Disturbed nutrient accumulation and cell wall metabolism in panicles are responsible for rice straighthead disease.

Rice straighthead disease substantially reduces crop yield, posing a significant threat to global food security. Dimethylarsinic acid (DMA) is the causal agent of straighthead disease and is highly toxic to the reproductive tissue of rice. However, the precise physiological mechanism underlying DMA toxicity remains unknown. In this study, six rice varieties with varying susceptibility to straighthead were utilized to investigate the growth performance and element distribution in rice panicles under DMA stress through pot experiments, as well as to explore the physiological response to DMA using transcriptomic methods. The findings demonstrate significant variations in both DMA accumulation and straighthead sensitivity among cultivars. The susceptible varieties exhibited higher DMA accumulation indices and displayed typical symptoms of straighthead disease, including erect panicles, deformed rachides and husks, and reduced seed setting rate and grain yield when compared to the resistant varieties. Moreover, DMA addition promoted mineral nutrients to accumulate in rachides and husks but less in grains. DMA showed preferential accumulation in rice grains with a distribution pattern similar to that of Copper (Cu) and zinc (Zn) within the panicle. Transcriptome analyses underscored the substantial impact of DMA on gene expression related to mineral metabolism. Notably, DMA addition significantly up-regulated the expression of pectin methylesterase, pectin lyase, polygalacturonase, and exogalacturonase genes in Nanjingxiangzhan, while these genes were down-regulated or weakly expressed in Ruanhuayou 1179. The alteration of pectin metabolic pathways induced by DMA may lead to abnormality of cell wall assembly and modification, thereby resulting in deformed rice panicles.

Inhibition of microelement accumulation and disorder of saccharide and amino acid metabolism explain rice grain empty under dimethylarsinic acid stress.

KEY MESSAGE: Metabolomic and transcriptomic analyses revealed an intensification of energy metabolism in rice grains under DMA stress, possibly causing the consumption of sugars or non-sugars and the development of unfilled grains Excessive dimethylarsinic acid (DMA) causes rice straighthead disease, a physiological disorder typically with erect panicle due to empty grain at maturity. Although the toxicity of DMA and its uptake and transport in rice are well recognized, the underlying mechanism of unfilled grains remains unclear. Therefore, a pot experiment was conducted using a susceptible variety (Ruanhuayou1179, RHY) and a resistant one (Nanjingxiangzhan, NJXZ) via the metabolomic and transcriptomic approaches to explore the mechanisms of empty grains in diseased rice under DMA stress. The results demonstrate an increase in total and methylated As in grains of RHY and NJXZ under DMA addition, with RHY containing higher levels of DMA. DMA addition increased the soluble sugar content in grains of RHY and NJXZ by 17.1% and 14.3% compared to the control, respectively, but significantly reduced the levels of amino acid, soluble protein, and starch. The decrease of grain Zn and B contents was also observed, and inadequate Zn might be a key factor limiting rice grain yield under DMA stress. Notably, DMA addition altered the expression levels of genes involved in the transport of sugar, amino acids, nitrates/peptides, and mineral ions. In sugar and amino acid metabolism, the reduction of metabolites and the upregulated expression of genes reflect positive regulation at the level of energy metabolism, implying that the reduction of grain starch and proteins might be ascribed to generate sufficient energy to resist the stress. This study provides a useful reference for understanding the molecular mechanism of grain emptying under DMA stress.

Antifungal effects of volatile organic compounds produced by Trichoderma hamatum against Neocosmospora solani.

Neocosmospora solani causes Fusarium wilt disease and root rot, which are serious problems worldwide. To determine the growth inhibition of Neocosmospora solani by Trichoderma hamatum volatile organic compounds (VOCs), the major chemical components of Trichoderma hamatum VOCs and the differences in their contents at different times were analysed, and the activity of these components was evaluated. The antifungal activity of Trichoderma hamatum was measured by a screening test, as Trichoderma hamatum exhibited strong antagonism against Neocosmospora solani in vitro. The double plate technique was used to verify the activity of Trichoderma hamatum VOCs, and the inhibition rate was 63.77%. Neocosmospora solani mycelia were uneven and expanded, the contents of the cells leaked, and the mycelia shrank and presented a diaphragm in the hyphae upon Trichoderma hamatum VOCs treatment. Trichoderma hamatum VOCs and their contents at different times were analysed by using gas chromatography-mass spectrometry. 6-Pentyl-2H-pyran-2-one clearly presented in greater amounts than the other components on day 3, 4, 5, and 6. VOCs from Trichoderma hamatum exhibited evident effects on the percentage of healthy fruit after day 3. Moreover, Trichoderma hamatum can improve the biological control of diseases caused by soilborne pathogens, and can be applied in biocontrol fields.

Asymmetric distribution of mineral nutrients aggravates uneven fruit pigmentation driven by sunlight exposure in litchi.

MAIN CONCLUSION: Sunlight boosts anthocyanin synthesis/accumulation in sunny pericarp of litchi fruit, directly leading to uneven pigmentation. Distribution discrepancy of mineral element aggravates uneven coloration by modulating synthesis/accumulation of anthocyanin and sugar. Uneven coloration, characterized by red pericarp on sunny side and green pericarp on shady side, impacts fruit quality of 'Feizixiao' (cv.) litchi. The mechanisms of this phenomenon were explored by investigating the distribution of chlorophyll, flavonoids, sugars, and mineral elements in both types of pericarp. Transcriptome analysis in pericarp was conducted as well. Sunny pericarp contained higher anthocyanins in an order of magnitude and higher fructose, glucose, co-pigments (flavanols, flavonols, ferulic acid), and mineral elements like Ca, Mg and Mn, along with lower N, P, K, S, Cu, Zn and B (P < 0.01), compared to shady pericarp. Sunlight regulated the expression of genes involved in synthesis/accumulation of flavonoids and sugars and genes functioning in nutrient uptake and transport, leading to asymmetric distribution of these substances. Anthocyanins conferred red color on sunny pericarp, sugars, Ca and Mg promoted synthesis/accumulation of anthocyanins, and co-pigments enhanced color display of anthocyanins. The insufficiencies of anthocyanins, sugars and co-pigments, and inhibition effect of excess K, S, N and P on synthesis/accumulation of anthocyanins and sugars, jointly contributed to green color of shady pericarp. These findings highlight the role of asymmetric distribution of substances, mineral elements in particular, on uneven pigmentation in litchi, and provide insights into coloration improvement via precise fertilization.

Effect of roxarsone metabolites in chicken manure on soil biological property.

Roxarsone (ROX), an organoarsenic feed additive, occurs as itself and its metabolites including As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in animal manure. Animal manure improves soil biological property, whereas As compounds impact microorganisms. The integral influence of animal manure bearing ROX metabolites on soil biological quality is not clear yet. Herein, the effect of four chicken manures excreted by chickens fed with four diets containing 0, 40, 80 and 120 mg ROX kg-1, on soil biological attributes. ROX addition in chicken diets increased total As and ROX metabolites in manures, but decreased manure total N, ammonium and nitrate. The elevated ROX metabolites in manures increased soil total As, As species and total N, and increased first and then decreased soil nitrate and nitrite, but did not affect soil ammonium in manure-applied soils. The promoting role of both soil As(III) and ammonium on soil microbial biomass carbon and nitrogen, respiration and saccharase activity, were exceeded or balanced by the inhibiting effect of soil nitrate. The suppression of soil catalase activity by soil As(V) was surpassed by the enhancement caused by soil nitrate and nitrite. Soil urease, acid phosphatase and polyphenol oxidase activities were not suitable bioindicators in the four manure-amended soils. Soil DMA did not affect soil biological properties, and MMA was not detectable in all manure-amended soils. The above highlights the complexity of joint influence of soil As and N on biological attributes. Totally, when ROX is used at allowable dose in chicken diet, soil biological quality would be suppressed in manure-amended soil.

Soil attribute regulates assimilation of roxarsone metabolites by rice (Oryza sativa L.).

Roxarsone (ROX), an organoarsenic feed additive, and its metabolites, can be present in animal manure used to fertilize rice. Rice is prone to absorb arsenic, and is subject to straighthead disorder, which reduces rice yield and is linked with organic arsenic compounds. This study aims to elucidate how soil property affect arsenic accumulation in rice plants fertilized with chicken manure containing ROX metabolites. Manures of chickens fed without or with ROX, designated as control manure and ROX treated manure (ROXCM), respectively, were applied in eight paddy soils of different origins, to investigate the assimilation of arsenic species in rice plants. The results show that inorganic arsenic (arsenate and arsenite), monomethylarsonic acid and dimethylarsinic acid (DMA) were detected in all brown rice and husk, trace tetramethylarsonium and trimethylarsine oxide were occasionally found in these both parts, whereas all these arsenic species were determined in straw, irrespective of manure type. ROXCM application specifically and significantly increased brown rice DMA (P = 0.002), which remarkably enhanced the risk of straighthead disease in rice. Although soil total As impacted grain biomass, soil free-iron oxides and pH dominated arsenic accumulation by rice plants. The significantly increased grain DMA suggests manure bearing ROX metabolites is not suitable to be used in soils with abundant free-iron oxides and/or high pH, if straighthead disorder is to be avoided in rice.

Encapsulation of a Metal-Organic Polyhedral in the Pores of a Metal-Organic Framework.

A new and efficient hydrophilicity-directed approach (HDA) is developed to encapsulate large guest molecules beyond the aperture size limitation in the nanospace of metal-organic frameworks (MOFs), as exemplified by the self-assembly of a metal-organic polyhedral (MOP) M6L4 into MIL-101. This strategy is based on the different hydrophilicities between inner and outer surfaces of the preformed MOF that may direct the self-assembly of the MOP in the MOF pores by using a two-solvent system. Importantly, as the MOP guest molecule is larger than the MOF aperture size, aggregation and leaching are effectively prevented, endowing the encapsulated MOP with significantly enhanced reactivity and stability in the catalytic transformations as compared to the pristine MOP.

Controllable Encapsulation of "Clean" Metal Clusters within MOFs through Kinetic Modulation: Towards Advanced Heterogeneous Nanocatalysts.

Surfactant-free tiny Pt clusters were successfully encapsulated within MOFs with controllable size and spatial distribution by a novel kinetically modulated one-step strategy. Our synthesis relies on the rational manipulation of the reduction rate of Pt ions and/or the growth rate of MOFs by using H2 as assistant reducing agent and/or acetic acid as MOF-formation modulator. The as-prepared Pt@MOF core-shell composites exhibited exceedingly high activity and excellent selectivity in the oxidation of alcohols as a result of the ultrafine "clean" Pt clusters, as well as interesting molecular-sieving effects derived from the outer platinum-free MOF shell.

Boosted simultaneous removal of chlortetracycline and Cu (II) by Litchi Leaves Biochar: Influence of pH, ionic strength, and background electrolyte ions.

The coexistence of heavy metals and antibiotics in the environment always results in greater toxicity compared to the individual precursors. Therefore, efficient and economic technology for the simultaneous removal of antibiotics and heavy metals is essential. Herein, litchi leaves biochar carbonized at 550 °C (L550) demonstrated high efficiency in co-removal of CTC (1838.1 mmol/kg) and Cu (II) (1212.9 mmol/kg) within wide range of pH (pH 4-7). Ionic strength obviously enhanced the Cu (II) removal but showed no significant effect on CTC removal. Although Al3+ and HPO42- decreased the adsorption capacities of CTC and Cu (II) on L550, the coexistence of Na+, K+, Mg2+, Cl-, NO3-, CO32- and SO42- showed a negligible effect on the simultaneous removal of CTC and Cu (II). Moreover, the adsorption capacities of CTC and Cu (II) on L550 were excellent in the river water, tap water, and lake water. In addition to electrostatic interactions, ion exchange governed Cu (II) adsorption, while surface complexation played a key role in CTC adsorption on L550. Our results demonstrated that litchi leaves biochar could be a promising adsorbent for remediating multi-contaminated environments.

The physiological and biochemical responses to dark pericarp disease induced by excess manganese in litchi.

Dark pericarp disease (DPD), a physiological disorder induced by excess Manganese (Mn) in litchi, severely impacts the appearance and its economic value. To elucidate the underlying mechanisms of DPD, this study investigated the variations of phenolic compound, antioxidant defense system, subcellular structure, and transcriptome profiles in both normal fruit and dark pericarp fruit (DPF) at three developmental stages (green, turning, and maturity) of 'Guiwei' litchi. The results reveal that excess Mn in DPF pericarp resulted in a significant increase in reactive oxygen species, especially H2O2, and subsequent alterations in antioxidant enzyme activities. Notably, SOD (EC 1.15.1.1) activity at the green stage, along with POD (EC 1.11.1.7) and APX (EC 1.11.1.11) activities at the turning and the maturity stages, and GST (EC 2.5.1.18) activity during fruit development, were markedly higher in DPF. Cell injury was observed in pericarp, facilitating the formation of dark materials in DPF. Transcriptome profiling further reveals that genes involved in flavonoid and anthocyanin synthesis were up-regulated during the green stage but down-regulated during the turning and maturity stages. In contrast, PAL (EC 4.3.1.24), C4H (EC 1.14.14.91), 4CL (EC 6.2.1.12), CAD (EC 1.1.1.195), and particularly POD, were up-regulated, leading to reduced flavonoid and anthocyanin accumulation and increased lignin content in DPF pericarp. The above suggests that the antioxidant system and phenolic metabolism jointly resisted the oxidative stress induced by Mn stress. We speculate that phenols, terpenes, or their complexes might be the substrates of the dark substances in DPF pericarp, but more investigations are needed to identify them.

Straw incorporation induces rice straighthead disease in As-contaminated paddy soil.

Rice straw incorporation is globally recognized as a viable alternative to incineration. However, it might lead to arsenic (As) methylation in soils, resulting in increased accumulation of methylated As in rice plants, potentially contributing to the emergence of rice straighthead disease. To evaluate the effect of straw incorporation on the As transformation in the paddy field system, we conducted a pot experiment for rice cultivation in two paddy soils with different As background levels and also characterized the response of the soil microbial community to straw incorporation. The results showed that straw incorporation elevated the total and methylated As concentration within the soil solution and rice plants, which in turn reduced rice seed setting rate and yield, and caused straighthead disorder in rice cultivated in soils with high As levels. 16S rRNA-based sequencing demonstrated reduced abundance and diversity of microorganisms upon adding straw. Notably, the dominant phylum, Bacteroidetes, exhibited a significant increase in abundance due to straw integration, while the abundance of Proteobacteria and Acidobacteria decreased. At the family level, the prevalence of Rikenellaceae increased only in soils contaminated with As following straw incorporation. Redundancy analysis showed positive associations between Rikenellaceae and levels of methylated As present in both soil porewater and rice husks, suggesting a potentially pivotal role of Rikenellaceae in the As methylation process after straw integration. These findings collectively emphasize that including straw can reshape the soil's microbial community and amplify As methylation in the soil, thereby promoting the uptake and accumulation of methylated As in rice and inducing straighthead disease in As-contaminated soil.

Cadmium, arsenic, and mineral nutrients in rice and potential risks for human health in South China.

Rice (Oryza sativa L.) is one of the most important staple food crops worldwide. For people fed on rice, toxic elements cadmium (Cd) and arsenic (As) and mineral nutrients in rice are pivotal to evaluate potential risks of harmful element intake and malnutrition. We collected rice samples of 208 cultivars (83 inbred and 125 hybrid) from fields in South China and determined Cd, As, As species, and mineral elements in brown rice. Chemical analysis shows that the average content of Cd and As in brown rice were 0.26 ± 0.32 and 0.21 ± 0.08 mg·kg-1, respectively. Inorganic As (iAs) was the dominative As species in rice. Rice Cd and iAs in 35.1% and 52.4% of the 208 cultivars exceeded rice Cd and iAs limits, respectively. Significant variations of rice subspecies and regions were found for Cd, As, and mineral nutrients in rice (P < 0.05). Inbred rice had lower As uptake and more balanced mineral nutrition than hybrid species. Significant correlation was observed between Cd, As versus mineral elements like Ca, Zn, B, and Mo (P < 0.05). Health risk assessment indicates that high risks of non-carcinogenic and carcinogenic of Cd and iAs, and malnutrition, in particular Ca, protein and Fe deficiencies, might be caused by rice consumption in South China.

Potassium Sulfate Spray Promotes Fruit Color Preference via Regulation of Pigment Profile in Litchi Pericarp.

Fruit color is a decisive factor in consumers' preference. The bright red color of litchi fruit is associated with its high anthocyanin; however, poor fruit coloration is a major obstacle in litchi plantation. The role of spraying mineral nutrient salts such as KH2PO4, KCl, K2SO4, and MgSO4 on litchi pericarp pigmentation was examined by a field trial, and the relation between human visual color preference versus pericarp pigments and hue-saturation-brightness (HSB) color parameters was investigated. K2SO4-sprayed litchi fruit gained the maximum popularity for its attractive red color. Spray of K and Mg salts decreased the buildup of yellowish pigments, but increased the accumulation of red ones, with the exception of slightly reduced anthocyanins in KH2PO4-sprayed fruit, by regulating the activities of enzymes involved in anthocyanidin metabolism and decreasing pericarp pH, leading to varied pericarp pigment composition. K2SO4 spray generated the highest percentage of cyanidin-3-glucoside over all pigments in pericarp. Correlation analysis shows the percent of cyanidin-3-glucoside, superior to anthocyanin concentration and HSB color parameters, was a reliable indicator to fruit color preference. This work demonstrates that spray of suitable mineral salt can regulate pericarp pigment profile, and is an effective approach to improve fruit pigmentation and promote its popularity.

MOF-derived cluster-shaped magnetic nanocomposite with hierarchical pores as an efficient and regenerative adsorbent for chlortetracycline removal.

The presence of large amounts of antibiotic residues can potentially threaten environmental sustainability and human health. Thus, it is imperative to develop convenient and effective technologies for eliminating antibiotics from aquatic environments, which are major contaminant reservoirs. Herein, based on Zn/Fe-MIL-88B, we designed and synthesized a magnetic nanocomposite (MC) that contains hierarchical pores and as an effective and regenerative adsorbent for the removal of chlortetracycline (CTC) from water. The characteristics of the MC and its CTC adsorption performance were investigated systematically. The synthesized MC sample pyrolyzed at 800 °C (MC-800) consisted of metallic iron and N/O-doped graphitic carbon along with cluster-like particles with a mesoporous structure. Further, the adsorption of CTC on MC-800 (maximum adsorption amount of 1158.0 mg/g) could be described using the Freundlich isotherm model and a pseudo-second-order model, indicating that the surface of MC-800 was heterogeneous. The adsorption is likely driven by weak chemical forces, including hydrogen bond formation, cation-π electron donor-acceptor (EDA), and π-π EDA interactions. Finally, MC-800 could be recovered readily through facile magnetic separation and regenerated such that its adsorption rate remained higher than 85% even after five cycles.

Magnetically separable Fe-MIL-88B_NH2 carbonaceous nanocomposites for efficient removal of sulfamethoxazole from aqueous solutions.

Extensive exposure to antibiotics could potentially be harmful to the environment and human health. The development of effective and convenient technologies to remove residual antibiotics from water is imperative. Herein, we successfully developed a facile method via pyrolysis of Fe-MIL-88B_NH2 to synthesize magnetic nanocomposites (MNC) as potential adsorbents, which exhibited cluster-shape structure and excellent magnetic response. Magnetic nanocomposites carbonized at 700 °C showed high efficiency for sulfamethoxazole (SMX) adsorption (73.53 mg/g). Some experimental conditions including solution pH, ionic strength, coexisting ions and SMX concentration were systematically investigated. The adsorption isotherm and kinetic followed Langmuir and the pseudo-second-order models, and the adsorption process was dependent on the solution pH. The adsorption mechanism hypothesis was pore filling effect, π-π EDA and electrostatic interactions. Moreover, MNC-700 exhibited good reusability and magnetic separation properties, being reused six times without significant loss in adsorption capacity.

Degradation of tetracyclines in manure-amended soil and their uptake by litchi (Litchi chinensis Sonn.).

The environmental and human health risk posed by veterinary antibiotics is of global concern. Antibiotic uptake by herbal plants has been studied, but little is known about perennial woody fruit crops. Litchi (Litchi chinensis Sonn.), a longevial fruit tree, is routinely fertilized with animal manure and, therefore, may be at risk of antibiotic uptake into its fruits. This study investigated the degradation of chlortetracycline and doxycycline present in manure used to amend orchard soil, and their subsequent assimilation by litchi plant, as affected by manure application rate. The results show that half-lives of chlortetracycline and doxycycline in soil were decreased by increased manure rate, with an average of 27 and 59 days, respectively. Chlortetracycline was readily transported to litchi shoots and increased with the growth of litchi plants. Doxycycline predominantly remained in the roots, and underwent growth dilution in the plants. The two tetracyclines could not be detected in fruits from litchi trees when applied with manures, at various rates, over 2 years. For litchi, chlortetracycline may pose human health risk through manure application, but doxycycline is unlikely to do so. Long-term field experiments are required to monitor antibiotic accumulation in fruits of perennial fruit trees fertilized with animal manure.

Soil calcium significantly promotes uptake of inorganic arsenic by garland chrysanthemum (ChrysanthemumL coronarium) fertilized with chicken manure bearing roxarsone and its metabolites.

Roxarsone (ROX), a widely used feed organoarsenic additive, occurs as itself and its metabolites in animal manure that is commonly land used as fertilizer. Soil property impacts arsenic (As) speciation and bioavailability. Fourteen soils across China were used to conduct culture experiments to investigate As uptake by garland chrysanthemum (ChrysanthemumL coronarium), with the soils fertilized with chicken manure bearing ROX and its metabolites. The results show As(III) was the sole As form in garland chrysanthemum shoots, and As(III) and As(V) occurred in roots. Only inorganic As was detected in all soils when the plants were harvested. Stepwise regression analysis shows soil-exchangeable Ca predominated shoot As(III) concentration (shoot As(III) = 1.60030 soil Ca, R 2 = 0.8832***). Therefore, ROX is transferred into the human food chain finally as inorganic As in plants. Application of animal manure bearing ROX and its metabolites is not recommended in Ca-rich soils to avoid excess inorganic As dietary exposure.

Delivery of roxarsone via chicken diet→chicken→chicken manure→soil→rice plant.

Roxarsone (ROX), a widely used feed additive, occurs as itself and its metabolites in animal manure. Rice is prone to accumulate As than other staple food. Four diets with 0, 40, 80 and 120mgROXkg(-1) were fed in chickens, and four chicken manures (CMs) were collected to fertilize rice plants in a soil culture experiment. Linear regression analysis shows that the slopes of As species including 4-hydroxy-phenylarsonic acid, As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in CM versus dietary ROX were 0.033, 0.314, 0.033, 0.054 and 0.138, respectively. Both As(III) and DMA were determined in all rice grains, and As(III), As(V), MMA and DMA in rice hull, but detectable As forms in rice straws and soils increased with increasing ROX dose. Grain As(III) was unrelated to ROX dose but exceeded the Chinese rice As limit (0.15mgAs(III)kg(-1)). Dietary ROX enhanced straw As(III) mostly, with the slope of 0.020, followed by hull DMA (0.006) and grain DMA (0.002). The slopes of soil As(V) and As(III) were 0.003 and 0.001. This is the first report illustrating the quantitative delivery of ROX via food chain, which helps to evaluate health and environmental risks caused by ROX use in animal production.

Activation of molecular oxygen by a metal-organic framework with open 2,2'-bipyridine for selective oxidation of saturated hydrocarbons.

A metal-organic framework with open 2,2'-bipyridine sites can efficiently activate molecular oxygen for selective oxidation of a variety of saturated hydrocarbons with unprecedented activities and selectivities.