Improvement in ORR Durability of Fe Single-Atom Carbon Catalysts Hybridized with CeO2 Nanozyme.

FeNC catalysts are considered one of the most promising alternatives to platinum group metals for the oxygen reduction reaction (ORR). Despite the extensive research on improving ORR activity, the undesirable durability of FeNC is still a critical issue for its practical application. Herein, inspired by the antioxidant mechanism of natural enzymes, CeO2 nanozymes featuring catalase-like and superoxide dismutase-like activities were coupled with FeNC to mitigate the attack of reactive oxygen species (ROS) for improving durability. Benefiting from the multienzyme-like activities of CeO2, ROS generated from FeNC is instantaneously eliminated to alleviate the corrosion of carbon and demetallization of metal sites. Consequently, FeNC/CeO2 exhibits better ORR durability with a decay of only 5 mV compared to FeNC (18 mV) in neutral electrolyte after 10k cycles. The FeNC/CeO2-based zinc-air battery also shows minimal voltage decay over 140 h in galvanostatic discharge-charge cycling tests, outperforming FeNC and commercial Pt/C.

Nanozyme Metabolism Controls Air Pollution over an Atomic Potassium Cyano Site.

Increasing threats of air pollution prompt the design of air purification systems. As a promising initiative defense strategy, nanocatalysts are integrated to catalyze the detoxification of specific pollutants. However, it remains a grand challenge to tailor versatile nanocatalysts to cope with diverse pollutants in practice. Here, we report a nanozyme metabolism system to realize broad-spectrum protection from air pollution. Atomic K-modified carbon nitride featuring flavin oxidase-like and peroxidase-like activities was synthesized to initiate nanozyme metabolism. In situ experiments and theoretical investigations collectively show that K sites optimize the geometric and electronic structure of cyano sites for both enzyme-like activities. As a proof of concept, the nanozyme metabolism was applied to the mask against volatile organic compounds, persistent organic pollutants, reactive oxygen species, bacteria, and so on. Our finding provides a thought to tackle global air pollution and deepens the understanding of nanozyme metabolism.

Grain-Boundary-Rich Ceria Metallene Nanozyme with Abundant Metal Site Pairs Boosts Phosphatase-like Activity.

Natural phosphatases featuring paired metal sites inspire various advanced nanozymes with phosphatase-like activity as alternatives in practical applications. Numerous efforts to create point defects show limited metal site pairs, further resulting in insufficient activity. However, it remains a grand challenge to accurately engineer abundant metal site pairs in nanozymes. Herein, we report a grain-boundary-rich ceria metallene nanozyme (GB-CeO2) with phosphatase-like activity. Grain boundaries acting as the line or interfacial defects can effectively increase the content of Ce4+/Ce3+ site pairs to 72.28%, achieving a 49.28-fold enhancement in activity. Furthermore, abundant grain boundaries optimize the band structure to assist the photoelectron transfer under irradiation, which further increases the content of metal site pairs to 88.96% and finally realizes a 114.39-fold enhanced activity over that of CeO2 without irradiation. Given the different inhibition effects of pesticides on catalysts with and without irradiation, GB-CeO2 was successfully applied to recognize mixed toxic pesticides.

In Situ Defect Engineering of Fe-MIL for Self-Enhanced Peroxidase-Like Activity.

Defect engineering is an effective strategy to enhance the enzyme-like activity of nanozymes. However, previous efforts have primarily focused on introducing defects via de novo synthesis and post-synthetic treatment, overlooking the dynamic evolution of defects during the catalytic process involving highly reactive oxygen species. Herein, a defect-engineered metal-organic framework (MOF) nanozyme with mixed linkers is reported. Over twofold peroxidase (POD)-like activity enhancement compared with unmodified nanozyme highlights the critical role of in situ defect formation in enhancing the catalytic performance of nanozyme. Experimental results reveal that highly active hydroxyl radical (•OH) generated in the catalytic process etches the 2,5-dihydroxyterephthalic acid ligands, contributing to electronic structure modulation of metal sites and enlarged pore sizes in the framework. The self-enhanced POD-like activity induced by in situ defect engineering promotes the generation of •OH, holding promise in colorimetric sensing for detecting dichlorvos. Utilizing smartphone photography for RGB value extraction, the resultant sensing platform achieves the detection for dichlorvos ranging from 5 to 300 ng mL-1 with a low detection limit of 2.06 ng mL-1. This pioneering work in creating in situ defects in MOFs to improve catalytic activity offers a novel perspective on traditional defect engineering.

Research on the Cell Wall Breaking and Subcritical Extraction of Astaxanthin from Phaffia rhodozyma.

This study focused on developing an effective cell wall-breaking method for Phaffia rhodozyma, followed by utilizing subcritical fluid extraction to isolate, extract, and concentrate astaxanthin from the complex fermentation products of P. rhodozyma. A comprehensive comparison of seven distinct methods for disrupting cell walls, including dimethyl sulfoxide treatment, lactic acid treatment, sodium hydroxide treatment, ß-glucanase enzymatic digestion, ß-mannanase enzymatic digestion, and a combined enzymatic treatment involving both ß-mannanase and ß-glucanase was conducted. The results identified the lactic acid method as the most effective in disrupting the cell walls of P. rhodozyma. The software, Design Expert, was used in the process of extracting astaxanthin from cell lysates using a subcritical extraction method. Through fitting analysis and response surface optimization analysis by Design Expert, the optimal extraction conditions were determined as follows: an extraction temperature of 41 °C, extraction frequency of two times, and extraction time of 46 min. These parameters facilitated the efficient extraction, concentration, and enrichment of astaxanthin from P. rhodozyma, resulting in an astaxanthin concentration of 540.00 mg/L. This result can establish the foundation for its high-value applications.

Dyslexia-related loci are significantly associated with language and literacy in Chinese-English bilingual Hong Kong Chinese twins.

A recent genome-wide association study on dyslexia in 51,800 affected European adults and 1,087,070 controls detected 42 genome-wide significant single nucleotide variants (SNPs). The association between rs2624839 in SEMA3F and reading fluency was replicated in a Chinese cohort. This study explores the genetic overlap between Chinese and English word reading, vocabulary knowledge and spelling, and aims at replicating the association in a unique cohort of bilingual (Chinese-English) Hong Kong Chinese twins. Our result showed an almost complete genetic overlap in vocabulary knowledge (r2 = 0.995), and some genetic overlaps in word reading and spelling (r2 = 0.846, 0.687) across the languages. To investigate the region near rs2624839, we tested proxy SNPs (rs1005678, rs12632110 and rs12494414) at the population level (n = 305-308) and the within-twin level (n = 342-344 [171-172 twin pairs]). All the three SNPs showed significant associations with quantitative Chinese and English vocabulary knowledge (p < 0.05). The strongest association after multiple testing correction was between rs12494414 and English vocabulary knowledge at the within-twin level (p = 0.004). There was a trend of associations with word reading and spelling in English but not in Chinese. Our result suggested that the region near rs2624839 is one of the common genetic factors across English and Chinese vocabulary knowledge and unique factors of English word reading and English spelling in bilingual Chinese twins. A larger sample size is required to validate our findings. Further studies on the relationship between variable expression of SEMA3F, which is important to neurodevelopment, and language and literacy are encouraged.

Four-Component Cyclization of Naphthol/Thionaphthol/Naphthylamine, Formaldehyde, and DBU in Water.

A practical and environmentally benign cascade multicomponent condensation of naphthol/thionaphthol/naphthylamine, formaldehyde, and DBU in water without any catalysts has been achieved. A wide variety of dihydrooxazine, dihydrothiazine, and tetrahydrobenzoquinazoline derivatives N-substituted with a tether bearing a caprolactam unit were afforded in moderate to good yields. The advantages of being cost-effective, metal-free, and easily handled and the use of water as medium made this protocol conform with the principle of green synthesis.

Problems of the Grid Size Selection in Differential Box-Counting (DBC) Methods and an Improvement Strategy.

The differential box-counting (DBC) method is useful for determining the fractal dimension of grayscale images. It is simple to learn and implement and has been extensively utilized. However, this approach has several problems, such as over- or undercounting the number of boxes due to inappropriate parameter choices, limiting the calculation accuracy. Many studies have been conducted to increase the algorithm's computational accuracy by improving the calculating parameters of the differential box-counting method. The grid size is a crucial parameter for the DBC method. Generally, there are two typical ways for selecting the grid size in relevant studies: consecutive integer and divisors of image size. However, both methods for grid size selection are problematic. The consecutive integer method cannot partition the image entirely and will result in the undercounting of boxes; the divisors of image size can partition the image completely. However, this method uses fewer grid sizes to compute fractal dimensions and has a relatively huge distance error (DE). To address the shortcomings of the above-mentioned two approaches, this research presents an improved grid size selection strategy. The improved method enhances computational accuracy by computing the discarded image edge areas in the consecutive integer method, allowing the original image information to be used as thoroughly as the divisor strategy. Based on fractional Brownian motion (FBM), Brodatz, and Aerials image sets, the accuracy of the three grid size selection techniques (consecutive integer method, divisors of image size method, and the improved algorithm) to compute the fractal dimension is then compared. The results reveal that, compared to the two prior techniques, the revised algorithm described in this study minimizes the distance error and increases the accuracy of the fractal dimension computation.

Directly Imaging Dynamic Electronic Coupling during Electrochemical Oxidation of Single Silver Nanoparticles.

The electronic coupling between a metal electrode and single nano-entities is of unfading significance which impacts the heterogeneous electron transfer. Herein, we demonstrated a simple optical technique for directly imaging the transient interfacial electronic coupling events during electrochemical oxidation of single Ag nanoparticles on Au electrode. The electronic coupling brings out a dramatic dip behavior of bright field imaging traces, and is conductive to cross the energy barrier of oxidation for single silver nanoparticles. This dip behavior is further verified by in situ vis-transmission spectroscopy, and the heterogeneity of the Au-Ag electronic coupling down to single-nanoparticle level is uncovered by unifying the morphology and size of individual silver nanoparticles. These results suggest the interfacial electronic coupling facilitates electron transfer of single nanoparticles, and provide important insight into understanding detailed mechanism of nanoelectrochemistry.

Accessing the Electrochemical Activity of Single Nanoparticles by Eliminating the Heterogeneous Electrical Contacts.

While single nanoparticle electrochemistry holds great promise for establishing the structure-activity relationship (SAR) of electroactive nanomaterials, as it removes the heterogeneity among individuals, successful SAR studies remain rare. When one nanoparticle is seen to exhibit better performance than the others, it is often simply attributed to better activity of the particular individual. By taking the ion insertion reaction of Prussian blue nanoparticles as an example, here we show that the electrical contact between nanoparticles and electrode, a previously overlooked factor, was greatly distinct from one nanoparticle to another and significantly contributed to the apparent heterogeneity in the reactivity and cyclability. An individual nanoparticle with intrinsically perfect structure (size, facet, crystallinity, and so on) could be completely inactive, simply due to poor electrical contacts, which blurred the SAR and likely caused failures. We further proposed a sputter-coating method to enhance the electrical contacts by depositing an ultrathin platinum layer onto the sample. Such an approach was routinely adopted in scanning electron microscopy to improve the electron mobility between nanoparticles and substrate. Elimination of heterogeneous contacts ensured that the electrochemical activity of single nanoparticles can be accessed and further correlated with their structural features, thus paving the way for single nanoparticle electrochemistry to deliver on its promises in SAR.

Real-Time In†Vivo Hepatotoxicity Monitoring through Chromophore-Conjugated Photon-Upconverting Nanoprobes.

Drug toxicity is a long-standing concern of modern medicine. A typical anti-pain/fever drug paracetamol often causes hepatotoxicity due to peroxynitrite ONOO- . Conventional blood tests fail to offer real-time unambiguous visualization of such hepatotoxicity in vivo. Here we report a luminescent approach to evaluate acute hepatotoxicity in vivo by chromophore-conjugated upconversion nanoparticles. Upon injection, these nanoprobes mainly accumulate in the liver and the luminescence of nanoparticles remains suppressed owing to energy transfer to the chromophore. ONOO- can readily bleach the chromophore and thus recover the luminescence, the presence of ONOO- in the liver leads to fast restoring of the near-infrared emission. Taking advantages of the high tissue-penetration capability of near-infrared excitation/emission, these nanoprobes achieve real-time monitoring of hepatotoxicity in living animals, thereby providing a convenient screening strategy for assessing hepatotoxicity of synthetic drugs.

Elimination of Chlorella using peracetic acid activated by dielectric barrier discharge plasma: Mechanism and cell deactivation process.

Excessive proliferation of algae in water depletes dissolved oxygen, resulting in the demise of aquatic life and environmental damage. This study delves into the effectiveness of the dielectric barrier discharge (DBD) plasma activated peracetic acid (PAA) system in deactivating Chlorella. Within 15 min, the algae removal effectiveness reached 89 % under ideal trial conditions. DBD plasma activation of PAA augmented the concentration of reactive species such as ·OH, 1O2, and organic radicals (RO·) in the solution, which are involved in the process of cell inactivation. Reactive oxygen species (ROS) within Chlorella cells continued to rise as a result of treatment-induced damage to the morphological structure and cell membrane of the organism. DNA and chlorophyll-a (Chl-a), were oxidized and destroyed by these invasive active compounds. This study presents an efficient advanced oxidation method to destroy algal cells and adds an alternative strategy for algal control in areas where eutrophication occurs.

Exploiting synthetic biology platforms for enhanced biosynthesis of natural products in Yarrowia lipolytica.

With the rapid development of synthetic biology, researchers can design, modify, or even synthesize microorganisms de novo, and microorganisms endowed with unnatural functions can be considered "artificial life" and facilitate the development of functional products. Based on this concept, researchers can solve critical problems related to the insufficient supply of natural products, such as low yields, long production cycles, and cumbersome procedures. Due to its superior performance and unique physiological and biochemical characteristics, Yarrowia lipolytica is a favorable chassis cell used for green biomanufacturing by numerous researchers. This paper mainly reviews the development of synthetic biology techniques for Y. lipolytica and summarizes the recent research progress on the synthesis of natural products in Y. lipolytica. This review will promote the continued innovative development of Y. lipolytica by providing theoretical guidance for research on the biosynthesis of natural products.

Efficient conversion of distillers grains as feed ingredient by synergy of probiotics and enzymes.

The direct feeding value of distillers grains is low due to the presence of higher cellulose, lignin and anti-nutritional factors such as mannan and xylan. In this study, complex enzymes and probiotic flora based on "probiotic enzyme synergy" technology were used to produce fermented distillers grains. The optimal substrate ratio, moisture content, fermentation time and temperature were determined. Subsequently, scale-up experiments were conducted to determine the performance of fermented feed. The results showed that multi-probiotic (Lactobacillus casei, Bacillus subtilis, Saccharomyces cerevisiae, and Aspergillus oryzae) cooperated with complex enzymes (glucanase, mannanase, xylanase) showed excellent fermentation effect, crude protein, trichloroacetic acid soluble protein and fat increased by 31.25, 36.68, and 49.11% respectively, while crude fiber, acidic fiber and neutral fiber decreased by 34.24, 26.91, and 33.20%, respectively. The anti-nutritional factors mannan and arabinoxylan were reduced by 26.96 and 40.87%, respectively. Lactic acid, acetic acid, and propionic acid in the fermented organic acids increased by 240.93, 76.77, and 89.47%, respectively. Butyric acid increased significantly from scratch, and the mycotoxin degradation effect was not significant. This study provides a potential approach for high-value utilization of distillers grains.

A C-shaped miniaturized coil for transcranial magnetic stimulation in rodents.

Objective.Transcranial magnetic stimulation (TMS) is a non-invasive technique widely used for neuromodulation. Animal models are essential for investigating the underlying mechanisms of TMS. However, the lack of miniaturized coils hinders the TMS studies in small animals, since most commercial coils are designed for humans and thus incapable of focal stimulation in small animals. Furthermore, it is difficult to perform electrophysiological recordings at the TMS focal point using conventional coils.Approach.We designed, fabricated, and tested a novel miniaturized TMS coil (4-by-7 mm) that consisted of a C-shaped iron powder core and insulated copper wires (30 turns). The resulting magnetic and electric fields were characterized with experimental measurements and finite element modeling. The efficacy of this coil in neuromodulation was validated with electrophysiological recordings of single-unit activities (SUAs), somatosensory evoked potentials (SSEPs), and motor evoked potentials (MEPs) in rats (n= 32) following repetitive TMS (rTMS; 3 min, 10 Hz).Main results.This coil could generate a maximum magnetic field of 460 mT and an electric field of 7.2 V m-1in the rat brain according to our simulations. With subthreshold rTMS focally delivered over the sensorimotor cortex, mean firing rates of primary somatosensory and motor cortical neurons significantly increased (154±5% and 160±9% from the baseline level, respectively); MEP and SSEP amplitude significantly increased (136±9%) and decreased (74±4%), respectively.Significance.This miniaturized C-shaped coil enabled focal TMS and concurrent electrophysiological recording/stimulation at the TMS focal point. It provided a useful tool to investigate the neural responses and underlying mechanisms of TMS in small animal models. Using this paradigm, we for the first time observed distinct modulatory effects on SUAs, SSEPs, and MEPs with the same rTMS protocol in anesthetized rats. These results suggested that multiple neurobiological mechanisms in the sensorimotor pathways were differentially modulated by rTMS.

A simple synthesis method of microsphere immunochromatographic test strip for time-resolved luminescence detection of folic acid.

Folic acid (FA) is an ingredient that must be added to infant milk powder to avoid potential defects. Rapid, sensitive and reliable detection methods are needed to determined FA addition levels. Thus, this study established a microsphere immunochromatographic test strip for time-resolved luminescence detection (TRLM-ICTS) based on carboxyl-functionalized time-resolved luminescent microspheres (Eu-TRLMs) prepared by a one-step method as fluorescent markers for the immediate quantitative detection of FA in milk powder. Eu-TRLMs prepared by the one-step method showed good dispersion, high stability and strong fluorescence intensity, which is improving the sensitivity of TRLM-ICTS. In the performance evaluation of TRLM-ICTS, the detection limit was 0.487 ng mL-1, the recovery rate was 97.3-105 %, and the actual sample detection results were in line with those of UPLC-MS/MS. TRLM-ICTS has the advantages of rapid, high sensitivity and strong specificity and could as a practical quantitative detection method for the detection of FA in milk powder.

Imaging the Self-Healing Dynamics of Single-Nanoparticle Electron Transfer Event Regulated by Local Electron Insertion.

The self-healing properties of nanomaterials to resist electron beam damage are of great concern, which is inspiring to improve the stability and electron transfer efficiency of nanoelectronic devices especially in an abnormal environment. However, the influence of electron beam insertion on the electron transfer efficiency of single nanoentities at a heterogeneous electrochemical interface is still in debate, which is a concern for the development of in situ liquid cell transmission electron microscopy of the next generation. Herein, we employ an electro-optical imaging technique and directly visualize the controllable recovery of electron transfer ability for single Prussian blue nanoparticle (PBNP) after electron beam insertion with different electron doses. While eliminating e-beam damage by decreasing charge accumulation, the precise control of electron insertion behaviors induces a lossless chemical reduction mechanism for metal ions on the framework structure of PBNP, which leads to static imbalance and temporarily blocks the electron transfer channels. A subsequent charge rebalance process at a sub-nanoparticle level driven by electrochemical cycling controllably rebuilds the ion migration channels on the outer layer of single PBNP to repair the electron transfer path, which is confirmed by single-nanoparticle spectral characterizations. This work provides a generic methodology to study the electron-particle interplay and mechanism of electrode materials for eliminating the heterogeneity of electrochemical activity down to a sub-nanoparticle level.

An in-depth insight into the simultaneous oxidation of sulfamethoxazole and reduction of Cr (VI) by one system of water film DBD plasma: The interaction effect, role of active species, and their dominant to pathways.

This study aims to deeply investigate the simultaneous elimination of sulfamethoxazole (SMZ) and Cr (VI) through one system of water film dielectric barrier discharge (WFDBD) plasma. The interaction effect of SMZ degradation and Cr (VI) reduction and dominant effect of active species were highlighted. Results showed that the oxidation of SMZ and the reduction of Cr (VI) directly promote each other. When the concentration of Cr (VI) raised from 0 to 2 mg L-1, the degradation rate of SMZ enhanced from 75.6% to 88.6%, respectively. Similarly, when the concentration of SMZ improved from 0 to 15 mg L-1, the removal efficiency of Cr (VI) improved from 70.8% to 84.3%, respectively. ·OH, 1O2 and ·O2- play crical roles for SMZ degradation, and e-, ·O2-, ·H and H2O2 dominated to the Cr (VI) reduction. The variations of pH, conductivity and TOC during the removal process were also explored. The removal process was studied by UV-vis spectroscopy and a three-dimensional excitation-emission matrix. Based on DFT calculation and LC-MS analysis, free radicals dominated SMZ degradation pathways in the WFDBD plasma system were clarified. Besides, the influence of Cr (VI) on SMZ degradation pathway was clarified. The ecotoxicity of SMZ and the toxicity of Cr (VI) into Cr (III) were greatly reduced. This study provides a significant reference value for the application and mechanism of plasma simultaneous removal of organic pollutants and heavy metals in wastewater.

Polymer Implantable Electrode Foundry: A shared resource for manufacturing polymer-based microelectrodes for neural interfaces.

Large scale monitoring of neural activity at the single unit level can be achieved via electrophysiological recording using implanted microelectrodes. While neuroscience researchers have widely employed chronically implanted electrode-based interfaces for this purpose, a commonly encountered limitation is loss of highly resolved signals arising from immunological response over time. Next generation electrode-based interfaces improve longitudinal signal quality using the strategy of stabilizing the device-tissue interface with microelectrode arrays constructed from soft and flexible polymer materials. The limited availability of such polymer microelectrode arrays has restricted access to a small number of researchers able to build their own custom devices or who have developed specific collaborations with engineering researchers who can produce them. Here, a new technology resource model is introduced that seeks to widely increase access to polymer microelectrode arrays by the neuroscience research community. The Polymer Implantable Electrode (PIE) Foundry provides custom and standardized polymer microelectrode arrays as well as training and guidance on best-practices for implantation and chronic experiments.

Loss of p53 enhances the tumor-initiating potential and drug resistance of clonogenic multiple myeloma cells.

Tumor relapse and drug resistance are major factors that limit the curability of multiple myeloma (MM). New regimens have improved overall MM survival rates, but patients with high-risk features continue to have inferior outcomes. Chromosome 17p13 deletion (del17p) that includes the loss of the TP53 gene is a high-risk cytogenetic abnormality and is associated with poor clinical outcomes owing to relatively short remissions and the development of pan-drug resistant disease. Increased relapse rates suggest that del17p enhances clonogenic growth, and we found that the loss of p53 increased both the frequency and drug resistance of tumor-initiating MM cells (TICs). Subsequent RNA sequencing (RNA-seq) studies demonstrated significant activation of the Notch signaling pathway and upregulation of inhibitor of DNA binding (ID1/ID2) genes in p53-knock out (p53-KO) cells. We found that the loss of ID1 or HES-1 expression or treatment with a gamma-secretase inhibitor (GSI) significantly decreased the clonogenic growth of p53-KO but not p53 wild-type cells. GSI treatment in a small set of MM specimens also reduced the clonogenic growth in del17p samples but not in non-del17p samples. This effect was specific as overexpression of the Notch intracellular domain (NICD) rescued the effects of GSI treatment. Our study demonstrates that the Notch signaling and ID1 expression are required for TIC expansion in p53-KO MM cells. These findings also suggest that GSI may be specifically active in patients with p53 mutant MM.