Copper-zinc nanoparticle-decorated nitrogen-doped carbon composite for electrochemical determination of triclosan.

A new sensor based on copper-zinc bimetal embedded and nitrogen-doped carbon-based composites (CuZn@NC) was prepared for triclosan (TCS) detection by pyrolyzing the precursor of Cu-Zn binuclear metal-organic framework (MOF). The performance for detecting TCS was evaluated using linear scanning voltammetry (LSV) and differential pulse voltammetry (DPV), and the proton and electron numbers during TCS oxidation have been proved to be one-to-one. The results indicated that CuZn@NC can present a satisfactory analysis performance for TCS detection. Under the optimized conditions, the linear response range was 0.2-600 µM and the detection limit was 47.9 nM. The sensor presented good stability (signal current dropped only 2.5% after 21 days) and good anti-interference of inorganic salts and small molecular organic acids. The good recovery (97.5-104.1%) for detecting spiked TCS in commercial products (toothpaste and hand sanitizer) suggested its potential for routine determination of TCS in real samples.

Ecological effect of microplastics on soil microbe-driven carbon circulation and greenhouse gas emission: A review.

Soil organic carbon (SOC) pool, the largest part of terrestrial ecosystem, controls global terrestrial carbon balance and consequently presented carbon cycle-climate feedback in climate projections. Microplastics, (MPs, <5 mm) as common pollutants in soil ecosystems, have an obvious impact on soil-borne carbon circulation by affecting soil microbial processes, which play a central role in regulating SOC conversion. In this review, we initially presented the sources, properties and ecological risks of MPs in soil ecosystem, and then the differentiated effects of MPs on the component of SOC, including dissolved organic carbon, soil microbial biomass carbon and easily oxidized organic carbon varying with the types and concentrations of MPs, the soil types, etc. As research turns into a broader perspective, greenhouse gas emissions dominated by the mineralization of SOC coming into view since it can be significantly affected by MPs and is closely associated with soil microbial respiration. The pathways of MPs impacting soil microbes-driven carbon conversion include changing microbial community structure and composition, the functional enzyme's activity and the abundance and expression of functional genes. However, numerous uncertainties still exist regarding the microbial mechanisms in the deeper biochemical process. More comprehensive studies are necessary to explore the affected footprint and provide guidance for finding the evaluation criterion of MPs affecting climate change.

Enhanced biotoxicity by co-exposure of aged polystyrene and ciprofloxacin: the adsorption and its influence factors.

Microplastics (MPs), as emerging contaminants, usually experience aging processes in natural environments and further affect their interactions with coexisted contaminants, resulting in unpredictable ecological risks. Herein, the effect of MPs aging on their adsorption for coexisting antibiotics and their joint biotoxicity have been investigated. Results showed that the adsorption capacity of aged polystyrene (PS, 100 d and 50 d) for ciprofloxacin (CIP) was 1.10-4.09 times higher than virgin PS due to the larger BET surface area and increased oxygen-containing functional groups of aged PS. Following the increased adsorption capacity of aged PS, the joint toxicity of aged PS and CIP to Shewanella Oneidensis MR-1 (MR-1) was 1.03-1.34 times higher than virgin PS and CIP. Combined with the adsorption process, CIP posed higher toxicity to MR-1 compared to aged PS due to the rapid adsorption of aged PS for CIP in the first 12 h. After that, the adsorption process tended to be gentle and hence the joint toxicity to MR-1 was gradually dominated by aged PS. A similar transformation between the adsorption rate and the joint toxicity of PS and CIP was observed under different conditions. This study supplied a novel perception of the synergistic effects of PS aging and CIP on ecological health.

Effect of Rubusoside, a Natural Sucrose Substitute, on Streptococcus mutans Biofilm Cariogenic Potential and Virulence Gene Expression In Vitro.

Dental caries is a biofilm-mediated disease in which Streptococcus mutans is the main pathogenic microorganism, and its incidence is closely related to sucrose. Rubusoside is a natural nonnutritive sweetener isolated from Rubus suavissimus S. Lee. This study was designed to determine the effect of this sucrose substitute on the cariogenic properties and virulence gene expression of S. mutans biofilms. S. mutans was exposed to brain heart infusion (BHI) medium (as a control), 1% sucrose-supplemented medium, 1% rubusoside-supplemented medium, and 1% xylitol-supplemented medium. The growth curve of the biofilm was monitored by crystal violet staining, and the pH was measured every 24 h. After 5 days, the biofilms formed on the glass coverslips were recovered to determine the biomass (dry weight and total amount of soluble proteins), numbers of CFU, and amounts of intra- and extracellular polysaccharides. Biofilm structural imaging was performed using a scanning electron microscope (SEM). Virulence gene expression (gtfB, gtfC, gtfD, ftf, spaP, gbpB, ldh, atpF, vicR, and comD) was determined by reverse transcription-quantitative PCR. Growth in rubusoside resulted in lower levels of acid production than observed during growth in sucrose, xylitol, and the control, while it also reduced the level of biofilm accumulation and bacterial viability and even reduced the level of production of extracellular polysaccharides. By SEM, the levels of biofilm formation and extracellular matrix during growth in rubusoside were lower than these levels during growth in sucrose and xylitol. From the perspective of virulence genes, growth in rubusoside and xylitol significantly inhibited the expression of virulence genes compared with their levels of expression after growth in sucrose. Among these genes, gtfB, gtfC, gbpB, ldh, and comD downregulation was found with growth in rubusoside compared with their expression with growth in xylitol. Therefore, rubusoside appears to be less potentially cariogenic than sucrose and xylitol and may become an effective sucrose substitute for caries prevention. Further studies are needed to deepen these findings.IMPORTANCE Dental caries is a major public health challenge and places heavy biological, social, and financial burdens on individuals and health care systems. To palliate the deleterious effect of sucrose on the virulence factors of S. mutans, massive commercial efforts have been oriented toward developing products that may act as sucrose substitutes. Rubusoside, a natural sucrose substitute, is a plant extract with a high level of sweetness. Although some studies have shown that rubusoside does not produce acids or inhibit the growth of S. mutans, little attention has been paid to its effect on dental biofilm and the underlying mechanisms. Our study focuses on the effect of rubusoside on the formation and structure of biofilms and the expression of virulence genes. The results confirm that rubusoside can inhibit accumulation, bacterial viability, polysaccharide production by the biofilm, and related gene expression. These results provide further insight into the cariogenicity of S. mutans biofilms and demonstrate a new perspective for studying the impact of sucrose substitutes on caries.

Mitigation of biofouling in membrane bioreactors by quorum-quenching bacteria during the treatment of metal-containing wastewater.

Quorum quenching (QQ) is an efficient way to mitigate membrane biofouling in a membrane bioreactor (MBR) during wastewater treatment. A QQ bacterium, Lysinibacillus sp. A4, was isolated and used to mitigate biofouling in an MBR during the treatment of wastewater containing metals. A QQ enzyme (named AilY) was cloned from A4 and identified as a metallo-ß-lactamase-like lactonase. The QQ activity of A4 and that of Escherichia coli BL21 (DE3) overexpressing AilY could be promoted by Fe2+, Mn2+, and Zn2+ while remaining unaffected by other metals tested. The two bacteria effectively mitigated biofouling by reducing the transmembrane pressure from around 30 to 20 kPa without negative influence on the COD, NH4+-N, or total phosphorus of the effluent. The relative abundance of Lysinibacillus sp. A4 increased greatly from 0.04 to 8.29% in the MBR with metal-containing wastewater, suggesting that Lysinibacillus sp. A4 could multiply quickly and adapt to this environment. Taken together, the findings suggested that A4 could tolerate metal to a certain degree, and this property could allow A4 to adapt well to metal-containing wastewater, making it a valuable strain for mitigating biofouling in MBR during the treatment of metal-containing wastewater.

Targeted Liposomes Sensitize Plastic Melanoma to Ferroptosis via Senescence Induction and Coenzyme Depletion.

Ferroptotic cancer therapy has been extensively investigated since the genesis of the ferroptosis concept. However, the therapeutic efficacy of ferroptosis induction in heterogeneous and plastic melanoma has been compromised, because the melanocytic and transitory cell subpopulation is resistant to iron-dependent oxidative stress. Here, we report a phenotype-altering liposomal nanomedicine to enable the ferroptosis-resistant subtypes of melanoma cells vulnerable to lipid peroxidation via senescence induction. The strategy involves the ratiometric coencapsulation of a cyclin-dependent kinase 4 and 6 (CDK4/6) inhibitor (palbociclib) and a ferroptosis inducer (auranofin) within cRGD peptide-modified targeted liposomes. The two drugs showed a synergistic anticancer effect in the model B16F10 melanoma cells, as evidenced by the combination index analysis (<1). The liposomes could efficiently deliver both drugs into B16F10 cells in a targeted manner. Afterward, the liposomes potently induced the intracellular redox imbalance and lipid peroxidation. Palbociclib significantly provoked cell cycle arrest at the G0/G1 phase, which sensitized auranofin-caused ferroptosis through senescence induction. Meanwhile, palbociclib depleted intracellular glutathione (GSH) and reduced nicotinamide adenine dinucleotide phosphate (NADPH), further boosting ferroptosis. The proof-of-concept was also demonstrated in the B16F10 tumor-bearing mice model. The current work offers a promising ferroptosis-targeting strategy for effectively treating heterogeneous melanoma by manipulating the cellular plasticity.

Attenuating Uncontrolled Inflammation by Radical Trapping Chiral Polymer Micelles.

As a clinical unmet need, uncontrolled inflammation is characterized by the crosstalk between oxidative stress and an inflammatory response. Ferroptotic cell death plays an essential role in uncontrolled inflammation. Hence ferroptosis inhibition is capable of managing hyper-inflammation, but the small molecular inhibitors show poor residence in cell membranes. The plasma membrane is the major site of lipid peroxidation that is the key event of ferroptosis. To address such a challenge, chiral radical trapping polymers were engineered by mimicking the structure of the cell membrane with imbedded helical proteins. The polymers were tailored to show an α-helix conformation that enabled increased hydrophobicity, prolonged membrane retention, and enhanced lipid radical trapping. The chiral polymers are amphiphilic, and the self-assembled micelles exhibited an extended blood circulation. At the lipopolysaccharide-induced macrophage and mice models, chiral polymer micelles effectively suppressed ferroptosis and repressed inflammatory cytokines. The current work provides an innovative means for attenuating uncontrolled inflammation by anti-ferroptotic polymer micelles.

Micelles based on polyvinylpyrrolidone VA64: A potential nanoplatform for the ocular delivery of apocynin.

Purpose of this work was to determine the feasibility of a nano-ophthalmic solution consisting of the nanocarrier polyvinylpyrrolidone VA64 (VA64) and encapsulated apocynin (APO) as treatment for ocular inflammatory diseases. Results showed the solution, termed APO-VA64 ophthalmic solution, could be fabricated via a simple process. This solution was clear, colorless, and possessed valuable characteristics, such as small micelle size (14.12 ± 1.24 nm), narrow micelle size distribution, and high APO encapsulation efficiency. Encapsulated APO was also found to have high aqueous solubility and in vitro release and antioxidant activities. APO-VA64 ophthalmic solution showed good ocular tolerance and demonstrated improved corneal permeation ability in mouse eyes. In an in vivo mice model, topically administered APO-VA64 ophthalmic solution was found to be significantly more effective against benzalkonium chloride-induced ocular damage than APO, VA64, and a mix of APO and VA64. Blockage of high mobility group box 1 signaling and its related proinflammatory cytokines were involved in this therapeutic effect. In conclusion, these in vitro and in vivo findings demonstrate that VA64 micelles are a potential nanoplatform for ocular drug delivery, and that the nanoformulation APO-VA64 ophthalmic solution may be a promising candidate for the efficacious treatment of ocular inflammatory diseases.

Ultra-small nanocomplexes based on polyvinylpyrrolidone K-17PF: A potential nanoplatform for the ocular delivery of kaempferol.

This study aims to create and evaluate a kaempferol (KAE) ophthalmic solution based on polyvinylpyrrolidone (PVP) nanocomplexes. KAE can be highly complexed with PVP K-17PF (17PF) to formulate an aqueous ophthalmic solution named 17PF-KAE. The optimized 17PF-KAE displays high complexing efficiency, an ultra-small size (8.628 ± 0.066 nm), and good aqueous dispersibility. 17PF-KAE did not show any obvious cytotoxicity or in vivo ocular tissue toxicity. Further, 17PF-KAE was observed to facilitate significant improvement in in vitro parallel artificial membrane permeability, in vitro cellular uptake, and ex vivo corneal permeation of KAE. Regarding the in vivo ocular absorption test, the KAE levels in the cornea and aqueous humor determined from the 17PF-KAE group were much higher than those in the free KAE solution group in addition to conjunctiva and the iris-ciliary body at certain time points. 17PF-KAE was also observed to promote remarkable improvement in in vitro antioxidant activity and in vivo anti-inflammatory activity. Moreover, a topical 17PF-KAE solution in mice eyes showed significant improvement in the treatment efficacy of corneal alkali burns over the free KAE solution. The therapeutic mechanism was also associated with inhibiting the production of key mediators of inflammation (CD54, IL-6, and TGF-ß1) and angiogenic factors (VEGF). Therefore, these results demonstrate that 17PF-KAE may be a promising new ophthalmic formulation for the prophylaxis and treatment of oxidative stress and inflammation-related ocular diseases.

Selective removal of phosphate by dual Zr and La hydroxide/cellulose-based bio-composites.

Bimetallic oxides nanocomposites always exhibited the better phosphate capacities than those monometallic oxides samples. Herein, the high carbohydrate-content biomaterials, shaddock peels (SP), were used as the bio-host for supporting the bimetallic oxides, zirconium (Zr) and lanthanum (La) hydroxides, forming the SP-Zr-La composites. Phosphate adsorption properties as well as stability of the novel composites were evaluated. The SP-Zr-La composites indicated that some rod-like or amorphous nanoparticles with sizes of 20-150 nm were anchored inside the SP, which exerted more available interface interactions toward the adsorbed ions. The Zr-La species were pH-sensitive and adsorption capacity of phosphate by SP-Zr-La was increased with the rise in temperature. As the molar ratio of accompanying ions/phosphate was increased from 0 to 10 times, the SP-Zr-La was observed with the adsorption loss of 27.2-36.7%. Whereas the adsorption loss of cationic SP (grafted with quaternary ammonium groups) was calculated up to 86.2-91.6%; this indicated the more feasibility of SP-Zr-La in real applications. In addition, the stability of impregnated Zr and La species in SP-Zr-La was greatly improved by the bio-carrier through the "shielding effect" in a low HA surrounding.

A multidimensional design of charge transfer interfaces via D-A-D linking fashion for electrophysiological sensing of neurotransmitters.

Donor-Acceptor (D-A) structure like host-guest pair serves as an organic charge-transfer (C-T) material with pregnant electrochemical and photochemical properties. Phenothiazine, a conjugated nitrogen-sulfur heterocyclic compound with broad pharmaceutical profile, is a strong electron donating system and applied in the synthesis of various classic antipsychotic drugs. In this proposal, a novel D-A molecule, 2,3-bis(4-(10H-phenothiazin-10-yl)phenyl)fumaronitrile (PTBFN), containig a diphenylfumaronitrile as the electrophilic central core and two phenothiazines as the peripheral electron donor functional groups is first designed and synthesized. Subsequently, the C-T layer based on the PTBFN polymer, poly(PTBFN), is obtained via a straightforward electrochemical method and used as an efficient electrocatalyst for dopamine (DA) detection. The logarithm of oxidation peak currents present an outstanding linear response to that of the DA concentration varying from 0.005 to 350µM with a detection limit down to 0.70nM, wherein the interferences of uric acid (UA) and ascorbic acid (AA) could be eliminated effectively. Moreover, the biosensor displays decent stability, excellent selectivity for different interfering compounds and applicability in real samples analysis. The favorable sensing performance suggests that the nontrivial D-A architecture is one of the promising bioaffinity catalysts for electrocatalysis and expected to provide wider application potential for biosensing construction and medical diagnostics.

A novel electrochemical biomimetic sensor based on poly(Cu-AMT) with reduced graphene oxide for ultrasensitive detection of dopamine.

A polymerized film of copper-2-amino-5-mercapto-1,3,4-thiadiazole (Cu(II)-AMT) complex (poly(Cu-AMT)) was successfully achieved via a simple and low-cost electrochemical methodology. Subsequently, a noncovalent nanohybrid of poly(Cu-AMT) with reduced graphene oxide (rGO) (rGO-poly(Cu-AMT)) was prepared through π-π stacking interaction as an efficient mimetic enzyme for the ultrasensitive and selective detection of dopamine (DA). The rGO-poly(Cu-AMT) nanocomposites showed considerable mimetic enzyme catalytic activity, which may be attributed to the significant promotion of the electron transfer between the substrate and graphene-based carbon materials, and also the synergistic electrocatalytic effect in mimetic enzyme between rGO sheet and poly(Cu-AMT). The electrocatalytic and sensing performances of the biomimetic sensor based on the rGO-poly(Cu-AMT) nanocomposites were evaluated in detail. The biomimetic sensor enables a reliable and sensitive determination of DA with a linear range of 0.01-40µM and a detection limit of 3.48nM at a signal-to-noise ratio of 3. In addition, we applied the proposed method to detect DA in real sample with satisfactory results. Accordingly, the rGO-poly(Cu-AMT) is one of the promising mimetic enzyme for electrocatalysis and biosensing.

Biomimetic sensor based on molecularly imprinted polymer with nitroreductase-like activity for metronidazole detection.

The utility of molecularly imprinted polymer (MIP) as electrochemical sensor often suffers from its limited catalytic efficiency. Here, we proposed an alternative approach by combining the concept of MIP with the use of mimetic enzyme. A metronidazole imprinted polymer with nitroreductase-like activity was successfully achieved via an electrochemical method, where melamine served two purposes: functional monomer of MIP and component of mimetic enzyme. During the imprinting process, the redox-active center, which is responsible for catalysis, was introduced into the imprinted cavities. Accordingly, the imprinted polymer, having both catalysis centers and recognition sites, exhibited enhanced electrocatalytic activity and selectivity. The sensing performances of this metronidazole imprinted biomimetic sensor were evaluated in detail. Results revealed that the response to metronidazole was linear in the concentration range of 0.5-1000 µM, and the detection limit was 0.12 µM (S/N=3). In addition, we applied the proposed sensor to detect metronidazole in an injection solution and the results implied its feasibility for practical application.

Catalytic amplification based on hole-transporting materials as efficient metal-free electrocatalysts for non-enzymatic glucose sensing.

Hole-transporting materials with tunable structures and properties are mainly applied in organic light-emitting diodes as transport layer. But their catalytic properties as signal amplifiers in biological assays are seldom reported. In this paper, a starburst molecule, 4,4,4″-tri(N-carbazolyl)-triphenylamine (TCT), containing a triphenylamine as the central core and three carbazoles as the peripheral functional groups was designed and synthesized. Subsequently, the hole-transporting material based on the TCT polymer, poly(TCT) (PTCT), was achieved via a low-cost electrochemical method and exploited as an efficient metal-free electrocatalyst for non-enzymatic glucose detection. Here, this hole-transporting material served three purposes: electrochemical recognition (owing to hydrogen bonding interaction and the biomimetic microenvironment created by the polymer), electrocatalysis (owing to the hole-transporting capability of triphenylamine and the catalytic property of carbazole), and signal amplification (owing to energy migration along the conductive polymer backbone). The electrocatalytic and sensing performances of the sensor based on PTCT were evaluated in detail. Results revealed that the PTCT film could efficiently catalyze the oxidation of glucose at a less-positive potential (+0.20 V) in the absence of any enzymes. The response to glucose was linear in the concentration range of 1.0-6000 µM, and the detection limit was 0.20 µM. With good stability and selectivity, the proposed sensor could be feasibly applied to detect glucose in practical samples. The encouraging sensing performances suggest that the hole-transporting material is one of the promising biomimetic catalysts for electrocatalysis and relevant fields.