly efficient method for the direct construction of amide bonds via a selective cleavage of C-H and C[double bond, length as m-dash]C bonds in indole structures using an iodine-promoted approach was developed. Mechanistic studies indicated the formation of superoxide radicals obtained from molecular oxygen activation as a key intermediate step, which provided a precursor for subsequent oxidative ring-opening and intermolecular cyclization. A broad range of quinazolin-4(3H)-ones and tryptanthrins were synthesized in moderate to good yields under mild and environmentally benign conditions.

Desilification of phytolith exacerbates the release of arsenic from rice straw.

Arsenic (As) turnover in rice paddy agro-ecosystems has received much attention because As can enter the food chain through its accumulation in rice, thereby affecting human health. Returning straw to soil is a common practice to retain nutrients for soil and crops, but it also cycles As within the rice paddy field ecosystems. However, there is still a lack of detailed understanding of the fate of As in rice straw, and how or to what extent it is recycled back into the soil environment. This study aims to elucidate the relationship between the microstructure of rice straw and the release of As during rice straw decomposition. The microstructure of rice straw was found to comprise both organic and silica (phytolith) components. These two constituents are inter-embedded to form a composite-like structure that contains up to 6.48 mg As Kg-1. The 30-day batch experiments revealed that the biochemical release of As simultaneously depends upon the decomposition of the organic component and the desilicification of the silica component. Accompanying the release of As was the release of other elements such as Fe, Al, P and S. These elements can further interact with As to form less mobile compounds. The introduction of either Trichoderma harzianum or Bacillus velezensis was expected to accelerate the decomposition of rice straw, and enhance the silica dissolution, hence contributing to an increase in the As release. Despite these expectations, our observations showed the opposite effects. Microorganisms presumably have facilitated the change in solution chemistry or the inclusion of As into the newly-formed precipitates. The biochemical decomposition process can reduce straw particle size, while the negatively-charge surface will involve microsized straw particles in the electrostatic interaction, thereby favoring the dispersibility state. Therefore, the co-transport of micro-sized straw particles with As under field conditions should not be neglected.

Earthworms can mobilize soil arsenic through their casts.

The mobilization of arsenic (As) in paddy soil has received much attention because it might accelerate the transfer of As from soil to rice. This study aims to elucidate whether earthworms can mobilize As through their casts. Cast samples were collected from 23 different paddy fields in the Red River delta. We first analysed different forms of As through fractionation and then performed batch experiments under reducing conditions to identify factors that govern the mobility of As in casts. Because the dissociation of casts may induce colloids that carry As, the colloidal properties of cast suspensions were also examined. The median value of As in casts (obtained from aqua regia digestion) was 5.11 mg kg-1, which was lower than that in the surrounding soil (6.7 mg kg-1). Compared with the surrounding soil, casts contain less As, possibly because cast As is more labile and more easily lost due to leaching. Various processes, including the reductive dissolution of Fe oxides, decomposition of organic matter, and sorption competition of soluble anionic substances, such as P, Si and DOC, were found to strongly correlate with the release of As from casts. We propose that earthworms, via their casts, may accelerate the As cycle in paddy soils, potentially intensifying As exposure to human health. The dissociation of cast could release colloids containing As; therefore, the cotransport of As with cast-induced colloids should also be considered in future works.

Sorption of cosmetic and personal care polymer ingredients to iron oxides, clay minerals and soil clays: An environmental perspective.

The increasing daily use of cosmetic and personal care ingredients (CPCIs) requires improved understanding of the fate and impacts of CPCIs in environmental systems. Effects of CPCIs on colloidal properties of various geocolloids such as iron oxides (goethite, haematite), clay minerals (kaolinite, bentonite) and soil clays (kaolinitic-, illitic- and lateritic soil clays) were studied by tracking time-resolved changes in zeta potential (ζ) and observing suspended particle density. Two polymers representing anionic CPCIs, i.e., polyacrylate crosspolymer-11 (PC11) and cationic CPCIs, i.e., polyDADMAC (PD) show contrast effects on ζ and colloidal properties of the selected materials. While PC11 tended to associate with Fe oxides, PD can be adsorbed by clay minerals and soil clays. The neutralization due to the sorption of either PC11 or PD onto opposite-charge sign surface sites can lower the net surface charge of the materials, thereby enhancing electrostatic attraction, stimulating particle size growth, and eventually intensifying co-aggregation. The observed colloidal properties of iron oxides, clay minerals and soil clays under the presence of PC11 and PD may reflect what are happening in many aquatic environments where CPCIs co-exist with various mineral colloids. Therein, CPCIs likely delay the transport of the opposite-charge sign colloids, while they increase the dispersibility and transportability of the same-charge sign colloids. This implies that intensifying presence of a given CPCI could have selective effects on colloid systems. As a whole, CPCIs can change the fate and the final destination of mineral colloids and themselves; therefore, their effects and relevant treatment techniques need to be included into the future agenda.

Comparative effects of crystalline, poorly crystalline and freshly formed iron oxides on the colloidal properties of polystyrene microplastics.

Colloid-sized microplastics (MPs) are ubiquitous in aquatic environments and can share the same transport route together with various crystalline, poorly crystalline and freshly formed iron oxides. However, the colloidal interactions between these colloid constituents are not fully understood. This study was designed to investigate the colloidal properties of polystyrene microplastics (PSMPs) under the influence of haematite, goethite, ferrihydrite and freshly formed Fe oxide (FFFO). Dynamic light scattering was coupled with a test tube method to observe changes in the surface charge and colloidal dynamics of suspensions of PSMPs and Fe oxides. The overall effects on the aggregation of PSMPs are found to decrease in the following order: FFFO > ferrihydrite > goethite > haematite. The effects of these Fe oxides are found to strongly depend on pH. While the crystalline oxides play a dominant role in the acidic environment, poorly crystalline oxides show greater effects on PSMP aggregation in an alkaline environment. Heteroaggregation due to decreasing electrostatic interactions is the major mechanism that governs the colloidal dynamics of PSMPs and Fe oxides. It can be inferred that the copresence of Fe oxides and MPs can delay the transport of MPs or even change the destination for MPs.

Polyacrylate crosspolymer-11 enhances soil clay dispersibility: An indication for inadvertent environmental impacts from personal care and cosmetic ingredients.

Polymer ingredients are commonly found in personal care and cosmetic industry and their "leakages" into the environment have recently been warned as an emerging environmental risk. Daily use of personal care and cosmetic products can inadvertently release large amounts of polymer ingredients into water courses. However, their fate and interaction with other constituents, especially colloids (e.g., clays), have not been fully understood. This study primarily evaluates the colloidal dynamics of soil clays under the presence of polyacrylate crosspolymer-11 (PC11) (a common ingredient of cosmetic and personal care products) with the aim of identifying possible induced changes in the clay-accumulated environments, e.g., soil and sediment. The test-tube experiments were coupled with a particle charge detector to mutually evaluate the colloidal dynamics and surface charge properties of the soil clays. It was revealed that adsorption of PC11 onto the clays shifted clay surface to more negative, thereby intensifying repulsive force and favouring the dispersion state of the soil clays. This implies that various polymer ingredients can act in the same way in stabilizing clay dispersion or even altering the fate of the soil clays. As the growing consumption of personal care and cosmetic products will likely continue, it requires a tighter consideration of the possible impacts of polymer ingredient residues, not limited to dispersion-induced effects, in various clay-accumulated environments such as paddy fields, river mouths or mangroves.