CoFe-Layered Double Hydroxide Coupled with Pd Particles for Electrocatalytic Ethanol Oxidation.

Electrocatalytic efficiency and stability have emerged as critical issues in the ethanol oxidation reaction (EOR) of direct ethanol fuel cells. In this paper, Pd/Co1Fe3-LDH/NF as an electrocatalyst for EOR was prepared by a two-step synthetic strategy. Metal-oxygen bonds formed between Pd nanoparticles and Co1Fe3-LDH/NF guaranteed structural stability and adequate surface-active site exposure. More importantly, the charge transfer of the formed Pd-O-Co(Fe) bridge could effectively modulate the electrical structure of hybrids, improving the facilitated absorption of OH- radicals and oxidation of COads. Benefiting from the interfacial interaction, exposed active sites, and structural stability, the observed specific activity for Pd/Co1Fe3-LDH/NF (17.46 mA cm-2) was 97 and 73 times higher than those of commercial Pd/C (20%) (0.18 mA cm-2) and Pt/C (20%) (0.24 mA cm-2), respectively. Besides, the jf/jr ratio representing the resistance to catalyst poisoning was 1.92 in the Pd/Co1Fe3-LDH/NF catalytic system. These results provide insights into optimizing the electronic interaction between metals and the support of electrocatalysts for EOR.

Regulation of Structure and Anion-Exchange Performance of Layered Double Hydroxide: Function of the Metal Cation Composition of a Brucite-like Layer.

As anion-exchange materials, layered double hydroxides (LDHs) have attracted increasing attention in the fields of selective adsorption and separation, controlled drug release, and environmental remediation. The metal cation composition of the laminate is the essential factor that determines the anion-exchange performance of LDHs. Herein, we review the regulating effects of the metal cation composition on the anion-exchange properties and LDH structure. Specifically, the internal factors affecting the anion-exchange performance of LDHs were analyzed and summarized. These include the intercalation driving force, interlayer domain environment, and LDH morphology, which significantly affect the anion selectivity, anion-exchange capacity, and anion arrangement. By changing the species, valence state, size, and mole ratio of the metal cations, the structural characteristics, charge density, and interlayer spacing of LDHs can be adjusted, which affect the anion-exchange performance of LDHs. The present challenges and future prospects of LDHs are also discussed. To the best of our knowledge, this is the first review to summarize the essential relationship between the metal ion composition and anion-exchange performance of laminates, providing important insights for regulating the anion-exchange performance of LDHs.

Medium-chain triglyceride/water Pickering emulsion stabilized by phosphatidylcholine-kaolinite for encapsulation and controlled release of curcumin.

Pickering emulsions have received widespread attention for encapsulating lipophilic guests in the biomedical and food fields. However, control of the stabilities and demulsification of Pickering emulsions to allow the release of encapsulated species remains a challenge in gastrointestinal conditions. In this work, phosphatidylcholine-kaolinite was prepared by modification of natural kaolinite with phosphatidylcholine and was used as an emulsifier to stabilize medium-chain triglyceride (MCT)/water Pickering emulsions for encapsulating curcumin, a natural antioxidant drug. Simulated gastric and intestinal digestion and a cell uptake assay were implemented for the curcumin-loaded MCT/water Pickering emulsion to study its demulsification and the bioavailability of curcumin. The results revealed that the wettability of phosphatidylcholine-kaolinite could be tailored by controlling the modification temperature so that it could control the emulsion stability. The prepared phosphatidylcholine-kaolinite, with a three-phase contact angle of 123°, was an optimal emulsifier for the enhanced stabilization of the MCT/water Pickering emulsion, especially in the presence of gastric acid. The phosphatidylcholine-kaolinite distributed at the water-oil interface and formed a dense shell structure on the surfaces of the emulsion droplets, controlling the demulsification efficiency to release the encapsulated curcumin. Only 18.9% of the curcumin was released in the simulated gastric conditions after 120 min of digestion due to the demulsification of the MCT/water Pickering emulsion, while it was completely released after 150 min of digestion in simulated intestinal conditions, as expected. This Pickering emulsion stabilized by phosphatidylcholine-kaolinite is a promising delivery system for lipophilic foods or drugs to enhance their bioavailability.

Genetic Analysis of Four Sexual Differentiation Process Proteins (isp4/SDPs) in Chaetomium thermophilum and Thermomyces lanuginosus Reveals Their Distinct Roles in Development.

Fungal sexual development requires the involvement of a large number of functional genes. Fungal genes encoding sexual differentiation process proteins (SDPs), isps, have been known for decades. isp4/SDP and its homologs function as oligopeptide transporters (OPTs), yet their roles in reproduction are unknown. Here, we genetically analyzed all four isp4/SDP homologs in the sexual species Chaetomium thermophilum and asexual species Thermomyces lanuginosus. Using single gene deletion mutants, we found that T. lanuginosus SDP (TlSDP) participated in asexual sporulation, whereas the other homologs participated in sexual morphogenesis. In complementary tests, C. thermophilum SDPs (CtSDP1-3) restored sporulation defects in TlSDP deletion strains (ΔTlSDP), and their translated proteins, which were localized onto the cytomembrane, possessed OPT activity. Interestingly, CtSDP2 accumulated at the top of the hyphae played a distinct role in determining the sexual cycle, glutathione transport, and lifespan shortening. A unique 72nt-insertion fragment (72INS) was discovered in CtSDP2. Biological analysis of the 72INS deletion and DsRED-tagged fusion strains implied the involvement of 72INS in fungal growth and development. In contrast to TlSDP, which only contributes to conidial production, the three CtSDPs play important roles in sexual and asexual reproduction, and CtSDP2 harbors a unique functional 72INS that initiates sexual morphogenesis.

ANXC7 Is a Mitochondrion-Localized Annexin Involved in Controlling Conidium Development and Oxidative Resistance in the Thermophilic Fungus Thermomyces lanuginosus.

Annexins (ANXs) are widely expressed and structurally related proteins which play multiple biological roles in animals, plants, and fungi. Although ANXs have been localized to the cytosol and the cell membrane and the molecular basis of the four annexin repeats is well established, the in vivo roles of these proteins are still far from clear, particularly with regard to the filamentous fungi. Thermomyces lanuginosus, a thermophilic fungus, is widely used in the fermentation industry; however, the role of ANX in this organism is unknown. In this study, a single ANX homologue (ANXC7) was identified and characterized in T. lanuginosus. The expression pattern indicated that ANXC7 is closely associated to conidium development, and it accumulated in the mitochondria of the forming conidia. The deletion of ANXC7 (ΔANXC7) resulted in no obvious phenotype related to colony growth on solid CM medium. However, when ΔANXC7 was grown in CM liquid culture, the mycelium masses appeared to be larger and looser compared to the wild-type. Additionally, the dry weight of the mutant mycelia was significantly increased. Under conditions that compromise cell-wall integrity, ΔANXC7 was less vulnerable than the wild-type with regard to such damage. Moreover, based on a surface hydrophobicity test, the ΔANXC7 strain was clearly less hydrophobic. The growth of ΔANXC7 was inhibited when grown under selected stress conditions, particularly with regard to salt stress; however, the oxidative resistance to exogenous H2O2 in ΔANXC7 was increased, and endogenous H2O2 levels within the ΔANXC7 were lower than in the wild-type, thereby suggesting that the ANXC7 specifically controls oxidative resistance. Based on microscopic observation, 4-day-conidia were more prevalent than 5-day conidia on the conidiophore stalk of ΔANXC7, even though the ΔANXC7 demonstrated an increased production of conidia during these days, indicating precocious conidial maturation and shedding from the conidiophore stalk in this strain. Taken together, our data indicate that ANXC7 localizes to the mitochondria and is involved in controlling conidium development and oxidative resistance in T. lanuginosus.

Mitochondrial and peroxisomal Lon proteases play opposing roles in reproduction and growth but co-function in the normal development, stress resistance and longevity of Thermomyces lanuginosus.

The ATP-dependent Lon enzyme is a highly conserved protease with multiple roles in diverse species such as fungi; however, there are few reports on Lon enzymes in filamentous fungi. Thermomyces lanuginosus, a typical thermophilic fungus, has been widely studied in physiology and cell biology; thus, studies on Thermomyces Lons are important. Two Lons were bioinformatically deduced in T. lanuginosus. Subcellular localization analysis showed that one is present in mitochondria (MLon), while the other is found in peroxisomes (PLon). Although both Lon enzymes were activated by H2O2, they were not induced by heat shock; instead, they were induced by low temperatures. Two single-deletion Lon mutants (ΔMLon and ΔPLon) were generated. Biological analysis demonstrated that ΔMLon decreased the production of conidia but increased the growth of mycelia. By contrast, ΔPLon increased the production of conidia but decreased the growth of mycelia. The lifespan was measured in time and in length of continuous growth. The wild-type strain showed continuous linear growth for 60days, whereas growth was impeded at 30 and 50days for ΔPLon and ΔMLon mutants, respectively, suggesting that PLon is more important for longevity than MLon. Interestingly, ΔPLon, which accumulated larger amount of H2O2 was not only more sensitive to exogenous H2O2 but also much more sensitive to other selected stressors. Taken together, our data indicate that mitochondrial and peroxisomal Lons play opposite roles in controlling growth and development, but exhibit synergistic effects on the normal states of vegetative growth, asexual development, stress resistance and longevity in T. lanuginosus.

Identification and characterization of an anti-oxidative stress-associated mutant of Aspergillus fumigatus transformed by Agrobacterium tumefaciens.

Aspergillus fumigatus is one of the most common opportunistic pathogenic fungi, surviving in various environmental conditions. Maintenance of the redox homeostasis of the fungus relies upon the well­organized regulation between reactive oxygen species generated by immune cells or its own organelles, and the activated anti­oxidative stress mechanism. To investigate such a mechanism, the present study obtained a number of randomly­inserted mutants of A. fumigatus, mediated by Agrobacterium tumefaciens. In addition, a high throughput hydrogen peroxide screening system was established to examine ~1,000 mutants. A total of 100 mutants exhibited changes in hydrogen peroxide sensitivity, among which a significant increase in sensitivity was observed in the AFM2658 mutant. Further investigations of the mutant were also performed, in which the sequence of this mutant was characterized using thermal asymmetric interlaced­polymerase chain reaction. This revealed that the insertion site was located on chromosome 2 afu1_92, and the 96 bp sequence was knocked out, which partially comprised a sequence localized between the integral membrane protein coding region and the helix­loop­helix transcription factor coding region. A decrease in the levels of anti­oxidative stress­associated mRNAs were observed, and an increase in reactive oxygen species were detected using fluorescence. The results of the present study demonstrated that this sequence may have a protective role in A. fumigatus in the presence of oxidative stress.

Carbon dots as fluorescent probe for "off-on" Detecting sodium dodecyl-benzenesulfonate in aqueous solution.

In this paper, we propose an "off-on" approach for the detection of sodium dodecyl-benzenesulfonate (SDBS) using carbon dots (CDs) as fluorescent probe. We firstly demonstrated that the fluorescence of CDs decreased apparently in the presence of ruthenium (Ru), and the system was thus "turn-off". The resulting CDs-Ru system was found to be sensitive to SDBS, SDBS not only serves to shelter the CDs effectively from being quenched, but also to reverse the quenching and restore the fluorescence due to its ability to remove Ru from the surface of CDs (turn-on). An eco-friendly, simple and sensitive platform for the detection of SDBS based on the CDs-Ru probes has been proposed. After the experimental conditions were optimized, the linear range for detection SDBS was 0.10-7.50 µg/mL, with correlation coefficient (r) 0.9988, detection limit was 0.033 µg/mL (3σ). This method is facile, rapid, low cost, environment-friendly, and possesses the potential for practical application.

cspA influences biofilm formation and drug resistance in pathogenic fungus Aspergillus fumigatus.

The microbial cell wall plays a crucial role in biofilm formation and drug resistance. cspA encodes a repeat-rich glycophosphatidylinositol-anchored cell wall protein in the pathogenic fungus Aspergillus fumigatus. To determine whether cspA has a significant impact on biofilm development and sensitivity to antifungal drugs in A. fumigatus, a ΔcspA mutant was constructed by targeted gene disruption, and we then reconstituted the mutant to wild type by homologous recombination of a functional cspA gene. Deletion of cspA resulted in a rougher conidial surface, reduced biofilm formation, decreased resistance to antifungal agents, and increased internalization by A549 human lung epithelial cells, suggesting that cspA not only participates in maintaining the integrity of the cell wall, but also affects biofilm establishment, drug response, and invasiveness of A. fumigatus.

A carbon dots-CdTe quantum dots fluorescence resonance energy transfer system for the analysis of ultra-trace chlortoluron in water.

In this paper, a fluorescence resonance energy transfer (FRET) system between fluorescence carbon dots (CDs, donor) and CdTe quantum dots (CdTe, acceptor) was constructed, and a novel platform for sensitive and selective determination of chlortoluron was accordingly proposed. It was found that in Tris-HCl buffer solution at pH=8.7, energy transfer from CDs to CdTe occurred, which resulted in a great enhancement of the fluorescence intensity of CdTe. Upon the addition of chlortoluron, in terms of strong interaction between chlortoluron and CdTe QDs through the formation of chlortoluron-CdTe ground state complex, resulted in CdTe fluorescence quenching. Under optimal conditions, in range of 2.4×10(-10)molL(-1)-8.5×10(-8)molL(-1), the change of CdTe fluorescence intensity was in good linear relationship with the chlortoluron concentration, and the detection limit was 7.8×10(-11)molL(-1) (S/N=3). Most of common relevant substance, cations and anions did not interfere with the detection of chlortoluron. The proposed method was applied to determine chlortoluron in water samples with satisfactory results.