Uncovering Origin of Chirality of Gold Nanoparticles Prepared through the Conventional Citrate Reduction Method.

Chiral nanoparticles are one of the research hotspots in the field of materials science, chemistry, and biology. Understanding and controlling the chirality of nanoparticles is one key step toward their use, but the origin of nanoparticles' chirality and its determinative factor are not well understood. In this work, we studied the chirality of gold nanoparticles (AuNPs) prepared through the conventional citrate reduction method. Unexpectedly, it was found that small AuNPs (∼13 nm) exhibited opposite chirality to the large AuNPs (>30 nm). The origin of the AuNPs chirality was revealed by comparing the crystal structure between small AuNPs and large AuNPs. It was proposed that the lattice orientation of fivefold-twinned AuNPs may be responsible for the intrinsic chirality of AuNPs. This work provides a deep mechanistic understanding of the intrinsic chirality of the AuNPs and will boost the development of the structure-controlled synthesis and application of chiral AuNPs and other chiral nanomaterials. Furthermore, based on the unexpected size effect, chiral AuNP probes were rationally constructed to improve the precision of chiral recognition.

Atomic Dispersion of Zn2+ on N-Doped Carbon Materials: From Non-Activity to High Activity for Catalyzing Luminol-H2O2 Chemiluminescence.

Fe and Co single-atom catalysts (SACs) have been widely explored in many fields, while Zn SACs are still in their infancy stage. Herein, we unexpectedly found that atomically dispersed Zn2+ on N-doped carbon material (Zn-N-C) exhibited high catalytic activity on luminol-H2O2 chemiluminescence (CL) reaction. The Zn-N-C SACs were readily prepared through simple pyrolyzation of the cheap precursors (dopamine and ZnCl2). The mechanism of Zn SAC-catalyzed CL reaction of luminol-H2O2 was investigated in detail. The activity of Zn SACs originated from the Zn-N sites in the Zn-N-C structure. The monoatomic dispersion makes Zn2+ catalytic performance change from no activity to high activity in luminol-H2O2 CL reaction. This study demonstrated the particularity of the monatomic metal catalyst over the conventional metal ion. This work provides the unprecedented perspective for design of new metal SACs in CL reaction.

Simply prepared electrocatalyst of CoFe alloy and nitrogen-doped carbon with multi-dimensional structure and high performance for rechargeable zinc-air battery.

Simple and green preparation of highly-performed electrocatalysts for reaction both at cathode (oxygen reduction reaction (ORR)) and anode (oxygen evolution reaction (OER)) is crucial for boosting the application of meta-air battery. CoFe alloy and nitrogen doped carbon (CoFe-NC) material was prepared by a one-step carbonization procedure to construct a highly efficient electrocatalysis in this work. CoFe-NC displays a three-dimensional (3D) flower-like morphology composed of ordered stacked 2D nanosheets, which is entangled by 1D carbon nanotubes (CNTs). Its structure and electrocatalytic performance are compared with that of nitrogen doped carbon materials obtained from 2D zeolitic-imidazolate frameworks (ZIF) with no metal or single metal, as well as 3D ZIF with bimetal. Benefiting from the multi-dimensional structure of bimetal nanoparticles, 1D CNTs, 2D nanosheets, and 3D flowers, as well as the abundant active sites of Co/Fe-Nxand pyridine nitrogen, CoFe-NC displays a high half-wave potential of 0.896 V for ORR and low overpotential of 370 mV at 10 mA cm-2for OER. Furthermore, compared with the primary and rechargeable Zn-air batteries fabricated with commercial Pt/C-RuO2catalysts, the CoFe-NC catalysts assembled Zn-air batteries show a higher specific capacity (812.2 mAh g-1), open circuit potential (1.59 V), power density (183.4 mW cm-2), and stability. Hence, a facile and environmental-friendly strategy is provided for rational design and synthesis of bifunctional electrocatalysts for zinc-air batteries.

Identification of miRNA-Target Gene Pairs in the Parietal and Frontal Lobes of the Brain in Patients with Alzheimer's Disease Using Bioinformatic Analyses.

Alzheimer's disease (AD) is a growing health concern worldwide. MicroRNAs (miRNAs) have been extensively studied in many diseases, including AD. To identify differentially expressed miRNAs (DEmiRNAs) and genes specific to AD, we used bioinformatic analyses to investigate candidate miRNA-mRNA pairs involved in the pathogenesis of AD. We focused on differentially expressed genes (DEGs) that are targets of DEmiRNAs. The GEO2R tool and the HISAT2-DESeq2 software were used to identify DEmiRNAs and DEGs. Bioinformatic tools available online, such as TAM and the Database for Annotation, Visualization and Integrated Discovery (DAVID), were used to perform functional annotation and enrichment analysis. Targets of miRNAs were predicted using the miRTarBase. The Search Tool for the Retrieval of Interacting Genes (STRING) and Cytoscape, which are available online, were utilized to construct protein-protein interaction (PPI) networks and identify hub genes. Furthermore, transcription factors (TFs) encoded by the DEGs were predicted using the TransmiR database and TF-miRNA-mRNA networks were constructed. Finally, the expression profile of a hub gene in peripheral blood mononuclear cells was compared between healthy individuals and AD patients. We identified 26 correlated miRNA-mRNA pairs. In the parietal lobe, miRNA-mRNA pairs involved in protein folding were enriched, and in the frontal lobe, miRNA-mRNA pairs involved in synaptic transmission, abnormal protein degradation, and apoptosis were enriched. In addition, HSP90AB1 in peripheral blood mononuclear cells was found to be significantly downregulated in AD patients, and this was consistent with its expression profile in the parietal lobe of AD patients. Our results provide brain region-specific changes in miRNA-mRNA associations in AD patients, further our understanding of potential underlying molecular mechanisms of AD, and reveal promising diagnostic and therapeutic targets for AD.

Metal-free N and O Co-doped carbon directly derived from bicrystal Zn-based zeolite-like metal-organic frameworks as durable high-performance pH-universal oxygen reduction reaction catalyst.

A simple and green approach is studied for the preparation of a high-activity metal-free N,O-codoped porous carbon (NOPC) electrocatalyst by one-step pyrolysis of pristine zinc-based zeolite-like metal-organic framework (Zn-ZMOF) synthesized by hydrothermal method from Zn2+and 4,5-imidazoledicarboxylic acid (H3IDC) in H2O solvent. It is found that the structure and electroactivity of Zn-ZMOF and NOPC vary with the molar ratio of H3IDC to zinc acetate. NOPC shows pH-universal electrocatalytic property for oxygen reduction reaction and its electrocatalytic performance is similar to that of Pt/C in alkaline and neutral electrolytes, and is close to that of Pt/C in acidic electrolyte, which is a relatively rare case for metal-free porous carbon derived from pristine MOF. Meanwhile, NOPC displays higher long-term stability and better tolerance to methanol and carbon monoxide poisoning than that of commercial Pt/C. The excellent performance of NOPC is mainly due to the special structure of the precursor Zn-ZMOF, and the synergism of abundant active sites, micro/mesoporous structure, large specific surface area, and high degree of graphitization.

Hollow and mesoporous lipstick-like nitrogen-doped carbon with incremented catalytic activity for oxygen reduction reaction.

Hollow structure and pore size are considered to be crucial to the performance of nitrogen-doped carbon materials. In this paper, a lipstick-like hollow and mesoporous nitrogen-doped carbon (HNC-1000) material is prepared using a bottom-up template participation strategy. The images by scanning electron microscopy and transmission electron microscopy show that the precursor ZnO particles, the intermediate ZnO@ZIF-8 core-shell particles, and the target HNC-1000 particles all maintain a lipstick-like morphology, and HNC-1000 is a hollow nitrogen-doped carbon material. The specific surface area and pore size analyses show that the synthesized HNC-1000 has a very rich mesoporous structure with Vmeso+macro/Vtotal of 94.8% and mean mesopore size at 13.67 nm. X-ray photoelectron spectroscopy results show that the nitrogen in the catalyst HNC-1000 is mainly pyridine nitrogen and graphite nitrogen. The prepared HNC-1000 has excellent ORR catalytic activity with onset potential (0.98 V versus RHE), half-wave potential (0.85 V versus RHE), and limiting current density (5.51 mA cm-2), which is comparable to that of commercial Pt/C (20 wt%) and superior to NC-1000 derived from pristine ZIF-8. HNC-1000 also has good stability and strong methanol tolerance, which is superior to commercial Pt/C catalyst. The improved performance of HNC-1000 is attributed to its hollow and mesoporous morphology. These findings demonstrate a stratage for the rational design and synthesis of practical electrocatalysts.

Persistent Helicobacter pylori infection for more than 3 years leads to elevated serum homocysteine concentration: A retrospective cohort study based on a healthy Chinese population.

BACKGROUND AND AIM: The relationship between the Helicobacter pylori (H. pylori) infection and homocysteine is unclear. We evaluated the effect of H. pylori on serum homocysteine in a healthy Chinese population. METHODS: A total of 21 184 individuals aged over 18 years underwent 13 C/14 C urease breath test (13 C/14 C-UBT) and blood tests and 5042 individuals with follow-up intervals greater than 6 months. Homocysteine levels are classified according to the Chinese expert consensus. RESULTS: The rates of H. pylori infection of normal level, mild level, moderate level, and severe level were 40.9%, 43.8%, 45.8%, and 46.6%, respectively (P = 0.000). H. pylori infection increased the risk of higher homocysteine concentration (OR = 1.406, P = 0.000). In the case-control study, the rates of persistent negative, new infection, persistent infection, and eradication infection were 43.6%, 11.2%, 22.9%, and 22.3%, respectively. The percentage of changes in serum homocysteine levels varied significantly among the different H. pylori infection statuses only in mild level (P = 0.024). Mean changed homocysteine values were higher in the subgroup of persistent infection than in the persistent negative subgroup (P = 0.004) and the eradication infection subgroup (P = 0.034). Serum homocysteine values were elevated only in the subgroup with over 3 years interval time and persistent infection (n = 107, mean paired differences = 1.1 ± 4.6 µmol/L, P = 0.014). CONCLUSIONS: There is a relationship between H. pylori and serum homocysteine, and persistent infection leads to elevation of the latter.

Thin NiFeCr-LDHs nanosheets promoted by g-C3N4: a highly active electrocatalyst for oxygen evolution reaction.

NiFeCr layered double hydroxides (NiFeCr-LDHs) supported on graphitic carbon nitride (g-C3N4) hybrids (NiFeCr-LDHs/g-C3N4) are synthesized and used as an electrocatalyst for oxygen evolution reaction (OER) in alkaline media. Effect of g-C3N4 on the structure and OER performance of NiFeCr-LDHs are investigated in detail. g-C3N4 can promote the formation of thin NiFeCr-LDHs nanosheets, thereby enhancing both the number of active sites and OER activity. X-ray photoelectron spectra measurements confirm the electronic interaction between g-C3N4 and NiFeCr-LDHs nanosheets. The OER performance of NiFeCr-LDHs/g-C3N4 hybrids highly relates to the weight ratio of g-C3N4 to NiFeCr-LDHs. When the weight ratio of g-C3N4 to NiFeCr-LDHs is 5%, the corresponding electrocatalyst shows the best OER activity. The component optimized NiFeCr-LDHs/g-C3N4 hybrids display the overpotential of ∼223 mV at 10 mA cm-2 and Tafel slope of 89 mV dec-1 for OER in 1 M KOH solution, which is better than that of pristine NiFeCr-LDHs, bare g-C3N4, and commercial RuO2.

Sulfonate-Functionalized Mesoporous Silica Nanoparticles as Carriers for Controlled Herbicide Diquat Dibromide Release through Electrostatic Interaction.

Environmental stimuli-responsive pesticide release is desirable for enhanced efficiency and reduced side effects. In most cases, the loading and release of pesticides mainly depends on hydrophobic interactions and hydrogen bonding. Electrostatic interaction is less investigated as a weapon for achieving high loading content and controlled pesticide release. In this work, negative-charge decorated mesoporous silica nanoparticles (MSNs) were facilely fabricated by introducing sulfonate groups onto MSNs through a post-grafting method. Sulfonate-functionalized MSNs (MSN-SO3) were synthesized by conversion of epoxy group into sulfonate group using a bisulfite ion as a ring opening reagent. Diquat dibromide (DQ), one of the globally used quaternary ammonium herbicides, was efficiently loaded into these negatively charged MSN-SO3 nanoparticles. The loading content was increased to 12.73% compared to those using bare MSNs as carriers (5.31%). The release of DQ from DQ@MSN-SO3 nanoparticles was pH and ionic strength responsive, which was chiefly governed by the electrostatic interactions. Moreover, DQ@MSN-SO3 nanoparticles exhibited good herbicidal activity for the control of Datura stramonium L., and the bioactivity was affected by the ionic strength of the release medium. The strategy of cargo loading and release dependent on the electrostatic interactions could be generally used for charge-carrying pesticides using carriers possessing opposite charges to mitigate the potential negative impacts on the environment.

The YebN Leader RNA Acts as a Mn2+ Sensor Required for the Interaction of Xanthomonas oryzae and Rice.

Riboswitches are RNA elements that sense metabolites and control gene expression. Recently, the yybP-ykoY riboswitches were found to sense manganese (Mn2+) and regulate the expression of diverse genes. Here, we show that the leader RNA (a yybP-ykoY RNA) of yebN in Xanthomonas oryzae pv. oryzae also functions as a sensor of Mn2+. This leader RNA detects Mn2+ levels in plants and is essential to X. oryzae pv. oryzae virulence. Our data also indicate that Mn2+ is not only required as a microelement for plant growth but also acts as a defense molecule to inhibit pathogen growth. This finding highlights that Mn2+ plays important roles in pathogen-plant interactions and that the yebN leader RNA can be a target candidate for anti-X. oryzae pv. oryzae drug development.

Uptake and Distribution of Fenoxanil-Loaded Mesoporous Silica Nanoparticles in Rice Plants.

Mesoporous silica nanoparticles (MSNs) can be used as carriers to deliver pesticides into plants, which is considered to be one method of improving the efficacy of pesticide usage in agricultural production. In the present work, MSNs with an average diameter of 258.1 nm were synthesized and loaded with Fenoxanil. The structure of the nanocarriers was observed by scanning electron microscopy. The loading content of Fenoxanil-loaded MSNs was investigated. After rice plants in a hydroponic system were treated with loaded MSNs, the concentrations of Fenoxanil in different samples were determined using high-performance liquid chromatography⁻tandem mass spectrometry. The results suggested that rice plants can absorb MSNs from water through their roots, and the dosage has almost no effect on the distribution of Fenoxanil in rice plants. The application of pesticide-loaded nanoparticles in a hydroponic system poses a low risk of Fenoxanil accumulation in rice.

Synthesis and Characterization of Stimuli-Responsive Poly(2-dimethylamino-ethylmethacrylate)-Grafted Chitosan Microcapsule for Controlled Pyraclostrobin Release.

Controllable pesticide release in response to environmental stimuli is highly desirable for better efficacy and fewer adverse effects. Combining the merits of natural and synthetic polymers, pH and temperature dual-responsive chitosan copolymer (CS-g-PDMAEMA) was facilely prepared through free radical graft copolymerization with 2-(dimethylamino) ethyl 2-methacrylate (DMAEMA) as the vinyl monomer. An emulsion chemical cross-linking method was used to expediently fabricate pyraclostrobin microcapsules in situ entrapping the pesticide. The loading content and encapsulation efficiency were 18.79% and 64.51%, respectively. The pyraclostrobin-loaded microcapsules showed pH-and thermo responsive release. Microcapsulation can address the inherent limitation of pyraclostrobin that is photo unstable and highly toxic on aquatic organisms. Compared to free pyraclostrobin, microcapsulation could dramatically improve its photostability under ultraviolet light irradiation. Lower acute toxicity against zebra fish on the first day and gradually similar toxicity over time with that of pyraclostrobin technical concentrate were in accordance with the release profiles of pyraclostrobin microcapsules. This stimuli-responsive pesticide delivery system may find promising application potential in sustainable plant protection.

Correction: A universal strategy for visual chiral recognition of α-amino acids with l-tartaric acid-capped gold nanoparticles as colorimetric probes.

Correction for 'A universal strategy for visual chiral recognition of α-amino acids with l-tartaric acid-capped gold nanoparticles as colorimetric probes' by Guoxin Song et al., Analyst, 2016, 141, 1257-1265.

Multidrug resistance protein 4 is a critical protein associated with the antiviral efficacy of nucleos(t)ide analogues.

BACKGROUND & AIMS: Multidrug resistance protein 4 (MRP4) has been associated with nucleos(t)ide analogue (NA) antiretroviral therapy failure, though is unclear if MRP4 is also correlated with the failure of anti-hepatitis B virus (HBV) therapy. METHODS: Multidrug resistance protein 4 expression in human peripheral blood mononuclear cells (PBMCs), liver tissues and human hepatoma cell lines was detected by real-time polymerase chain reaction (PCR), western blotting and immunohistochemistry assays. Supernatant and intracellular HBV DNA levels of MRP4-overexpressing or silenced HepG2.4D14 (wild-type) and HepG2.A64 (entecavir-resistant mutant) cells were measured by quantitative PCR. NA concentrations and HBV mutational analysis were assessed by liquid chromatography/mass spectrometry assays and DNA sequencing. Multivariate analysis was used to assess predictive factors for treatment failure. RESULTS: High expression of MRP4 was found in hepatoma cell lines and PBMCs, and up- or down-regulation of MRP4 expression altered the susceptibility of cells to NAs. MRP inhibitors increased NA intracellular accumulation and decreased extracellular levels. Moreover, MRP4 expression in PBMCs was correlated with that in paired liver tissues. Furthermore, multivariate analysis showed MRP4 mRNA expression to be an independent predictor of NA treatment failure. CONCLUSIONS: Multidrug resistance protein 4 is a critical protein associated with the antiviral efficacy of NAs, and combination therapy of NA and MRP inhibitors could reduce the dosage for long-term NA use. This is the first report to demonstrate that MRP4 expression is an important factor predicting treatment failure in chronic hepatitis B patients and will provide a potential therapeutic target against HBV.

A universal strategy for visual chiral recognition of α-amino acids with L-tartaric acid-capped gold nanoparticles as colorimetric probes.

The ability to recognize and quantify the chirality of alpha-amino acids constitutes the basis of many critical areas for specific targeting in drug development and metabolite probing. It is still challenging to conveniently distinguish the enantiomer of amino acids largely due to the lack of a universal and simple strategy. In this work, we report a strategy for the visual recognition of α-amino acids. It is based on the chirality of L-tartaric acid-capped gold nanoparticles (L-TA-capped AuNPs, ca. 13 nm in diameter). All of 19 right-handed α-amino acids can induce a red-to-blue color change of L-TA-capped AuNP solution, whereas all of the left-handed amino acids (except cysteine) cannot. The chiral recognition can be achieved by the naked eye and a simple spectrophotometer. This method does not require complicated chiral modification, and excels through its low-cost, good availability of materials and its simplicity. Another notable feature of this method is its high generality, and this method can discriminate almost all native α-amino acid enantiomers. This versatile method could be potentially used for high-throughput chiral recognition of amino acids.

Naked-eye rapid recognition of tyrosine enantiomers using silver triangular nanoplates as colorimetric probe.

Recognizing and quantifying enantiomers of chiral molecule is of great importance in chemical, biological and pharmaceutical fields. Herein, we presented one simple-yet-efficient method of sensing tyrosine (Tyr) enantiomers. In this sensing, silver triangular nanoplates (AgTNPs) were used as colorimetric probes. L-Tyr quickly induced the color of AgTNPs solution to change from dark blue to light gray, whereas D-Tyr induced no change of the AgTNPs solution color. The obvious color change enables the naked eye to recognize Tyr enantiomer. The visual method was used to detect the enantiometric excess value of L-Tyr in the whole range (-100 % ∼ 100 %). This chiral sensing can be finished within 5 min using one simple ultraviolet-visible spectrometer or naked eye. Furthermore, the mechanism of this chiral sensing was explored. It was confirmed that this chiral sensing was based on AgTNPs' intrinsic chirality. This chiral sensing is rapid, simple, and low-cost, and has great potential for chiral determination of Tyr.

Application of red mud as a basic catalyst for biodiesel production.

Red mud was investigated in triglyceride transesterification with a view to determine its viability as a basic catalyst for use in biodiesel synthesis. The effect of calcination temperature on the structure and activity of red mud catalysts was investigated. It was found that highly active catalyst was obtained by simply drying red mud at 200 degrees C. Utilization of red mud as a catalyst for biodiesel production not only provides a cost-effective and environmentally friendly way of recycling this solid red mud waste, significantly reducing its environmental effects, but also reduces the price of biodiesel to make biodiesel competitive with petroleum diesel.

The Multiple Facets and Disorders of B Cell Functions in Hepatitis B Virus Infection.

Chronic hepatitis B virus (HBV) infection continues to be a global public health burden. B cells play a pivotal role in mediating HBV clearance and can participate in the development of anti-HBV adaptive immune responses through multiple mechanisms, such as antibody production, antigen presentation, and immune regulation. However, B cell phenotypic and functional disorders are frequently observed during chronic HBV infection, suggesting the necessity of targeting the disordered anti-HBV B cell responses to design and test new immune therapeutic strategies for the treatment of chronic HBV infection. In this review, we provide a comprehensive summary of the multiple roles of B cells in mediating HBV clearance and pathogenesis as well as the latest developments in understanding the immune dysfunction of B cells in chronic HBV infection. Additionally, we discuss novel immune therapeutic strategies that aim to enhance anti-HBV B cell responses for curing chronic HBV infection.

Biodegradable electrospun fibers as sustained-release carriers of insect pheromones for field trapping of Spodoptera litura (Lepidoptera: Noctuidae).

BACKGROUND: Insect pheromones are highly effective and environmentally friendly, and are widely used in the monitoring and trapping of pests. However, many researchers have found that various factors such as ultraviolet light and temperature in the field environment can accelerate the volatilization of pheromones, thus affecting the actual control effect. In recent years, electrospinning technology has demonstrated remarkable potential in the preparation of sustained carriers. Moreover, the utilization of biodegradable materials in electrospinning presents a promising avenue for the advancement of eco-friendly carriers. RESULTS: In this study, homogeneous and defect-free pheromone carriers were obtained by electrospinning using fully biodegradable polyhydroxybutyrate materials and pheromones of Spodoptera litura. The electrospun fibers with porous structure could continuously release pheromone (the longest can be ≤80 days). They also had low light transmission, hydrophobic protection. More importantly, the pheromone-loaded electrospun fiber carriers showed stable release and good trapping effect in the field. They could trap pests for at least 7 weeks in the field environment without other light stabilizers added. CONCLUSION: Sustained-release carriers constructed by electrospinning and green materials could improve the efficacy of pheromones and ensure environmental friendliness, and provided a tool for the management of S. litura and other pests and sustainable development of agricultural. © 2023 Society of Chemical Industry.

General anesthesia in children and long-term neurodevelopmental deficits: A systematic review.

Background: Millions of children experienced surgery procedures requiring general anesthesia (GA). Any potential neurodevelopmental risks of pediatric anesthesia can be a serious public health issue. Various animal studies have provided evidence that commonly used GA induced a variety of morphofunctional alterations in the developing brain of juvenile animals. Methods: We conducted a systematic review to provide a brief overview of preclinical studies and summarize the existing clinical studies. Comprehensive literature searches of PubMed, EMBASE, CINAHL, OVID Medline, Web of Science, and the Cochrane Library were conducted using the relevant search terms "general anesthesia," "neurocognitive outcome," and "children." We included studies investigating children who were exposed to single or multiple GA before 18, with long-term neurodevelopment outcomes evaluated after the exposure(s). Results: Seventy-two clinical studies originating from 18 different countries published from 2000 to 2022 are included in this review, most of which are retrospective studies (n = 58). Two-thirds of studies (n = 48) provide evidence of negative neurocognitive effects after GA exposure in children. Neurodevelopmental outcomes are categorized into six domains: academics/achievement, cognition, development/behavior, diagnosis, brain studies, and others. Most studies focusing on children <7 years detected adverse neurocognitive effects following GA exposure, but not all studies consistently supported the prevailing view that younger children were at greater risk than senior ones. More times and longer duration of exposures to GA, and major surgeries may indicate a higher risk of negative outcomes. Conclusion: Based on current studies, it is necessary to endeavor to limit the duration and numbers of anesthesia and the dose of anesthetic agents. For future studies, we require cohort studies with rich sources of data and appropriate outcome measures, and carefully designed and adequately powered clinical trials testing plausible interventions in relevant patient populations.