One-to-Nine Single Spectroscopic Intelligent Probe for Risk Assessment of Multiple Metals in Drinking Water.

26% of the world's population lacks access to clean drinking water; clean water and sanitation are major global challenges highlighted by the UN Sustainable Development Goals, indicating water security in public water systems is at stake today. Water monitoring using precise instruments by skilled operators is one of the most promising solutions. Despite decades of research, the professionalism-convenience trade-off when monitoring ubiquitous metal ions remains the major challenge for public water safety. Thus, to overcome these disadvantages, an easy-to-use and highly sensitive visual method is desirable. Herein, an innovative strategy for one-to-nine metal detection is proposed, in which a novel thiourea spectroscopic probe with high 9-metal affinity is synthesized, acting as "one", and is detected based on the 9 metal-thiourea complexes within portable spectrometers in the public water field; this is accomplished by nonspecialized personnel as is also required. During the processing of multimetal analysis, issues arise due to signal overlap and reproducibility problems, leading to constrained sensitivity. In this innovative endeavor, machine learning (ML) algorithms were employed to extract key features from the composite spectral signature, addressing multipeak overlap, and completing the detection within 30-300 s, thus achieving a detection limit of 0.01 mg/L and meeting established conventional water quality standards. This method provides a convenient approach for public drinking water safety testing.

Photodegradation Kinetics and Deep Learning-Based Intelligent Colorimetric Method for Bioavailability-Based Dissolved Iron Speciation.

Via the photodegradation of dissolved iron (dFe) complexes in the euphotic zone, released free Fe(III) is the most important source of bioavailable iron for eukaryotic phytoplankton. There is an urgent need to establish bioavailability-based dissolved iron speciation (BDIS) methods. Herein, an intelligent system with dFe pretreatment and a colorimetric sensor is developed for real-time monitoring of newly generated Fe(III) ions. According to the photodegradation kinetics of dFe, including kinetic constant and photogenerated time of free Fe(III) ions, 3 sources, 6 kinds, and 12 species of dFe are determined by our photocatalytic-assisted colorimetric sensor and deep learning model within 20.0 min. The algal dFe-uptake for 4 days can be predicted by BDIS with correlation coefficient 0.85, which could be explained by the hard and soft acids and bases theory (HSAB) and density functional theory (DFT). These results successfully demonstrate the proof-of-concept for photodegradation kinetics-based speciation and bioavailability assessments of dissolved metals.

[Anti-arthritic-related metal bioavailability for optimal compatibility ratio of Aconiti Radix Cocta and Paeoniae Radix Alba].

Trace metals deficiency or excess are associated with the etiology and pathogenesis of rheumatoid arthritis(RA). Aconiti Radix Cocta(A) and Paeoniae Radix Alba(B) are commonly used together for the treatment of RA. In this study, we aim to determine anti-arthritic-related metal bioavailability in the compatibility of herb A and B for avoiding metal deficiency or excess, and optimize the combination ratio of herb A and B, accordingly. Anti-arthritic-related metal bioaccessibility were evaluated by in vitro simulator of all gastrointestinal tract(including mouth, stomach, small and large intestines), and the roles of gastrointestinal digestive enzymes and intestinal microflora were investigated. Anti-arthritic-related metal bioavailability was assessed by the affinity adsorption with liposomes. The results indicated that compatibility proportion of corresponding herbal plants, gastrointestinal digestion and microbial metabolic, which could affect metal digestion and absorption. The optimal compatibility proportion of 1 A∶1 B is recommended, according to the dose of anti-arthritic-related metal bioavailability, which is often chosen for clinical practice of RA therapy. Thus, anti-arthritic-related metal bioavailability might be the key active substances for RA treatment.

Monodisperse hollow spheres with sandwich heterostructured shells as high-performance catalysts via an extended SiO2 template method.

To improve and extend the SiO2 template method for preparing metal oxide hollow spheres, a general and facile "sol-gel and hydrothermal" method is developed to replace the current "sol-gel, calcination, and base-etching" processes for the construction of well-defined sandwich metal oxide@noble metal NP@metal oxide hollow spheres. As-synthesized hollow spheres exhibit high performances in various catalytic reactions.

Constituting fully integrated visual analysis system for Cu(II) on TiO2/cellulose paper.

As a cheap and abundant porous material, cellulose filter paper was used to immobilize nano-TiO2 and denoted as TiO2/cellulose paper (TCP). With high adsorption capacity for Cu(II) (more than 1.65 mg), TCP was used as an adsorbent, photocatalyst, and colorimetric sensor at the same time. Under the optimum adsorption conditions, i.e., pH 6.5 and 25 °C, the adsorption ratio of Cu(II) was higher than 96.1%. Humic substances from the matrix could be enriched onto TCP but the interference of their colors on colorimetric detection could be eliminated by the photodegradation. In the presence of hydroxylamine, neocuproine, as a selective indicator, was added onto TCP, and a visual color change from white to orange was generated. The concentration of Cu(II) was quantified by the color intensity images using image processing software. This fully integrated visual analysis system was successfully applied for the detection of Cu(II) in 10.0 L of drinking water and seawater with a preconcentration factor of 10(4). The log-linear calibration curve for Cu(II) was in the range of 0.5-50.0 µg L(-1) with a determination coefficient (R(2)) of 0.985 and its detection limit was 0.073 µg L(-1).

[Application of in vitro bionic digestion and biomembrane extraction for metal speciation analysis, bioavailability and risk assessment in lianhua qingwen capsule].

One of the causes of the high cost of pharmaceuticals and the major obstacles to rapidly assessing the bioavailability and risk of a chemical is the lack of experimental model systems. A new pre-treatment technology, in vitro bionic digestion was designed for metal analysis in Lianhua Qingwen capsule. The capsule was digested on 37 degrees C under the acidity of the stomach or intestine, and with the inorganic and organic compounds (including digestive enzymes) found in the stomach or intestine, and then the chyme was obtained. Being similar to the biomembrane between the gastrointestinal tract and blood vessels, monolayer liposome was used as biomembrane model Affinity-monolayer liposome metals (AMLMs) and water-soluble metals were used for metal speciation analysis in the capsule. Based on the concentration of AMLMs, the main absorption site of trace metals was proposed. The metal total contents or the concentration of AMLMs in the capsule were compared to the nutritional requirements, daily permissible dose and heavy metal total contents from the "import and export of medicinal plants and preparation of green industry state standards". The metal concentrations in the capsule were within the safety baseline levels for human consumption. After in vitro bionic digestion, most of trace metals were absorbed mainly in intestine. The concentration of As, Cd, Pb was 0.38, 0.07, 1.60 mg x kg(-1), respectively, far less than the permissible dose from the "import and export of medicinal plants and preparation of green industry state standards".

Carbon sequestration reduced by the interference of nanoplastics on copper bioavailability.

Microplastics (MPs) have been recognized as a serious new pollutant, especially nanoplastics (NPs) pose a greater threat to marine ecosystem than larger MPs. Within these ecosystems, phytoplankton serve as the foundational primary producers, playing a critical role in carbon sequestration. Copper (Cu), a vital cofactor for both photosynthesis and respiration in phytoplankton, directly influences their capacity to regulate atmospheric carbon. Therefore, we assessed the impact of NPs on Cu bioavailability and carbon sequestration capacity. The results showed that polystyrene nanoplastics (PS-NPs) could inhibit the growth of Thalassiosira weissflogii (a commonly used model marine diatom) and Chlorella pyrenoidosa (a standard strain of green algae). The concentration of Cu uptake by algae has a significant negative correlation with COPT1 (a Cu uptake protein), but positive with P-ATPase (a Cu efflux protein). Interestingly, PS-NPs exposure could reduce Cu uptake and carbon Cu sequestration capacity of algae, i.e., when the concentration of PS-NPs increases by 1 mg/L, the concentration of fixed carbon dioxide decreases by 0.0023 ppm. This provides a new perspective to reveal the influence mechanisms of PS-NPs on the relationship between Cu biogeochemical cycling and carbon source and sink.

No-interfered and visual evaluation of global warming impacts on phytoplankton-based copper bioavailability and then carbon sequestration.

Global warming has an increasingly serious impact on the ecological environment. Copper bioavailability plays an important physiological role in revealing the mechanism of carbon cycle, photosynthesis, and respiration. Here we reported a multifunctional carbon quantum dots fluorescence probe for no-interfered and visual determination of phytoplankton-based intracellular Cu(II), glucose, and reactive oxygen species (ROS). Glucose and ROS were explored to reflect the change in primary biomass and carbon sequestration. H2O2 is acted as the standard material of ROS, and the fitting parameter for glucose and H2O2 concentrations was 0.42(r = 0.9972). Both glucose, ROS, and Cu2+ detection have advantages of wide linear range (24.8-3.96 × 105 µg/L, 6-9.6 × 105 ng/L and 5-15 × 103 nmol/L, respectively), high precision (1.22 %, 6.38 %, and 7.37 %, respectively), and low detection limit (86.7 ng/L, 5.32 ng/L, and 0.367 nmol/L, respectively). Cu2+ uptake was increased with the increasing of temperature, and the copper bioavailability in increasing order was Cu-PorPhyr > Cu-phthalate > Cu-EDTA. There were significant positive correlation between glucose and Cu2+(r = 0.9943). Copper bioavailability would directly affect the carbon sequestration, i.e., when the concentration of intracellular copper increases by 1 mg/L, the content of intracellular glucose increases by 412 mg/L approximately, equally to 2.47 g/L of carbon dioxide was fixed.

[Application of bionic technology to speciation analysis and bioavailability assessment of nickel in transgenic soybean].

The safety of transgenic food has been paid the most attention to by the public and scientists. Trace metal bioavailability could provide information for safety assessment of transgenic food. The critical functional digestion and absorption in the gastrointestinal tract were simulated by bionic gastrointestinal digestion, metabolism of gut microbiota, and bionic biomembrane adsorption with liposome and then used for the pretreatment of transgenic and general soybeans. Ni speciation in the chyme was defined as affinity-liposome and water soluble Ni. Nickel bioavailability was assessed by the content of affinity-liposome Ni. Water soluble Ni was the main species of nickel complex in the chyme. Nickel bioavailability was 4.1% for transgenic soybean and 3.3% for general soybean, which could be enhanced by gastrointestinal digestion and metabolism of gut microbiota. After transgene, nickel bioavailability was increased 24% but the content of affinity-liposome Ni was 122.3 ng x g(-1) for transgenic soybean, just as 36% as that of general soybean.

The interference of marine accidental and persistent petroleum hydrocarbons pollution on primary biomass and trace elements sink.

More than 80 % of the primary biomass in marine environments is provided by phytoplankton. The primary mechanism in the trace element sink is the absorption of trace elements by phytoplankton. Because of their difficult degradability and bioaccumulation, petroleum hydrocarbons are one of the most significant and priority organic contaminants in the marine environment. This study chose Chlorella pyrenoidosa as the model alga to be exposed to short and medium-term petroleum hydrocarbons. The ecological risk of accidental and persistent petroleum hydrocarbon contamination was thoroughly assessed. The interaction and intergenerational transmission of phytoplankton physiological markers and trace element absorption were explored to reflect the change in primary biomass and trace element sink. C. pyrenoidosa could produce a large number of reactive oxygen species stimulated by the concentration and exposure time of pollutants, which activated their antioxidant activity (superoxide dismutase (SOD) activity, ß-carotene synthesis, antioxidant trace elements uptake) and peroxides production (hydroxyl radicals and malondialdehyde). The influence of the growth phase on SOD activity, copper absorption, and manganese adsorption in both persistent and accidental pollution was significant (p < 0.05, F > Fα). Adsorption of manganese and selenium positively connected with SOD, malondialdehyde, and Chlorophyl-a (p < 0.01). These findings convincingly indicate that petroleum hydrocarbon contamination can interfere with primary biomass and trace element sinks.

Nitrogen-doped carbon@TiO2 double-shelled hollow spheres as an electrochemical sensor for simultaneous determination of dopamine and paracetamol in human serum and saliva.

As the most commonly used antipyretic and analgesic drug, paracetamol (PA) coexists with neurotransmitter dopamine (DA) in real biological samples. Their simultaneous determination is extremely important for human health, but they also interfere with each other. In order to improve the conductivity, adsorption affinity, sensitivity, and selectivity of TiO2-based electrochemical sensor, N-doped carbon@TiO2 double-shelled hollow sphere (H-C/N@TiO2) is designed and synthesized by simple alcoholic and hydrothermal method, using polystyrene sphere (PS) as a template. Meanwhile, TiO2 hollow spheres (H-TiO2) or N-doped carbon hollow spheres (H-C/N) are also prepared by the same method. H-C/N@TiO2 has good conductivity, charge separation, and the highly enhanced and stable current responses for the detection of PA and DA. The detection limit and linear range are 50.0 nmol/L and 0.3-50 µmol/L for PA, 40.0 nmol/L and 0.3-50 µmol/L for DA, respectively, which are better than those of carbon-based sensors. Moreover, this electrochemical sensor, with high selectivity, strong anti-interference, high reliability, and long time durability, can be used for the simultaneous detection of PA and DA in human blood serum and saliva. The high electrochemical performance of H-C/N@TiO2 is attributed to the multi-functional combination of different layers, because of good conductivity, absorption and electrons transfer ability from in-situ N-doped carbon and electrocatalytic activity from TiO2.

A dual-confinement strategy to construct cobalt-based phosphide nanoclusters within carbon nanofibers for bifunctional water splitting electrocatalysts.

It is a challenging task to explore highly active and stable noble-metal-free bifunctional electrocatalysts for water splitting, both in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a new dual-confinement strategy for the fabrication of cobalt-base phosphide in the carbon nanofibers (CNFs) was proposed via electrospinning, followed by the corresponding pyrolysis. The ultrafine phosphides derived from the pore confinement of ZIF and space confinement of the polymer revealed abundant active sites and P defects. More importantly, by introducing a second metal element Ni or Cu, the electronic structure and synergistic effect were further enhanced, and the obtained bimetallic CoNiPx-CNF electrocatalyst exhibited the remarkable performance for HER and OER, featuring the low η10 values of 154 and 269 mV in 1.0 M KOH electrolyte, respectively. CoNiPx-CNFs as a catalyst for both anode and cathode showed a current density of 10 mA cm-2 at a voltage of 1.56 V, exceeding better stability, which is superior to most non-noble metal electrocatalysts reported in a previous research. The dual-confinement strategy is believed to provide an effective and simple approach for the synthesis of high-performance and cost-efficient bifunctional electrocatalysts for overall water splitting.

Benefit-Risk Assessment of Dietary Patterns by Bioavailable Metals, Gut Microbes, and Their Interaction for Human Health.

The high-carbohydrate, low-fat, low-protein (HC-LFP) and low-carbohydrate, high-fat, high-protein (LC-HFP) diets are the main dietary patterns worldwide. The influence of dietary patterns on bioavailable metals, gut microbes, and their interaction is still unknown. A biomimetic digestive tract with full functions is constructed to transform the diets into chyme, and the gut microbes are cultured with the corresponding chyme. The diet species-specificity in bioavailable metal content and the positive and negative correlations between bioavailable metals and microbial reproductions are disclosed. The safe dosage and maximum consumption are 369.5 and 858.6 g/d and 268.6 and 3119.0 g/d for LC-HFP and HC-LFP, respectively. When replacing HC-LFP with LC-HFP for 21 days, the bioavailability of Fe and Cr is increased 83.2% and 268.4%, respectively; the reproductions of harmful and benefical microbes are significantly increased and decreased. The prevalences of obesity, inflammation, septicemia, and cancer are increased, and then the risk of dietary pattern shift is disclosed.

Long-term stable, high accuracy, and visual detection platform for In-field analysis of nitrite in food based on colorimetric test paper and deep convolutional neural networks.

Nitrite is one of the most common carcinogens in daily food. Its simple, rapid, inexpensive, and in-field measurement is important for food safety, based on the requirements of the standard from Codex Alimentarius Commission and China. Using polyacrylonitrile (PAN) and thin layer silica gel (SG), p-aminophenylcyclic acid (SA) and naphthalene ethylenediamine hydrochloride (NEH), as carriers and chromogenic agents, respectively, PAN-NSS as nitrite color sensor is proposed. After fixing and protecting of SA and NEH with layer-upon-layer PAN, the validity period of the test paper can be prolonged from 7 days to more than 30 days. The reproducibility of PAN-NSS preparation is ensured by electrospinning. Combined with PAN-NSS, deep convolutional neural network (DCNN) and APP as a visual monitoring platform, which has the functions of rapid sampling, data processing and transmission, intuitive feedback, etc., and provides a fully integrated detection system for field detection.

Low-toxic, fluorescent labeled and size-controlled graphene oxide quantum dots@polystyrene nanospheres as reference material for quantitative determination and in vivo tracing.

Polystyrene (PS) is selected as a representative nanoplastic and persistent pollutant for its difficult degradation and wide application. The environmental risk assessment of PS is obstructed by the toxic dye-based fluorescent PS, which false positives could be induced by the leakage of dye. For high biocompatibility, low toxicity, hydrophilicity, good water dispersibility, strong fluorescent stability, graphene oxide quantum dots (o-CQDs) are selected and embedded into PS microspheres, i.e., o-CQDs@PS, by microemulsion polymerization and denoted as CPS. Meanwhile, the sizes of CPS, e.g., 100, 150, and 200 nm, could be controlled by optimizing the type and number of water-soluble initiators. The anti-interference, low toxicity, and in vivo fluorescent tracing of CPS are proven by the coexistence of metals (including Fe2+, Fe3+, K+, Ba2+, Al3+, Zn2+, Mg2+, Ca2+, and Na+) on the fluorescence intensity of CPS, the growth of Chlorella pyrenoidosa and Artemia cysts as aquatic phytoplankton and zooplankton cultured with CPS, and the transfer of CPS from water into brine shrimp. In the concentration range of 0.1-100 mg/L, CPS can be quantitatively determined, which is suitable for coastal water and wastewater treatment plants. Therefore, CPS with standard size is suitable as reference material of PS.

Benefit-risk assessment of metal bioavailability in edible fungi by biomimetic whole digestive tracts with digestion, metabolism, and absorption functions.

As worldwide edible fungi, Lentinula edodes and Agaricus bisporus accumulate both essential and harmful metals. Metal bioavailability is important for metal benefit-risk assessment. A full functional model of digestive tracts (including digestion, metabolism, and absorption) is established. Under the digestive tract functions, the bioaccessible and bioavailable metals are released from edible fungi and absorbed by intestinal tract, respectively. Based on bioavailable metal contents in the intestine, safe dosage and maximum consumption are 43.52 g/d and 248.7 g/d for Agaricus bisporu, 20.59/328.9 g/d (for males/ female) and 132.9 g/d for Lentinus edodes; V, Co, Ni, Cu, Zn, Se, Cr, Cd and Pb in Agaricus bisporus and Lentinula edodes are absorbed mainly in the large intestine; Fe is mainly absorbed in small intestine; edible fungi species-specificity in metal bioavailability is observed for As and Mn, which are mainly absorbed by small and large intestine for Agaricus bisporus and Lentinus edodes, respectively; and then metal toxicity on small and large intestine is disclosed. Metal benefit-risk is assessed by the content of monolayer liposome-extracted metal in the chyme from small and large intestine, which is controlled by the gastrointestinal functions, metal and edible fungi species.

Speciation analysis, bioavailability and risk assessment of trace metals in herbal decoctions using a combined technique of in Vitro digestion and biomembrane filtration as sample pretreatment method.

Sample preparation is the first crucial step in the speciation analysis, bioavailability and risk assessment of trace metals in plant samples such as herb and vegetables. Two bionic technologies titled 'in vitro digestion' and 'extraction with biomembrane' were developed for pre-treatment of herbal decoction. The decoctions of Aconiteum carmichaeli and Paeonia lactiflora were digested at body temperature, at the acidity of the stomach or intestine and with inorganic and organic materials (digestive enzymes were included for whole-bionic and excluded for semi-bionic) found in the stomach or intestine. Being similar to the biomembrane between the gastrointestinal tract and blood vessels, monolayer liposome was used as a biomembrane model. Affinity-monolayer liposome metals and water-soluble metals were used for speciation analysis and bioavailability assessment of copper and zinc in herbal decoction. In the decoction of Aconiteum carmichaeli and Paeonia lactiflora, Zn was mainly absorbed in the intestine and Cu was mainly absorbed by both stomach and intestine. The safe dosage for males and females is below 257.1 g/day Aconiteum carmichaeli and 529.4 g/day Paeonia lactiflora.

Hybrid multi-objective control allocation strategy for compound high-speed rotorcraft.

To address the problem of control surface redundancy for compound high-speed rotorcraft in multi-mode conversion process, a hybrid multi-objective control allocation strategy based on adaptive particle swarm optimization (PSO) algorithm is proposed. First, the control allocation problem is converted to a hybrid multi-objective optimization problem to solve the control redundancy, and a hybrid multi-objective optimization performance function is designed to satisfy the multiple requirements of flight mission. Second, a preference matrix is designed to determine the weight coefficients of the optimization performance function. The preference matrix can simplify the complexity of hybrid multi-objective optimization problem. Finally, an adaptive PSO algorithm is designed to solve the hybrid multi-objective control allocation dynamically. The simulation verifies the feasibility and effectiveness of the control allocation strategy, which eliminates the need of extra controllers in the mode conversion, reduces the difficulty of flight control system design and improves the system security.

Complete chloroplast genome sequence of Gigantochloa verticillata (Bambusodae).

Gigantochloa verticillata is produced in Mengla and Jinghong, Yunnan Province, China, and cultivated in Hong Kong. Vietnam, Thailand, India, Indonesia, and Malaysia are distributed and cultivated. We determined the complete chloroplast genome sequence for G. verticillata using Illumina sequencing data. The complete chloroplast sequence is 139,489 bp, including large single-copy (LSC) region of 83,062 bp, small single-copy (SSC) region of 12,877 bp, and a pair of invert repeats (IR) regions of 21,775 bp. Plastid genome contain 132 genes, 85 protein-coding genes, 39 tRNA genes, and 8 rRNA genes. Phylogenetic analysis based on 23 chloroplast genomes indicates that G. verticillata is closely related to Dendrocalamus latiflorus in Bambusodae.

Prognostic significance of elevated preoperative neutrophil-to-lymphocyte ratio for patients with colorectal cancer undergoing curative surgery: A meta-analysis.

BACKGROUND: Preoperative neutrophil-to-lymphocyte ratio (NLR) has been suggested as a useful predictive factor for prognosis in patients with various cancers. However, the prognostic value of NLR in patients with colorectal cancer (CRC) remains controversial. Therefore, the goal of this study was to perform a meta-analysis to evaluate the prognostic value of NLR in patients with CRC undergoing curative surgery. METHODS: PubMed, EMBASE and Cochrane Library databases were searched to screen the relevant studies. Pooled hazard ratio (HR) with 95% confidence interval (CI) was used to assess the associations of preoperative NLR and overall survival (OS), disease-free survival (DFS), recurrence free survival (RFS) and disease specific survival (DSS) by STATA 13.0 software. RESULTS: Sixteen studies involving 5897 patients were included in our meta-analysis. Our pooled results demonstrated that high NLR was associated with poor OS (HR: 1.66, 95%CI: 1.36-2.02, P < .001), DFS (HR = 1.54, 95%CI: 1.18-2.02, P = .002), RFS (HR = 2.31, 95%CI: 1.68-3.17, P < .001) and DSS (HR = 2.27; 95% CI: 1.75-2.96, P < .001). When the patients were stratified according to country, sample size, NLR cut-off, follow up and postoperative chemotherapy, high NLR was still significantly correlated with OS. The limitation was that the majority of enrolled studies were retrospective. CONCLUSION: Preoperative NLR may be an effective predictive biomarker for prognosis in patients with CRC. Detection of NLR may be beneficial to identify the high-risk patients who need other antitumor therapies in addition to surgery.