The use of lanthanum-anchored zinc oxide distorted hexagon (La@ZnO DH) nanoclusters as an active material for the photodegradation of rhodamine B (Rh–B) dye via hydrogen bonding, electrostatic, and π-π interactions is examined herein. The active photocatalyst is derived from porous zeolite imidazole frameworks (ZIF-8) via a combined ultrasonication and calcination process. The distorted hexagon nanocluster morphology with controlled surface area is shown to provide excellent catalytic activity, chemical stability and demarcated pore volume. In addition, the low bandgap (3.57 eV) of La@ZnO DH is shown to expand the degradation of Rh–B under irradiation of UV light as compared to the pristine ZIF-8-derived ZnO photocatalyst due to inhibited recombination of electrons and holes. The outstanding physicochemical stability and enhanced performance of La@ZnO DH could be ascribed to the synergistic interaction among La3+ particles and the ZnO nanoclusters and provide a route for their utilization as a promising catalyst for the detoxification of Rh–B.

Imazalil (IMZ) is an imidazole fungicide commonly used by fruit-packaging plants (FPPs) to control fungal infections during storage. Its application leads to the production of pesticide-contaminated wastewaters, which, according to the European Commission, need to be treated on site. Considering the lack of efficient treatment methods, biodepuration systems inoculated with tailored-made inocula specialized on the removal of such persistent fungicides appear as an appropriate solution. However, nothing is known about the biodegradation of IMZ. We aimed to isolate and characterize microorganisms able to degrade the recalcitrant fungicide IMZ and eventually to test their removal efficiency under near practical bioengineering conditions. Enrichment cultures from a soil receiving regular discharges of effluents from a FPP, led to the isolation of a Cladosporium herbarum strain, which showed no pathogenicity on fruits, a trait essential for its biotechnological exploitation in FPPs. The fungus was able to degrade up to 100 mg L⁻¹ of IMZ. However, its degrading capacity and growth was reduced at increasing IMZ concentrations in a dose-dependent manner, suggesting the involvement of a detoxification rather than an energy-gain mechanism in the dissipation of IMZ. The isolate could tolerate and gradually degrade the fungicides fludioxonil (FLD) and thiabendazole (TBZ), also used in FPPs and expected to coincide alongside IMZ in FPP effluents. The capacity of the isolate to remove IMZ in a practical context was evaluated in a benchtop immobilized-cell bioreactor fed with artificial IMZ-contaminated wastewater (200 mg L⁻¹). The fungal strain established in the reactor, completely dominated the fungal community and effectively removed >96% of IMZ. The bioreactor also supported a diverse bacterial community composed of Sphingomonadales, Burkholderiales and Pseudomonadales. Our study reports the isolation of the first IMZ-degrading microorganism with high efficiency to remove IMZ from agro-industrial effluents under bioengineering conditions.

In this study, N-functionalized biochars with varied structural characteristics were designed by loading poplar leaf with different amounts of urea at 1:1 and 1:3 ratios through pyrolysis method. The addition of urea significantly increased the N content of biochar and facilitated the formation of amine (-NH-, -NH₂), imine (-HCNH), benzimidazole (-C₇H₅N₂), imidazole (-C₃H₃N₂), and pyrimidine (-C₄H₃N₂) groups due to substitution reaction and Maillard reaction. The effect of pH on Cr(VI) removal suggested that decrease in solution pH favored the formation of electrostatic attraction between the protonated functional groups and HCrO₄⁻. And, experimental and density functional theory study were used to probe adsorption behaviors and adsorption mechanism which N-functionalized biochars interacted with Cr(VI). The protonation energy calculations indicated that N atoms in newly formed N-containing groups were better proton acceptors. Adsorption kinetics and isotherm experiments exhibited that N-functionalized biochars had greater removal rate and removal capacity for Cr(VI). The removal rate of Cr(VI) on N-functionalized biochar was 10.5–15.5 times that of untreated biochar. Meanwhile, N-functionalized biochar of NB3 with the largest number of adsorption sites for -C₇H₅N₂, -NH₂, -OH, -C₃H₃N₂, and phthalic acid (-C₈H₅O₄) exhibited the supreme adsorption capacity for Cr(VI) through H bonds and the highest adsorption energy was −5.01 kcal/mol. These mechanistic findings on the protonation and adsorption capacity are useful for better understanding the functions of N-functionalized biochars, thereby providing a guide for their use in various environmental applications.

Hexavalent chromium (Cr(VI)) has significantly threatened the environmental health because of its distinct toxicity. A novel magnetic core-shell structured NZVI@ZD composite was designed for simultaneous adsorption and reduction of Cr(VI). NZVI@ZD was synthesized by carbonization of the as-prepared core-shell structure NZVI@zeolitic imidazole framework-67 (ZIF-67). After carbonization, the original ZIF-67 shell shape was preserved well with marginal parts developing to graphitized carbon. Both cobalt (Co) and NZVI nanoparticles were finely dispersed in the porous ZIF-67 derivative (ZD). NZVI@ZD exhibited excellent removal performance for Cr(VI), owing to its high specific surface area and large pore size favorable for Cr(VI) adsorption and diffusion. The maximum adsorption capacity of NZVI@ZD for Cr(VI) was surprisingly as high as 226.5 mg g⁻¹, surpassing the pristine ZIF-67 (29.35 mg g⁻¹) and NZVI@ZIF-67 (36.53 mg g⁻¹). Zeta potential and X-ray photoelectron spectroscopy (XPS) spectra revealed that electrostatic attraction, reduction and precipitation might be involved in the Cr(VI) removal process by NZVI@ZD, resulting in the conversion of the adsorbed Cr(VI) to Cr(III) of lower toxicity and an eventual immobilization on the NZVI@ZD. The magnetic core-shell structured NZVI@ZD possessed superior adsorptive reactivity for Cr(VI) to most other traditional or newly reported materials, thus should be deemed highly efficient for Cr(VI)-contaminated wastewater treatment.

A novel eco-friendly molecularly imprinted polymer (MIP) was proposed as solid-phase extraction (SPE) adsorbent to selective adsorption tylosin (TYL) in animal muscle samples. The MIP was synthesized in aqueous by using 1,4-butanediyl-3,3-bis-1-vinyl imidazolium chloride and 2-acrylamide-2-methylpropanesulfonic acid as bifunctional monomer. The obtained MIP had excellent selectivity towards TYL in water, and the maximum binding capacity can reach 123.45 mg g⁻¹. Combined with high-performance liquid chromatography, the presented MIP can be used as SPE sorbent to recognize and detect TYL in the range of 0.008 to 0.6 mg L⁻¹ (R² = 0.9995). The limit of detection and limit of quantification were 0.003 mg L⁻¹ and 0.008 mg L⁻¹, and the intraday and interday precision were 1.05% and 3.36%, respectively. Under the optimal condition, the established MIP-SPE-HPLC method was successfully applied to separate and determine trace TYL in chicken, pork, and beef samples with satisfactory recoveries ranged from 94.0 to 106.3%, and the MIP-SPE cartridge can be cycled at least 20 times. This study implies a promising green MIP-SPE-HPLC method for highly selective adsorption and analysis trace TYL in complex matrices.

Demand of clean water is always a major concern due to continuous use of toxic pesticides and herbicides to overcome food scarcity. In Asian countries, wide use of ionizable 2,4-D herbicide has worsen problem due to its less binding ability with soil and can easily contaminate drinking water that causes potential risks to humans and environment. The present research focused on synthesis of amino-factionalized coordination complexes using imidazole-based amino benzoic acid ligands for remediation of acidic 2,4-D herbicide. Coordination complexes characterized with FTIR, ¹H-NMR, elemental analysis, thermogravimetric analysis, powder XRD, and BET revealed successful incorporation of functionalized groups with high thermal stability and surface area that make them suitable for adsorption experiments. Batch adsorption experiments conducted at different temperature conditions depicted the spontaneous physisorption process (− ∆G) having endothermic nature (∆H, ∆S). The removal efficiency of the amino-functionalized coordination complex is found to be higher (73%) compared to non-functionalized (35%) and acetic anhydride-functionalized coordination complex (42%). Kinetic studies supported pseudo 2nd-order kinetics with three phases of adsorption depicted by intra-particle diffusion model. Amino-functionalized complexes favored Langmuir isotherm while Freundlich isotherm is best fitted for non-functionalized complexes. The synthesized adsorbents were also proven to be effective for removal of herbicide from irrigated wastewater with average percent removal of 56% for amino functionalized, acetic anhydride functionalized (23%), and non-functionalized (20%).

With increasing environment pollution and bacterial transmitted viral diseases globally, the development of new, effective, and low-cost materials/strategies is the current major challenge. To combat with this alarming problem, three new multi-functional and thermally stable SnO₂NPs@ZIF-8 composites (NC1, NC2, and NC3) were synthesized by a facile and sustainable approach involving in situ encapsulation of SnO₂NPs (150, 300, and 500 μL suspension in methanol) within zeolitic imidazole framework at room temperature. The morphology and crystallinity of ZIF-8 remained unchanged upon the proper encapsulation of SnO₂NPs in its matrix. Herein, for the first time, the antiviral potential of ZIF-8 and SnO₂NPs@ZIF-8 against chikungunya virus is reported by investigating their cytotoxicity against Vero cell line (employing MTT ((3-(4,5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide)) assay). The maximum non-toxic doses were 0.04 mg mL⁻¹ for ZIF-8 and SnO₂NPs@ZIF-8 and 0.1 mg mL⁻¹ for SnO₂NPs. Further, NC1 exhibited (based on plaque assay) reduction in viral load/titers up to > 80% during post-treatment and > 50% during pre-treatment, greater than that of ZIF-8 and SnO₂NPs due to synergistic effect. Further, NC1 (10 mg) exhibited enhanced photocatalytic efficiency (≥ 96%) for degradation of methylene blue (0.5 × 10⁻⁵ M) at pH ˃ 7.0. The probable mechanism for their antiviral activity and photocatalytic activity has been discussed. The multi-functional composites can effectively be used to reduce water pollution and as remedy for mosquito/bacterial transmitted viral diseases.

Ketoconazole is an imidazole fungicide which is commonly used as pharmaceutical and healthcare products. Residual amount of this compound can cause adverse ecological health problems. The present study investigated ketoconazole photocatalytic degradation using Ag₃PO₄/graphene oxide (GO). Ag₃PO₄/GO and Ag₃PO₄ as visible light-driven photocatalysts was synthesized using the in situ growth method. Degradation of ketoconazole at the concentration of 1–20 mg/L in aqueous solutions was optimized in the presence of Ag₃PO₄/GO nanocomposite with the dosage of 0.5–2 g/L, contact time of 15–20 min, and pH of 5–9 using response surface methodology. A second-order model was selected as the best fitted model with R² value and lack of fit as 0.935 and 0.06, respectively. Under the optimized conditions, the Ag₃PO₄/GO catalyst achieved a photocatalytic efficiency of 96.53% after 93.34 min. The photocatalytic activity, reaction kinetics, and stability were also investigated. The results indicated that the Ag₃PO₄/GO nanocomposite exhibited higher photocatalytic activity for ketoconazole degradation, which was 2.4 times that of pure Ag₃PO₄. Finally, a direct Z-scheme mechanism was found to be responsible for enhanced photocatalytic activity in the Ag₃PO₄/GO nanocomposite. The high photocatalytic activity, acceptable reusability, and good aqueous stability make the Ag₃PO₄/GO nanocomposite a promising nanophotocatalyst for photocatalytic degradation of azoles contaminants.

Imazalil (IMZ), a fungicide containing imidazole group, is extensively used for the prevention and treatment of fungal diseases in plants. Current study was performed to examine cyto-genotoxic potential of IMZ on Allium cepa roots by following Allium ana-telophase and single cell gel electrophoresis (comet) assays. The concentration which reduced the growth of the root tips of IMZ by 50% compared to the negative control group (EC₅₀) was found to be 1 μg/mL by Allium root growth inhibition test. 0.5, 1, and 2 μg/mL concentrations of IMZ were exposed to Allium roots for intervals of 24, 48, 72, and 96 h. 10 μg/mL of methyl methane sulfonate (MMS) and distilled water were used as control groups, both positive and negative. Statistical analysis was performed by using one-way ANOVA with Duncan’s multiple comparison tests at p ≤ 0.05 and Pearson correlation test at p = 0.01. IMZ showed cytotoxic effect by statistically decreasing root growth and mitotic index (MI) and also genotoxic effect by statistically increasing chromosomal aberrations (CAs) and DNA damage compared to the negative control group. With these cyto-genotoxic effects, it should be used carefully and further cyto-genotoxic mechanisms should be investigated along with other toxicity tests.

Endocrine-disrupting compounds are attracting attention worldwide because of their effects on living things in the environment. Ten endocrine disrupting compounds: 4-nonylphenol, 2,4-dichlorophenol, estrone, 17β-estradiol, bisphenol A, 4-tert-octylphenol, triclosan, atrazine, imidazole and 1,2,4-triazole were investigated in four rivers and wastewater treatment plants in this study. Rivers were sampled at upstream, midstream and downstream reaches, while the influent and effluent samples of wastewater were collected from treatment plants near the receiving rivers. Sample waters were freeze-dried followed by extraction of the organic content and purification by solid-phase extraction. Concentrations of the compounds in the samples were determined with ultra-high performance liquid chromatography-tandem mass spectrometry. The instrument was operated in the positive electrospray ionization (ESI) mode. The results showed that these compounds are present in the samples with nonylphenol > dichlorophenol > bisphenol A > triclosan > octylphenol > imidazole > atrazine > triazole > estrone > estradiol. Nonylphenol has its highest concentration of 6.72 μg/L in King Williams Town wastewater influent and 2.55 μg/L in midstream Bloukrans River. Dichlorophenol has its highest concentration in Alice wastewater influent with 2.20 μg/L, while it was 0.737 μg/L in midstream Bloukrans River. Uitenhage wastewater effluent has bisphenol A concentration of 1.684 μg/L while it was 0.477 μg/L in the downstream samples of the Bloukrans River. Generally, the upstream samples of the rivers had lesser concentrations of the compounds. The wastewater treatment plants were not able to achieve total removal of the compounds in the wastewater while runoffs and wastes dump from the cities contributed to the concentrations of the compounds in the rivers.