Benzimidazole Research Articles

Broad-spectrum detection of benzimidazoles with lateral flow immunoassay: A computational chemistry-assisted hapten design strategy and explore of molecular recognition mechanism

Benzimidazoles (BMZs) are a class of veterinary drugs with a benzimidazole ring, the abuse of which poses a serious threat to ecological balance and human health. Consequently, the development of broad-spectrum antibodies and rapid assays are crucial for detecting BMZs in food samples. Herein, we scientifically designed three hapten structures, predicted the availability of the hapten with computational chemistry, and subsequently verified the broad-spectrum with immunological experiments. A broad-spectrum monoclonal antibody (6F10) was prepared based on the predicted hapten-2. Molecular recognition studies illustrated intricate interactions between mAb 6F10 binding to BMZs attributed to halogen bonds and π-π/π-alkyl interactions, revealing key amino acid sites and demonstrating the reliability of the hapten prediction strategies. Finally, a broad-spectrum, rapid, and sensitive lateral flow immunoassay based on aggregation-induced emission microspheres with high fluorescence intensity was established. The LOD values of the proposed method for eight kinds of BMZs were 0.027, 0.032, 0.058, 0.091, 0.087, 0.246, 0.369, and 0.311 ng mL−1, respectively. In this work, a hapten prediction strategy based on a computational chemistry method effectively guided the preparation of antibodies for broad-spectrum recognition of BMZs, and the molecular recognition studies verified the interaction of mAb 6F10 with BMZs, enabling broad-spectrum and sensitive detection of BMZs in milk.

An inhibitive system to mitigate the corrosion of AA2024-T3 in 3.5 wt% NaCl solution: Utilizing the synergistic effect of cerium cations and benzimidazole molecules

This study aims to improve the anti-corrosion protection performance of AA2024-T3 using the synergistic effect of organic and inorganic corrosion inhibitors in saline solution. Combining the Ce3+ cations and benzimidazole (BI) molecules was employed as the inhibitive system for the AA2024-T3. Electrochemical properties of the metallic substrate in the presence and absence of the inhibitive system were studied utilizing EIS, PD, and OCP techniques. In addition, GIXRD, ATR-FTIR, XPS, OM, FE-SEM/EDS, water contact angle, and AFM were hired to study the protection mechanism. Based on the results obtained, the inhibitive system has a synergistic effect in improving the anti-corrosion protection performance of AA2024-T3. The synergistic index for the Ce + BI system was calculated to be around 19. Also, the efficiency of the synergistic system in the simultaneous presence of Ce3+ cations and BI molecules as the corrosion inhibitor was 99.3 %, which is higher than that of other inhibitive systems. Finally, the surface analysis outcomes revealed that the inhibitive film forming on the samples' surface during the immersion of the sample in the saline solution in the presence of the inhibitive species is the main factor in boosting the anti-corrosion properties of the aluminum substrate.

Effectiveness of benzimidazole treatments against Haemonchus contortus in sheep and goats – Do they produce similar responses?

The primary aim of this study was to compare the in vivo responses to orally administered doses of albendazole (5 mg/kg body weight) between experimentally infected sheep and goats. Fifty-four Improved Valachian lambs and 54 Saanen goat kids were split into six groups of nine animals. The sheep and goats were infected with larvae of the gastrointestinal nematode parasite Haemonchus contortus containing 10, 20, 30, 40, 60, and 80 % of the isotype-1 β-tubulin gene codon 200 alleles previously shown to be associated with benzimidazole (BZ)-resistance. All groups of goats generally had higher mean eggs per gram (EPG) before treatment, which was significant (p<0.05) only for the group with 80 % resistance alleles. An in vivo faecal egg reduction test (FECRT) was used to determine the efficacy of albendazole (ABZ) eight days after treatment. Anthelmintic treatment significantly reduced the EPGs in the groups with 10, 20, and 80 % resistance alleles in sheep and with 10, 20, 30, and 40 % resistance alleles in goats. Differences in efficacy between the sheep and goats after the application of doses of ABZ recommended for sheep mostly ranged from 2 % to 10 %. The largest variation was in the group infected with worms containing 60 % resistance alleles, where the efficacy was 13 % higher in goats. Our secondary aims were to evaluate the data obtained from an in vitro egg hatch test (EHT) in sheep and goats and to compare these data with the results from the isotype-1 β-tubulin gene codon 200 pyrosequencing and the FECRT. The percentages of the BZ-resistance alleles were comparable with the mean hatching obtained in the EHT and were also supported by the FECRT data for all groups. The results of the in vivo tests should be verified in the future using in vivo surveys conducted in mixed breeds and infections in multiple species.

Structural Snapshots of Proteus vulgaris Tryptophan Indole-Lyase Reveal Insights into the Catalytic Mechanism.

Tryptophan indole lyase (TIL; [E.C. 4.1.99.1]) is a bacterial pyridoxal-5'-phosphate (PLP)-dependent enzyme that catalyzes reversible β-elimination of indole from L-tryptophan. The mechanism of elimination of indole from L-tryptophan starts with the formation of an external aldimine of the substrate and PLP, followed by deprotonation of the α-CH of the substrate, forming a resonance-stabilized quinonoid intermediate. Proton transfer to C3 of the indole ring and carbon-carbon bond cleavage of the quinonoid intermediate provide indole and aminoacrylate bound to PLP, which then releases indole, followed by iminopyruvate. We have now determined the X-ray crystal structures of TIL complexes with (3S)-dioxindolyl-l-alanine, an inhibitor, and with substrates L-tryptophan, 7-aza-L-tryptophan, and S-ethyl-l-cysteine (SEC) in the presence of benzimidazole (BZI), an isostere of the product indole. These structures show a mixture of gem-diamine, external aldimine, quinonoid, and aminoacrylate intermediates, in both open and closed active site conformations. In the closed conformations of L-tryptophan, (3S)-dioxindolyl-l-alanine, and 7-aza-L-tryptophan complexes, hydrogen bonds form between Asp-133 with N1 of the ligand heterocyclic ring and NE2 of His-458 in the small domain of TIL. This hydrogen bond also forms in the BZI complex with the aminoacrylate intermediates formed from both L-tryptophan and SEC. The closed quinonoid complex of 7-aza-L-tryptophan shows that the azaindole ring in the closed conformation is bent out of plane of the Cβ-C3 bond by about 40°, putting it in a geometry that leads toward the transition-state geometry. Thus, both conformational dynamics and substrate activation play critical roles in the reaction mechanism of the TIL.

Enhancing the therapeutic potential of P29 protein-targeted monoclonal antibodies in the management of alveolar echinococcosis through CDC-mediated mechanisms.

Alveolar echinococcosis (AE) is a highly lethal helminth infection. Current chemotherapeutic strategies for AE primarily involve the use of benzimidazoles (BZs) such as mebendazole (MDZ) and albendazole (ABZ), which exhibit limited efficacy. In a previous study, the vaccine of recombinant Echinococcus granulosus P29 (rEgP29) showed significant immunoprotection against E. granulosus in both mice and sheep. In the current study, we utilized hybridoma technology to generate five monoclonal antibodies (mAbs) against P29, among which 4G10F4 mAb exhibited the highest antigen-specific binding capacity. This mAb was selected for further investigation of anti-AE therapy, both in vivo and in vitro. In vitro, 4G10F4 inhibited a noteworthy inhibition of E. multilocularis protoscoleces and primary cells viability through complement-dependent cytotoxicity (CDC) mechanism. In vivo, two experiments were conducted. In the first experiment, mice were intraperitoneally injected with Em protoscoleces, and subsequently treated with 4G10F4 mAb (2.5/5/10 mg/kg) at 12 weeks postinfection once per week for 8 times via tail vein injection. Mice that were treated with 4G10F4 mAb only in dosage of 5mg/kg exhibited a significant lower mean parasite burden (0.89±0.97 g) compared to isotype mAb treated control mice (2.21±1.30 g). In the second experiment, mice were infected through hepatic portal vein and treated with 4G10F4 mAb (5mg/kg) at one week after surgery once per week for 8 times. The numbers of hepatic metacestode lesions of the 4G10F4 treatment group were significantly lower in comparison to the isotype control group. Pathological analysis revealed severe disruption of the inner structure of the metacestode in both experiments, particularly affecting the germinal and laminated layers, resulting in the transformation into infertile vesicles after treatment with 4G10F4. In addition, the safety of 4G10F4 for AE treatment was confirmed through assessment of mouse weight and evaluation of liver and kidney function. This study presents antigen-specific monoclonal antibody immunotherapy as a promising therapeutic approach against E. multilocularis induced AE.

The first molecular detection of benzimidazole resistance in Haemonchus contortus from sheep in Hejing and Minfeng counties of Southern Xinjiang.

To understand the benzimidazole (BZ) resistance of Haemonchus contortus in Southern Xinjiang, three single nucleotide polymorphisms (SNPs) designated as F167Y, E198A, and F200Y, in the isotype-1 β-tubulin gene which are associated with BZ resistance, were investigated for H. contortus populations from sheep in Hejing and Minfeng counties of Southern Xinjiang. In brief, a total of 190 H. contortus adults were collected from 52 out of 70 slaughtered sheep in city abattoirs across two regions in Southern Xinjiang. The species identity of each adult worm was confirmed by PCR amplification of ITS-2 using H. contortus-specific primers targeting the ITS-2. The samples were then investigated for BZ-related SNPs at locus 167, 198, and 200, by PCR-sequencing of the isotype-1 β-tubulin gene. The results showed that only E198A and F200Y mutations were detected in the investigated H. contortus populations. The E198A mutation (homozygous and heterozygote resistant: found in 40% and 30% of sequenced samples from Minfeng and Hejing counties, respectively) was predominant compared with the F200Y mutation (homozygous and heterozygote resistant: found in 14% and 13.3% of sequenced samples from Minfeng and Hejing counties, respectively). The results indicate a high prevalence of BZ resistance in H. contortus populations from certain areas of Southern Xinjiang. Our findings provide valuable information for the prevention and control of H. contortus in areas with similar conditions.

Quantitative tests of albendazole resistance in Caenorhabditis elegans beta-tubulin mutants

Benzimidazole (BZ) anthelmintics are among the most important treatments for parasitic nematode infections in the developing world. Widespread BZ resistance in veterinary parasites and emerging resistance in human parasites raise major concerns for the continued use of BZs. Knowledge of the mechanisms of resistance is necessary to make informed treatment decisions and circumvent resistance. Benzimidazole resistance has traditionally been associated with mutations and natural variants in the C. elegans beta-tubulin gene ben-1 and orthologs in parasitic species. However, variants in ben-1 alone do not explain the differences in BZ responses across parasite populations. Here, we examined the roles of five C. elegans beta-tubulin genes (tbb-1, mec-7, tbb-4, ben-1, and tbb-6) in the BZ response as well as to determine if another beta-tubulin acts redundantly with ben-1. We generated C. elegans strains with a loss of each beta-tubulin gene, as well as strains with a loss of tbb-1, mec-7, tbb-4, or tbb-6 in a genetic background that also lacks ben-1. We found that the loss of ben-1 conferred the maximum level of resistance following exposure to a single concentration of albendazole, and the loss of a second beta-tubulin gene did not alter the level of resistance. However, additional traits other than larval development could be affected by the loss of additional beta-tubulins, and the roles of other beta-tubulin genes might be revealed at different albendazole concentrations. Therefore, further work is needed to fully define the possible roles of other beta-tubulin genes in the BZ response.

High rates of benzimidazole-resistance-associated alleles in Haemonchus contortus and detection of resistance against macrocyclic lactones in strongylids from German alpaca herds

The population of South American camelids (SAC) has been steadily growing in Europe, where they are confronted with the regional endoparasite population of ruminants. As there are no anthelmintic drugs registered for use against nematode infections in SACs, anthelmintics (AH) available for ruminants or horses are usually applied. Reports indicating potential failures in administered AH are increasing. However, the generally low egg counts in SACs complicate the application of resistance tests in the field. The present study reports a follow-up study on SAC farms where anthelmintic resistance (AR) was suspected. The aims were (i) to repeat faecal egg count reduction tests (FECRTs) on potentially affected farms identified in a previous study with larger sample sizes, (ii) to verify suspected AR of Haemonchus contortus against benzimidazoles (BZ) by performing a single-nucleotide polymorphism (SNP) analysis using digital polymerase chain reaction (dPCR), and (iii) to apply the mini-FLOTAC technique for more reliable results at low egg counts in line with current recommendations. Seven farms (9–46 animals each) were examined by coproscopy, larval differentiation and SNP analysis. A FECRT was performed on six of these farms with moxidectin (three farms), monepantel (two farms) and ivermectin (one farm). The FEC was calculated according to the current World Association for the Advancement of Veterinary Parasitology (WAAVP) guidelines with the clinical protocol (a newly introduced variant of FECRT which can be used for smaller sample sizes and lower egg counts on the cost of sensitivity) and an expected efficacy of 99%. A high level (> 90%) of BZ-resistance-associated SNPs on codon 200 of H. contortus was observed on all farms. With the FECRT, resistance was demonstrated for ivermectin (74% FECR), while it remained inconclusive for one farm for moxidectin treatment. Sustained efficacy was demonstrated for the remaining treatments. This study showed an advanced level of BZ resistance in H. contortus of SACs and the development of AR against macrocyclic lactones on some farms. Thus, constant monitoring of AH treatment and sustainable worm control methods both need to be applied.Graphical

Strategic design of magnetic ionic covalent organic frameworks incorporating amino acid ionic liquids for enhanced selectivity adsorption of benzimidazoles

Advancing the frontier of material design, our innovative magnetic ionic covalent organic framework (MiCOF) masterfully overcomes traditional barriers in selective adsorption, pioneering new functionalities and surface engineering techniques to effectively target and mitigate the impacts of benzimidazoles (BZDs). In previous studies, the idea of designing magnetic nanomaterials through theoretical screening of ionic liquids has been successfully proposed. This work proposed a theoretical and practical design for MiCOFs, aimed at providing a sensitive, selective, rapid, and straightforward method for analyzing trace substances in complex biological matrices. In a gentle one-pot process, the surface of Fe3O4 was coated with covalent organic frameworks (COFs) layer, followed by the modification with amino acid ionic liquid (AAIL) through covalent radical polymerization, facilitated by the abundant unsaturated vinyl groups present. This resulted in MiCOFs (Fe3O4@COF-AAIL) with a stable structure. Compared to unmodified Fe3O4@COF, Fe3O4@COF-AAIL exhibited excellent adsorption selectivity for BZDs. This enhanced selectivity is primarily due to the strong hydrogen bonds and π-π interactions between AAIL and BZDs, aligning well with COSMO-RS theoretical screening predictions. The development of magnetic dispersive solid-phase extraction (MDSPE) enabled rapid processing of BZDs in plasma with low matrix effects (0.9–1.3). This study not only validates a robust framework for the selective separation of trace contaminants in complex biological matrices but also advances the design and application of MiCOFs, setting a new paradigm in material science that could transform the design of novel materials for specific tasks.

Surveillance of Ancylostoma caninum in naturally infected dogs in Quebec, Canada, and assessment of benzimidazole anthelmintics reveal a variable efficacy with the presence of a resistant isolate in imported dogs.

Ancylostoma caninum is a widely prevalent parasitic nematode in dogs across the world. There has been a notable increase in reports of anthelmintic resistance in A. caninum within the United States of America in recent years, which has led us to investigate the potential of this scenario in Canada. The study objectives were to assess the prevalence of A. caninum in two different groups, including a colony of rescued dogs in Canada and three imported Greyhound dogs from USA, and to evaluate the efficacy of two benzimidazole (BZ) anthelmintics against A. caninum, complemented with a molecular genetic analysis adapted to low prevalence. Fecal samples were collected at pre- and post-treatment with fenbendazole for the native shelters-origin group, and a combination of anthelmintic formulations, including the pro-BZ febantel for the USA-origin group. The coprology analyses found several genera of internal parasites. Canine ancylostomiasis was the most prevalent parasitosis with 30.77% in the native group and 100% in the USA group, but with overall low average of A. caninum eggs per gram. Through the fecal egg count reduction test (FECRT), applying a cut-off at 90% as baseline of egg reduction for successful efficacy, BZ showed variable efficacy. Furthermore, molecular analysis confirmed the presence of A. caninum in both groups of dogs and found differences in the genetics linked to BZ resistance on the A. caninum β-tubulin isotype 1 gene. In the isolate from the native group, both codons 167 and 200 were homozygous without the presence of single nucleotide polymorphism (SNP). In contrast, the selected isolate from the USA group, showed a homozygous allele at position 200 and a heterozygous SNP at position 167. The latter was congruent with the low efficacy in FECRT and agrees with the recent findings of USA A. caninum isolate resistant phenotype to the BZ anthelmintics. The limitations of the study include an overall low eggs-per-gram in both canine groups, and the shortage of additional fecal samples from the USA group, restraining the molecular analysis only to one out of the three Greyhounds. This study provided some insights on the efficacy of BZs against A. caninum and revealed the presence of BZ resistant isolates in imported dogs in Quebec, Canada. All this information should be considered, for choosing the best strategy in the control of A. caninum using anthelmintic drugs.

Preparation and characterization of thermo-processable poly(benzimidazole imide)s with soluble and high heat-resistance containing N-phenyl-benzimidazole

In this paper, we present a synthetic strategy for N-phenyl substituted benzimidazole-derived diamines, including 2-(4-(4-aminophenoxy) phenyl)-1-phenyl-1H-benzo[d]imidazole-5-amine (para-diamine) and 2-(3-(4-aminophenoxy) phenyl)-1-phenyl-1H-benzo[d]imidazole-5-amine (meta-diamine). Two distinct series of N-phenyl substituted poly (benzimidazole imide)s (PBIPIs) were synthesized via reaction with different aromatic dianhydrides. The simulation reveals distinct amine reaction activities of two diamine monomers. The obtained PBIPIs exhibit exceptional heat resistance attributed to N-phenyl substituted benzimidazole (BI). The temperature at which weight loss of 5 % (T5%) is in the range of 491–595 °C under N2 environment, while the glass transition temperature is 237–329 °C. The PBIPIs exhibit specific solubility characteristics due to the flexible ether linkage groups' non-coplanarity and bulky pendant benzene groups. The PBIPIs possess tensile strength between 108 and 142 MPa, a tensile modulus of 4.0–5.9 GPa, and an elongation at a break of 4.2–26.4 %, indicating excellent mechanical properties. Additionally, the PBIPI with controlled molecular weight generated from BPADA incorporating 2-(3-(4-aminophenoxy) phenyl)-1-phenyl-1H-benzo[d]imidazole-5-amine (B-BPADA-PA) demonstrates exceptional melt processability. B-BPADA-PA possesses remarkable melt stability since its minimum complex viscosity is only 2100 Pa⋅s at 400 °C, and its melt viscosity ratio is 1.34 at 380 °C.

One-step synthesis of hydroxyl-functionalized ionic hyper-cross-linked polymers with high surface areas for efficient CO2 capture and fixation

Ionic liquid-based functional materials have attracted significant attention for their distinctive structure in the field of CO2 capture and conversion. In this work, a series of hydroxyl-functionalized ionic hyper-cross-linked polymers are prepared through a one-step Friedel-Crafts reaction involving hypoxanthine (HX) and benzimidazole (BI) as the monomers, along with various halohydrocarbon crosslinking agents. These polymers demonstrate a high specific surface area (558–1480 m2·g−1), well-developed microporous structure, and unique ion sites, enabling them to exhibit remarkable and reversible CO2 adsorption properties. Particularly noteworthy is their CO2 adsorption capacity, which surpasses that of similar ionic polymers documented in the literature, reaching 157.5 mg·g−1 at 273 K and 1 bar. Additionally, these polymers function as recyclable catalysts in the cycloaddition reaction of CO2 and epoxides, enabling the conversion of CO2 into cyclic carbonates with yields of up to 99 % even without a co-catalyst. Mechanism investigation reveals that the introduction of hydroxyl groups in the polymer is the key to improving catalytic activity through a synergistic catalytic effect. This research provides a novel concept for designing ionic functional materials with capabilities in both CO2 adsorption and catalytic activity.

L-Cysteine-Tuned the Hierarchical Structure Based on Benzimidazole: Synthesis, Characterization, and Application in Ratiometric Electrochemiluminescence Immunoassay.

Efficient and robust electrochemiluminescence (ECL) emitters are crucial for enhancing the ECL immunosensor sensitivity. This study introduces a novel ECL emitter, CoBIM/Cys, featuring a hierarchical core-shell structure. The core of the structure is created through the swift coordination between the sulfhydryl and carboxyl groups of l-cysteine (l-Cys) and cobalt ions (Co2+), while the shell is constructed by sequentially coordinating benzimidazole (BIM) with Co2+. This design yields a greater specific surface area and a more intricate porous structure compared to CoBIM, markedly enhancing mass transfer and luminophore accessibility. Moreover, the l-Cys and Co2+ core introduces Co-S and Co-O catalytic sites, which improve the catalytic decomposition of H2O2, leading to an increased production of hydroperoxyl radicals (OOH•). This mechanism substantially amplifies the ECL performance. Leveraging the competitive interaction between isoluminol and BIM for OOH• during ECL emission, we developed a ratiometric immunosensor for cardiac troponin I (cTnI) detection. This immunosensor demonstrates a remarkably broad detection range (1 pg mL-1 to 10 ng mL-1), a low detection limit (0.4 pg mL-1), and exceptional reproducibility and specificity.

A SURVEY OF ANTHELMINTIC EFFICACY IN DAIRY GOAT FARMS IN SOUTH-EAST FRANCE

Goat’s milk production is an important activity in France. Gastrointestinal nematodes (GIN) remain a main threat for grazing goats, usually controlled using anthelmintic drugs (AH). However, 1) eprinomectin (EPN) is the sole molecule yet available without withdrawal time for milk in France; 2) nematodes AH resistances increase dramatically. First, a survey was performed on 13 farms in the Auvergne-Rhône-Alpes (AURA) region to evaluate the efficacy of 2 AH authorized for dairy goats: a benzimidazole (BZ) and a macrocyclic lactone (EPN pour-on). Fecal Egg Count Reduction Tests (FECRT) were carried out using 3 groups of 10 goats per farm: a control group, one treated with BZ (oxfendazole) and one treated with EPN. The results indicate a resistance to BZ in 11 out of 13 farms (84.6%) and a lack of efficacy for EPN pour-on in at least 10 farms (76.9%). Secondly, EPN was given orally or subcutaneously in 4 farms of the previous trial showing a lack of efficacy to EPN pour-on. A resistance to EPN was confirmed in 3 out of 4 farms. Although based on a few farms, these results confirm the high prevalence of resistance of GIN to BZ in dairy goat farms. They also highlight a high level of resistance to EPN and the lack of efficacy of EPN when used pour-on. Given the level of resistance to marketed drugs, there is an urgent need to explore alternative options to AH to prepare integrated, sustainable control of GIN.

Nitrogen-reliant degradation behaviors of characteristic NHCs by UV-based advanced oxidation processes: Kinetics, pathways and toxicity assessment

In recent decades, nitrogen-containing heterocyclic compounds (NHCs) have been widely synthesized and applied due to their excellent coordination capability of heterocyclic N atoms. However, their high toxicity and poor biodegradability pose significant hazards to aquatic ecosystems. Three characteristic NHCs (cNHCs) with similar molecular structures but minor differences in the number and position of N atoms, namely benzotriazole (BTA), benzimidazole (BMZ), and indazole (IDZ), were selected to evaluate impacts of these differences on their degradation behaviors during UV/H2O2 treatments. It was found that the key mechanism for the removal of BTA, BMZ, and IDZ in the UV/H2O2 processes was the generation of ∙OH through UV-excited H2O2 decomposition. Density functional theory (DFT) calculations revealed that the variation in the number and position of heterocyclic ring N atoms significantly affected the electron cloud distribution of the cNHCs, thereby resulting in different reactivities. Mineralization results and N evolution experiments indicated that N elements were initially released in the form of ammonia nitrogen during UV/H2O2 treatments, which then underwent oxidation to form nitrite and nitrate. The two ortho-N atoms were most easily mineralized and release inorganic nitrogen, followed by the two meta-N atoms. However, the BTA compound containing three N atoms, exhibited inertness towards radicals after hydroxylation, thereby hindering mineralization. A dual-directional transformation products (TPs) identification protocol was employed to identify 30 TPs of the cNHCs and propose recommended degradation pathways. Furthermore, Vibrio fischeri bioluminescence inhibition bioassay and QSAR prediction models were used to preliminarily screen and identify 13 toxic TPs with potential ecological risks.

Fine tuning of porphyrin based-paddlewheel framework by imidazole derivative to boost electrochemiluminescence performance

Precise tuning the structure of catalytic center is of great importance for the construction of enhanced electrochemiluminescence (ECL) emitters and the development of ECL amplification strategies, which is a key factor in improving the sensitivity of biosensors. In this work, we report the enhanced ECL emitters based on the porphyrin-based paddlewheel framework (PPF) with axial coordinated imidazole-like ligands (PPF/X, X = 2-methylimidazole (MeIm), imidazole (Im), benzimidazole (BIM)). In this system, the electron-donating ability of the axial ligands is positively correlated to its coordination ability to the paddlewheel units and the catalytic ability of the axially coordinated paddlewheel units. In addition, the electrochemical and ECL behavior of PPF/X (X = MeIm, Im, BIM) with different axial coordinated ligands are explored.

Phosphate Triester Hydrolysis by Mononuclear Iron(III) Complexes: The Role of Benzimidazole in the Second Coordination Sphere

AbstractOver the years, phosphate ester hydrolysis catalyzed by coordination compounds has attracted extensive research on developing new bioinspired compounds. However, the literature lacks sufficient examples displaying activity toward phosphate triesters specifically, limiting the understanding of efficient strategies for the hydrolysis of this compound hydrolysis. Herein, we report preparing and characterizing three mononuclear iron(III) complexes (1, 2, and 3) and their hydrolase‐like activity. Complexes 2 and 3 have benzimidazole (BIMZ) moieties and were strategically designed to separate the BIMZ moiety from the first coordination sphere, and complex 1 (without BIMZ) was used as a reference. Several techniques provided structural information, including spectrophotometry, spectrometry, electrochemistry, elemental analysis, and 57Fe Mossbauer. Density functional theory (DFT) revealed distorted octahedral geometries due to the presence of the BIMZ groups. These groups also directly affected the protonation equilibria and catalytic activity. The phosphate triester diethyl‐2,4‐dinitrophenylphosphate (DEDNPP) hydrolysis was enhanced at least 27 times compared to the uncatalyzed reaction, with complexes 2 and 3, thus showing higher catalytic rates (kcat). Moreover, a longer carbon chain led to a higher hydrolysis rate but less interaction with substrate. These findings provide background for further investigations and the development of efficient catalysts for agrochemical degradation.

Multidimensional response of dopamine nano-system for on-demand fungicides delivery: Reduced toxicity and synergistic antibacterial effects

Considering the microenvironment of pathogens, the use of highly biocompatible antibacterial materials loaded with fungicides and the on-demand delivery of fungicides through controlled release can effectively improve the biocompatibility and antibacterial effect of existing fungicides. In this study, we used mesoporous poly-dopamine nanoparticles (MPDA NPs) as a carrier, prochloraz (Pro) as a loading agent, and benzimidazole (BIZ) and β-cyclodextrin (β-CD) complex as a blocking agent to prepare the on-demand delivery nano-pesticides Pro@MPDA-BIZ@β-CD (hereinafter abbreviated as PMBD), which can be administered at different stages. Sclerotinia sclerotiorum secretes oxalic acid factor to create an acidic microenvironment, and the nano-system quickly releases fungicide Pro into the mycelium. MPDA materials also responds to oxalic acid to jointly reduce the pathogenicity of Sclerotinia sclerotiorum, effectively inhibiting the growth of Sclerotinia sclerotiorum, and realizing the treatment of Sclerotinia sclerotiorum infection. On the other hand, when plants are not infected with Sclerotinia sclerotiorum, MPDA with a photothermal effect triggers the release of fungicides under the irradiation of near-infrared light, thus preventing Sclerotinia sclerotiorum infection. The in vitro release experiment showed that the cumulative release of Pro under low pH and near-infrared light irradiation was 2.68 times and 2.04 times higher than that under neutral and no light conditions, respectively. On the other hand, the rich functional groups on MPDA-BIZ@β-CD(hereinafter abbreviated as MBD) gave the system good wettability, and the contact angles of MBD on Chinese cabbage and tomato leaves were reduced by 14.85° and 41.54°, respectively, which enhanced its resistance to rainwater erosion and prevented the fungicides from being lost to the environment. In addition, bio-safety experiments have shown that PMBD has good biocompatibility to plant germination and soil microorganisms.

Quasi‐CW Amplified Spontaneous Emission in Air‐Processed Quasi‐2D Perovskite Thin Films with High Stability

AbstractDue to the hydrophobic organic cations, quasi‐two‐dimensional (quasi‐2D) lead halide perovskite materials have shown better moisture resistance. However, the inappropriate multiphase structure in the quasi‐2D perovskite films seriously affects the efficient transport of energy from low‐n domains to high‐n domains, especially when prepared in air. Herein, the study develops efficient quasi‐2D perovskite films in 30% ± 10% humidity and studies their amplified spontaneous emission (ASE) properties. It can be seen that the phase disproportionation of the quasi‐2D perovskite films prepared in air is greatly suppressed by manipulating the crystallization kinetics of the multiphase structure via using the organic additive benzimidazole (BI), thereby enabling a narrowed phase distribution. Due to the improvement in energy transfer efficiency, surface roughness, and humidity stability, the ASE with a low threshold of 13.4 µJ cm−2 is realized under the quasi‐continuous pumping condition, which is significantly &lt;28.8 µJ cm−2 of the pristine film. Furthermore, the introduction of BI organic additive enhanced the number of peak intensity half‐decay pulses to as high as 5.6 × 107, indicating a good operating stability of the BI‐treated films. This work suggests that the BI‐treated quasi‐2D perovskite films provide the possibility for preparing high‐performance lasers in air.

Refugia, climatic conditions and farm management factors as drivers of adaptation in Nematodirus battus populations

Parasites are known for their ability to rapidly adapt to changing conditions. For parasitic helminths, changes in climate, along with farming and management practices associated with the intensification of livestock farming, provide novel challenges which can impact on their epidemiology and control. The sustainability of livestock production partially relies on effective control of helminth infection. Therefore, understanding changes in parasite behaviour, and what drives these, is of great importance. Nematodirus battus is an economically important helminth in the UK and temperate regions. Its infective larvae typically overwinter in eggs on pasture and hatch synchronously in spring, causing acute disease in lambs. Attempts to control disease typically rely on whole-flock benzimidazole (BZ) treatments. In recent years, the emergence of BZ-resistance, alongside the hatching of eggs without the classical over-winter ‘chill stimulus’, have made N. battus more difficult to control. In three previous studies, after collecting a large number of N. battus populations alongside farm management data from commercial farms, we explored the prevalence of genetic mutations associated with BZ-resistance (n = 253 farms), the ability of eggs to hatch with and without a chill stimulus (n = 90 farms) and how farm management practices varied throughout the UK (n = 187 farms). In the present study, we identify factors which may be acting as drivers, or barriers, to either the development of resistance or the variable hatching behaviour of N. battus eggs. Generalised linear mixed effect models were applied to regress experimental hatching and genotyping data on farm management and additional environmental data. Both variable hatching and resistance development appeared associated with the maintenance of parasite refugia as well as grazing management, particularly reseeding of pasture routinely grazed by young lambs each spring and the practice of set-stocked grazing. Effective quarantine measures were identified as the main protective factor for the development of BZ-resistance whereas set stocked grazing and population bottlenecks, resulting from reseeding heavily contaminated pastures, were risk factors. Spring maximum temperature and other climatic factors were associated with ‘typical’ hatching of eggs following a chill stimulus whilst several management factors were linked with hatching without prior chilling. For example, practices which reduce parasite numbers on pasture (e.g. re-seeding) or restrict availability of hosts (e.g. resting fields), were found to increase the odds of non-chill hatching. Retention of the timing of lambing and infection level of the host within the fitted model indicated that requirement for a chill stimulus prior to hatching may be plastic, perhaps subject to change throughout the grazing season, in response to immune development or parasite density-dependence within the host. Further investigation of the influence of the factors retained within the fitted models, particularly the theme of parasite refugia which was highlighted in relation to both the presence of BZ-resistance alleles and alternative hatching, is required to establish robust, sustainable parasite control and farm management strategies.