Synergistic impacts of antibiotics and heavy metals on Hermetia illucens: Unveiling dynamics in larval gut bacterial communities and microbial metabolites.

Hermetia illucens larvae showcases remarkable bioremediation capabilities for both antibiotics and heavy metal contaminants. However, the distinctions in larval intestinal microbiota arising from the single and combined effects of antibiotics and heavy metals remain poorly elucidated. In this study, we delved into the details of larval intestinal bacterial communities and microbial metabolites when exposed to single and combined contaminants of oxytetracycline (OTC) and hexavalent chromium (Cr(VI)). After conversion, single contaminant-spiked substrate showed 75.5% of OTC degradation and 95.2% of Cr(VI) reductiuon, while combined contaminant-spiked substrate exhibited 71.3% of OTC degradation and 93.4% of Cr(VI) reductiuon. Single and combined effects led to differences in intestinal bacterial communities, mainly reflected in the genera of Enterococcus, Pseudogracilibacillus, Gracilibacillus, Wohlfahrtiimonas, Sporosarcina, Lysinibacillus, and Myroide. Moreover, these effects also induced differences across various categories of microbial metabolites, which categorized into amino acid and its metabolites, benzene and substituted derivatives, carbohydrates and its metabolites, heterocyclic compounds, hormones and hormone-related compounds, nucleotide and its metabolites, and organic acid and its derivatives. In particular, the differences induced OTC was greater than that of Cr(VI), and combined effects increased the complexity of microbial metabolism compared to that of single contaminant. Correlation analysis indicated that the bacterial genera, Preudogracilibacillus, Enterococcus, Sporosarcina, Lysinibacillus, Wohlfahrtiimonas, Ignatzschineria, and Fusobacterium exhibited significant correlation with significant differential metabolites, these might be used as indicators for the resistance and bioremediation of OTC and Cr(VI) contaminants. These findings are conducive to further understanding that the metabolism of intestinal microbiota determines the resistance of Hermetia illucens to antibiotics and heavy metals.

The underlying mechanisms of oxytetracycline degradation mediated by gut microbial proteins and metabolites in Hermetia illucens.

Hermetia illucens larvae can enhance the degradation of oxytetracycline (OTC) through its biotransformation. However, the underlying mechanisms mediated by gut metabolites and proteins are unclear. To gain further insights, the kinetics of OTC degradation, the functional structures of gut bacterial communities, proteins, and metabolites were investigated. An availability-adjusted first-order model effectively evaluated OTC degradation kinetics, with degradation half-lives of 4.18 and 21.71 days for OTC degradation with and without larval biotransformation, respectively. Dominant bacteria in the larval guts were Enterococcus, Psychrobacter, Providencia, Myroides, Enterobacteriaceae, and Lactobacillales. OTC exposure led to significant differential expression of proteins, with functional classification revealing involvement in digestion, transformation, and adaptability to environmental stress. Upregulated proteins, such as aromatic ring hydroxylase, acted as oxidoreductases modifying the chemical structure of OTC. Unique metabolites, aclarubicin and sancycline identified were possible OTC metabolic intermediates. Correlation analysis revealed significant interdependence between gut bacteria, metabolites, and proteins. These findings reveal a synergistic mechanism involving gut microbial metabolism and enzyme structure that drives the rapid degradation of OTC and facilitates the engineering applications of bioremediation.

Enhanced biodegradation of microplastic and phthalic acid ester plasticizer: The role of gut microorganisms in black soldier fly larvae.

Hermetia illucens larvae are recognized for their ability to mitigate or eliminate contaminants by biodegradation. However, the biodegradation characteristics of microplastics and phthalic acid esters plasticizers, as well as the role of larval gut microorganisms, have remained largely unrevealed. Here, the degradation kinetics of plasticizers, and biodegradation characteristics of microplastics were examined. The role of larval gut microorganisms was investigated. For larval development, microplastics slowed larval growth significantly (P < 0.01), but the effect of plasticizer was not significant. The degradation kinetics of plasticizers were enhanced, resulting in an 8.11 to 20.41-fold decrease in degradation half-life and a 3.34 to 3.82-fold increase in final degradation efficiencies, compared to degradation without larval participation. The depolymerization and biodeterioration of microplastics were conspicuously evident, primarily through a weight loss of 17.63 %-25.52 %, variation of chemical composition and structure, bio-oxidation and bioerosion of microplastic surface. The synergistic effect driven by larval gut microorganisms, each with various functions, facilitated the biodegradation. Specifically, Ignatzschineria, Paenalcaligenes, Moheibacter, Morganella, Dysgonomonas, Stenotrophomonas, Bacteroides, Sphingobacterium, etc., appeared to be the key contributors, owing to their xenobiotic biodegradation and metabolism functions. These findings offered a new perspective on the potential for microplastics and plasticizers biodegradation, assisted by larval gut microbiota.

Highly Active and Water-Resistant Cu-Doped OMS-2 Catalysts for CO Oxidation: The Importance of the OMS-2 Synthesis Method and Cu Doping.

Porous cryptomelane-type Mn oxide (OMS-2) has an outstanding redox property, making it a highly desirable substitute for noble metal catalysts for CO oxidation, but its catalytic activity still needs to be improved, especially in the presence of water. Given the strong structure-performance correlation of OMS-2 for oxidation reactions, herein, OMS-2 is synthesized by solid state (OMS-2S), reflux (OMS-2R), and hydrothermal (OMS-2H) methods, aiming to improve its CO oxidation performance through manipulating synthesis parameters to tailor its particle size, morphology, and crystallinity. Characterization shows that OMS-2S has the highest CO oxidation activity in the absence of water due to its low crystallinity, high specific surface area, large oxygen vacancy content, and good redox property, but the presence of water can greatly reduce its CO oxidation activity. Doping Cu into an OMS-2 can not only improve its CO oxidation activity but also greatly improve its water tolerance. The Cu-doped OMS-2S catalyst with ∼4 wt % Cu can achieve a T90 of 49 °C (1% CO/10% O2/N2 and WHSV = 60,000 mL·g-1·h-1), ranking among the lowest reported T90 values for Mn oxide-based CO oxidation catalysts, and it can maintain nearly 100% CO conversion in the presence of 5 vol % water for over 50 h. In situ DRIFTs characterization indicates that the good water resistance of Cu-doped OMS-2S can be attributed to the significantly suppressed surface hydroxyl group generation because of Cu doping. This work demonstrates the importance of the synthesis method and Cu doping in determining the CO oxidation activity and water resistance of OMS-2 and will provide guidance for synthesizing highly active and water-resistant CO oxidation catalysts.

Integrated pretreatment of poplar biomass employing p-toluenesulfonic acid catalyzed liquid hot water and short-time ball milling for complete conversion to xylooligosaccharides, glucose, and native-like lignin.

This work aimed to study an integrated pretreatment technology employing p-toluenesulfonic acid (TsOH)-catalyzed liquid hot water (LHW) and short-time ball milling for the complete conversion of poplar biomass to xylooligosaccharides (XOS), glucose, and native-like lignin. The optimized TsOH-catalyzed LHW pretreatment solubilized 98.5% of hemicellulose at 160 °C for 40 min, releasing 49.8% XOS. Moreover, subsequent ball milling (20 min) maximized the enzymatic hydrolysis of cellulose from 65.8% to 96.5%, owing to the reduced particle sizes and cellulose crystallinity index. The combined pretreatment reduced the crystallinity by 70.9% while enlarging the average pore size and pore volume of the substrate by 29.5% and 52.4%, respectively. The residual lignin after enzymatic hydrolysis was rich in ß-O-4 linkages (55.7/100 Ar) with less condensed structures. This lignin exhibited excellent antioxidant activity (RSI of 66.22) and ultraviolet absorbance. Thus, this research suggested a sustainable waste-free biorefinery for the holistic valorization of biomass through two-step biomass fractionation.

Visible-light-driven photocatalytic N2 fixation to nitrates by 2D/2D ultrathin BiVO4 nanosheet/rGO nanocomposites.

Photocatalytic nitrogen fixation is a promising approach owing to its environmental friendliness and cost-effectiveness. The 2D/2D BiVO4/rGO hybrid developed in this study exhibits a high nitrate-production rate of 1.45 mg h-1 g-1 and an apparent quantum efficiency (QE) of 0.64% at 420 nm, which represents one of the most highly active photocatalysts reported thus far.

Highly porous Fe/N/C catalyst for oxygen reduction: the importance of pores.

Fe/N/C full of ultrafine Fe-based species and pores is synthesized by pyrolyzing a g-C3N4-coordinated Fe matrix embedded in carbon for oxygen reduction. Enhanced oxygen reduction activity is observed on Fe/N/C with higher pore volume and the Fe/N/C catalyst with the largest pore volume shows the highest half-wave potential of 0.890 V.

Investigations of CO2 Capture from Gas Mixtures Using Porous Liquids.

Porous liquids, a new porous material with fluidity, can be applied in numerous fields, such as gas storage and/or separation. In this work, the separation of binary gas mixtures CO2/N2 and CO2/CH4 with porous liquids was examined by molecular dynamics (MD) simulations. The pure gas adsorption capacity was analyzed with different concentrations of porous liquids. The dependence of the separation effect of a gas mixture on the total pressure and temperature was investigated. Meanwhile, for both CO2/N2 and CO2/CH4 systems, the adsorption and separation effects of porous liquids with a cage:solvent ratio of 1:12 are better than those of 1:91 and 1:170. The results of the spatial distribution function and/or trajectories indicated that porous liquids prefer CO2, leading to the location of CO2 in the channels formed in porous liquids. However, N2 and CH4 are hardly adsorbed into the bulk. The diffusion of gas molecules follows the order of CO2 > N2 (for CO2/N2) and CH4 > CO2 (for CO2/CH4) in the bulk and N2 > CO2 (for CO2/N2) and CH4 > CO2 (for CO2/CH4) at the interface of porous liquids. Upon increasing the concentrations of porous liquids, the working capacities of CO2 show small decreases in CO2/N2 and CO2/CH4 systems, but the sorbent selection parameters are higher in pressure- and temperature-swing adsorption processes. The porous liquid with a cage:solvent ratio of 1:12 is more suitable for the separation of CO2/N2 and CO2/CH4 systems than ratios of 1:91 and 1:170.

Multi-role graphitic carbon nitride-derived highly porous iron/nitrogen co-doped carbon nanosheets for highly efficient oxygen reduction catalyst.

Pyrolyzing precursors containing iron, nitrogen and carbon elements is a commonly used process for synthesizing FeNC catalysts for oxygen reduction reaction (ORR). Generally, aggregation of iron-based species is prone to occur because of a lack of chemical bonds between iron-based species and carbon matrix and synthesizing highly porous FeNC catalysts is difficult because carbon skeleton is prone to collapse during pyrolysis. Herein, highly porous FeNC catalysts with fine iron-based species are synthesized by selecting glucose as carbon source, FeCl3 as iron source, and urea-derived g-C3N4 as nitrogen source, iron anchoring and stabilizing species, and pore-forming template. The multi-role g-C3N4-derived catalyst synthesized at 1100 °C (FeNC1100) has fine iron-based species, large specific surface area (737 m2 g-1), and extremely high pore volume (2.66 cm3 g-1). Accordingly, FeNC1100 shows a larger half-wave potential (E1/2 = 0.894 V), a higher stability (ΔE1/2 = 6 mV) after 10,000 potential cycles in alkaline media, and a higher peak power density (P = 152 mW cm-2) when employed as ORR catalyst of zinc-air battery, which are all superior to those of the commercial Pt/C catalyst (E1/2 = 0.864 V, ΔE1/2 = 30 mV, P = 134 mW cm-2). The present work brings a new method for synthesizing highly porous FeNC catalysts decorated with fine active sites for ORR.

Zinc, sulfur and nitrogen co-doped carbon from sodium chloride/zinc chloride-assisted pyrolysis of thiourea/sucrose for highly efficient oxygen reduction reaction in both acidic and alkaline media.

Zn and N co-doped carbon (Zn-N-C) shows encouraging catalytic stability for oxygen reduction reaction (ORR) because of the fulfilled d orbital of Zn, but its catalytic activity is not satisfactory. Herein, hierarchically porous Zn, S and N co-doped carbon (Zn-S-N-C) with large specific surface area (2433 m2 g-1) and pore volume (3.007 cm3 g-1) is synthesized by using NaCl/ZnCl2-assisted pyrolysis of sucrose and thiourea. The Zn-S-N-C catalyst exhibits superior ORR activity with half-wave potentials (E1/2) up to 0.774 V in 0.1 M HClO4 and 0.894 V in 0.1 M KOH, good ORR stability with 19- and 4-mV loss in E1/2 values after 10,000 potential cycles in 0.1 M HClO4 and 0.1 M KOH, respectively, and excellent methanol tolerance. The good ORR performance of Zn-S-N-C can be attributed to its enhanced intrinsic ORR activity resulting from the formation of S, N doped carbon and ZnS in Zn-S-N-C, its hierarchically porous structure resulting from the pore-forming roles played by ZnCl2, NaCl and thiourea, and its improved graphitization degree resulting from the added ZnCl2 during Zn-S-N-C synthesis. This work will provide a novel strategy for the synthesis of hierarchically porous Zn, S and N co-doped carbon materials for ORR.

Porous Material Screening and Evaluation for Deep Desulfurization of Dry Air.

We employ molecular simulations to screen the best microporous materials for deep desulfurization of dry air. Pressure-swing adsorption and temperature-swing adsorption in desulfurization processes are investigated. The selectivity, working ability, selection parameters, and diffusivity of mixed gases are examined to evaluate those materials. The results show that UiO-66, ZIF-71, ZIF-69, and ZIF-97 exhibit good performance for the separation of H2S from air. The selectivity and adsorption capacity of H2S are larger than 300 and 0.01 mmol/g at room temperature and atmospheric pressure, respectively. UiO-66, ZIF-71, ZIF-69, MIL-100, Zn-DOBDC, ZnBDC, IRMOF-11, and MIL-140B are ideal materials to remove SO2 in air. The selectivity of SO2 is higher than 500 and the adsorption capacity is higher than 0.06 mmol/g. The diffusivity of sulfides is determined by the competition between the sterically hindered effect and the intermolecular synergistic effect. Comprehensive analysis found that zeolitic imidazolate frameworks (ZIFs) are good materials for the removal of sulfides.

A ZIF-derived hierarchically porous Fe-Zn-N-C catalyst synthesized via a two-stage pyrolysis for the highly efficient oxygen reduction reaction in both acidic and alkaline media.

A ZIF-derived Fe-Zn-N-C catalyst with sufficient exposure of bimetallic active sites and well-balanced micro/mesopores is synthesized by a two-stage pyrolysis process and exhibits superior oxygen reduction activity with high half-wave potentials of up to 0.819 V in 0.1 M HClO4 and 0.918 V in 0.1 M KOH.

Electrogenerated alkaline hydrogen peroxide for rice straw pretreatment to enhance enzymatic hydrolysis.

In this work, alkaline hydrogen peroxide (AHP) solution with 1 wt% H2O2 was electrogenerated by oxygen reduction with a current efficiency of 75.2% in a home-made gas diffusion electrode-based electrochemical cell and used for rice straw pretreatment (0.1 g H2O2/g rice straw, 10% (w/v) biomass loading, 55 °C, 2 h). Results showed that the AHP pretreatment removed 97.56% of the initial lignin, 85.75% of the initial hemicellulose, and only 0.56% of the initial cellulose, and the specific surface area and porosity of the AHP pretreated rice straw (AHP-RS) were greatly increased. Saccharification results showed that after 48 h of enzymatic hydrolysis AHP-RS achieved a 3.2-fold increase in reducing sugar concentration compared to the untreated rice straw (5.81 and 1.81 g L-1), highlighting the potential use of this AHP solution for lignocellulose pretreatment.

Effect of iron salt type and dosing mode on Fenton-based pretreatment of rice straw for enzymatic hydrolysis.

Fenton-based processes with four different iron salts in two different dosing modes were used to pretreat rice straw (RS) samples to increase their enzymatic digestibility. The composition analysis shows that the RS sample pretreated by the dosing mode of iron salt adding into H2O2 has a much lower hemicellulose content than that pretreated by the dosing mode of H2O2 adding into iron salt, and the RS sample pretreated by the chloride salt-based Fenton process has a much lower lignin content and a slightly lower hemicellulose content than that pretreated by the sulphate salt-based Fenton process. The higher concentration of reducing sugar observed on the RS sample with lower lignin and hemicellulose contents justifies that the Fenton-based process could enhance the enzymic hydrolysis of RS by removing hemicellulose and lignin and increasing its accessibility to cellulase. FeCl3·6H2O adding into H2O2 is the most efficient Fenton-based process for RS pretreatment.

Ultrasound-assisted alkaline pretreatment for enhancing the enzymatic hydrolysis of rice straw by using the heat energy dissipated from ultrasonication.

Rice straw samples were exposed to ultrasound-assisted alkaline (NaOH) pretreatment by using the heat energy dissipated from ultrasonication to increase their enzymatic digestibility for saccharification. The characterization shows that the pretreatment could selectively remove lignin and hemicellulose without degrading cellulose, and increase porosity and surface area of rice straw. The porosity, surface area and cellulose content of rice straw increased with the increasing concentration of NaOH used. The rice straw sample pretreated by using the heat energy dissipated from ultrasonication has a higher surface area and a lower crystallinity index value than that pretreated by using the external source of heating, and the amount of reducing sugar released from the former sample at 48h of enzymatic saccharification, which is about 3.5 times as large as that from the untreated rice straw sample (2.91vs. 0.85gL-1), is slightly larger than that from the latter sample (2.91vs. 2.73gL-1). The ultrasound-assisted alkaline pretreatment by using the heat energy dissipated from ultrasonication was proved to be a reliable and effective method for rice straw pretreatment.

Pretreatment of rice straw by ultrasound-assisted Fenton process.

Fenton's reagent, ultrasound, and the combination of Fenton's reagent and ultrasound were used to pretreat rice straw (RS) to increase its enzymatic digestibility for saccharification. The characterization shows that compared with ultrasound, Fenton's reagent pretreatment was more efficient in increasing the specific surface area and decreasing the degree of polymerization (DP) of RS. The enzymatic hydrolysis results showed that the RS pretreated by ultrasound-assisted Fenton's reagent (U/F-RS), which exhibited the largest specific surface area and the lowest DP value, had the highest enzymatic activity, and the amount of reducing sugar released from U/F-RS at 48h of enzymatic saccharification is about 4 times as large as that from raw RS and 1.5 times as large as that from Fenton's reagent pretreated RS. The ultrasound-assisted Fenton process provides a reliable and effective method for RS pretreatment.

The leaching kinetics of K-feldspar in sulfuric acid with the aid of ultrasound.

The leaching kinetics of K-feldspar in H2SO4-CaF2 system with the assistant of ultrasound was investigated. The effects of various factors, such as sulfuric acid concentration, liquid-to-solid ratio, CaF2 dosage and leaching temperature were comprehensively studied. The dissolution fraction of potassium can reach more than 83% under the optimum operation conditions with ultrasound. Because of the cavitation effect, the intensified effect with ultrasound has more obvious at lower temperature than higher temperature. The leaching kinetics of K-feldspar with and without ultrasound was successfully modeled by a classic shrinking core model with the product layer diffusion as the rate-controlling step. The activation energies over the temperature range from 60 to 90°C with and without ultrasound were found to be 55.67kJmol-1 and 72.33kJmol-1, respectively. It was found that the rate constant increases greatly in the presence of ultrasound due to the decreased apparent activation energy, resulting in the improved dissolution fraction of potassium.

Depolymerization of microcrystalline cellulose by the combination of ultrasound and Fenton reagent.

In this study, the combined use of Fenton reagent and ultrasound to the pretreatment of microcrystalline cellulose (MCC) for subsequent enzyme hydrolysis was investigated. The morphological analysis showed that the aspect ratio of MCC was greatly reduced after pretreatment. The X-ray diffraction (XRD) and degree of polymerization (DP) analyses showed that Fenton reagent was more efficient in decreasing the crystallinity of MCC while ultrasound was more efficient in decreasing the DP of MCC. The combination of Fenton reaction and ultrasound, which produced the lowest crystallinity (84.8 ± 0.2%) and DP (124.7 ± 0.6) of MCC and the highest yield of reducing sugar (22.9 ± 0.3 g/100 g), provides a promising pretreatment process for MCC depolymerization.