Oxygen Vacancy Engineering of FeOx toward Oxygen-Tolerant Hydrogen Peroxide Reduction for Reliable Bioassays.

The accurate determination of hydrogen peroxide (H2O2), an important clinical disease relevant biomarker, is of great importance for the diagnosis and management of illnesses. By using the cathodic monitoring approach, H2O2 can be accurately detected because interfering signals from easily oxidizable endogenous and exogenous species in biofluids can be avoided. However, the simultaneous occurrence of the oxygen reduction reaction (ORR) restricts the practical use of this cathodic method. In this study, via oxygen vacancy modulation, we synthesized FeOx catalysts that can selectively reduce H2O2 over O2. The H2O2 detection system based on this catalyst exhibits an outstanding ORR inhibition ability. Furthermore, by integrating this catalyst with glucose oxidase, a model enzyme, a reliable bioassay system was developed that can selectively detect glucose over a wide variety of interferents in artificially simulated tissue fluids. The bioassay system employing this catalyst in conjunction with oxidases is generally applicable to accurate detect a wide range of biomarkers.

Hydrophobicity Promoted Efficient Hydroxyl Radical Generation in Visible-Light-Driven Photocatalytic Oxidation.

Hydroxyl radical (• OH) with strong oxidation capability is one of the most important reactive oxygen species. The generation of • OH from superoxide radicals (• O2 - ) is an important process in visible-light-driven photocatalysis, but the conversion generally suffers from slow reaction kinetics. Here, a hydrophobicity promoted efficient • OH generation in a visible-light-driven semiconductor-mediated photodegradation reaction is reported. Hydrophobic TiO2 that is synthesized by modifying the TiO2 surface with a thin polydimethylsiloxane (PDMS) layer and rhodamine B (RhB) are used as model semiconductors and dye molecules, respectively. The surface hydrophobicity resulted in the formation of a solid-liquid-air triphase interface microenvironment, which increased the local concentration of O2 . In the meanwhile, the saturated adsorption quantity of RhB on hydrophobic TiO2 is improved by five-fold than that on untreated TiO2 . These advantages increased the density of the conduction band photoelectrons and • O2 - generation, and stimulated the conversion of • O2 - to • OH. This consequently not only increased the kinetics of the photocatalytic reaction by an order of magnitude, but also altered the oxidation route from conventional decolorization to mineralization. This study highlights the importance of surface wettability modulation in boosting • OH generation in visible-light-driven photocatalysis.

Differential Gene Expression and Immune Cell Infiltration in Patients with Steroid-induced Necrosis of the Femoral Head.

OBJECTIVE: The study aimed to study the differential gene expression and immune cell infiltration in patients with steroid-induced necrosis of the femoral head (SANFH), identify the key genes and immune cells of SANFH, and explore the relationship between immune cells and SANFH. METHODS: The high-throughput gene chip dataset GSE123568 was downloaded from the GEO database, and the differential gene expression was analyzed with the R language. The STRING database and Cytoscape software were used to analyze the protein interaction network and screen key genes, and enrichment analysis was carried out on key genes. The infiltration of immune cells in SANFH patients was analyzed and verified by immunohistochemistry. RESULTS: EP300, TRAF6, STAT1, JAK1, CASP8, and JAK2 are key genes in the pathogenesis of SANFH, which mainly involve myeloid cell differentiation, cytokine-mediated signaling pathway, tumor necrosis factor-mediated signaling pathway, and cellular response to tumor necrosis factor through JAK-STAT, NOD-like receptor, toll-like receptor, and other signaling pathways, leading to the occurrence of diseases; immune infiltration and immunohistochemical results have shown the expression of memory B cells and activated dendritic cells as reduced in SANFH patients, while in the same SANFH samples, M1 macrophages have been positively correlated with monocytes, and neutrophils have been negatively correlated with monocytes expression. CONCLUSION: EP300, TRAF6, STAT1, JAK1, CASP8, and JAK2 have exhibited significant differences in SANFH (spontaneous osteonecrosis of the femoral head). Memory B cells, activated dendritic cells, M1 macrophages, monocytes, and neutrophils have shown abnormal expression in SANFH.

Potential-Resolved Electrochemiluminescence Multiplex Immunoassay for Florfenicol and Chloramphenicol in a Single Sample.

The simultaneous detection of multiple antibiotic residues in food is of great significance for food safety. In this work, a novel dual-potential electrochemiluminescence (ECL) immunoassay was designed for the simultaneous detection of chloramphenicol and fluorfenicol residues in food. Ru@MOF was used as an anodic probe, and SnS2 QDs-PEI-Au-MoS2 was used as a cathodic probe. Notably, the coreactant for both luminophores was K2S2O8, avoiding interactions caused by different kinds of coreactants. Au nanoparticles functionalized with a nitrogen- and sulfur-doped graphene oxide-modified glassy carbon electrode to improve the electron transfer efficiency and provide a larger surface area for immobilization of antigen. The linear range for the detection of florfenicol was determined to be 0.1-1000 ng mL-1 with a detection limit of 0.03 ng mL-1, and the linear range for the detection of chloramphenicol was 0.01-1000 ng mL-1 with a detection limit of 3.2 pg mL-1 by recording the ECL responses at two different excitation potentials. The proposed immunoassay achieved a more stable recovery in the detection of actual samples and provided a new analytical method for the simultaneous detection of florfenicol and chloramphenicol residues with high sensitivity and specificity.

Durability of Plant Fiber Composites for Structural Application: A Brief Review.

Environmental sustainability and eco-efficiency stand as imperative benchmarks for the upcoming era of materials. The use of sustainable plant fiber composites (PFCs) in structural components has garnered significant interest within industrial community. The durability of PFCs is an important consideration and needs to be well understood before their widespread application. Moisture/water aging, creep properties, and fatigue properties are the most critical aspects of the durability of PFCs. Currently, proposed approaches, such as fiber surface treatments, can alleviate the impact of water uptake on the mechanical properties of PFCs, but complete elimination seems impossible, thus limiting the application of PFCs in moist environments. Creep in PFCs has not received as much attention as water/moisture aging. Existing research has already found the significant creep deformation of PFCs due to the unique microstructure of plant fibers, and fortunately, strengthening fiber-matrix bonding has been reported to effectively improve creep resistance, although data remain limited. Regarding fatigue research in PFCs, most research focuses on tension-tension fatigue properties, but more attention is required on compression-related fatigue properties. PFCs have demonstrated a high endurance of one million cycles under a tension-tension fatigue load at 40% of their ultimate tensile strength (UTS), regardless of plant fiber type and textile architecture. These findings bolster confidence in the use of PFCs for structural applications, provided special measures are taken to alleviate creep and water absorption. This article outlines the current state of the research on the durability of PFCs in terms of the three critical factors mentioned above, and also discusses the associated improvement methods, with the hope that it can provide readers with a comprehensive overview of PFCs' durability and highlight areas worthy of further research.

Engineering a Hollow Carbon Sphere-Based Triphase Microenvironment for Enhanced Enzymatic Reaction Kinetics and Bioassay Performance.

Electrochemical bioassays based on oxidase reactions are frequently used in biological sciences and medical industries. However, the enzymatic reaction kinetics are severely restricted by the poor solubility and slow diffusion rate of oxygen in conventional solid-liquid diphase reaction systems, which inevitably compromises the detection accuracy, linearity, and reliability of the oxidase-based bioassay. Herein, an effective solid-liquid-air triphase bioassay system is provided that uses hydrophobic hollow carbon spheres (HCSs) as oxygen nanocarriers. The oxygen stored in the cavity of HCS can rapidly diffuse to the oxidase active sites through the mesoporous carbon shell, providing sufficient oxygen for oxidase-based enzymatic reactions. As a result, the triphase system can significantly improve the enzymatic reaction kinetics and obtain a 20-fold higher linear detection range than the normal diphase system. Other biomolecules can also be determined using this triphase technique, and the triphase design strategy offers a new route to address the gas deficiency problem in catalytic reactions that involve gas consumption.

Laser-Induced Graphene Arrays-Based Three-Phase Interface Enzyme Electrode for Reliable Bioassays.

Electrochemical oxidase biosensors have been widely applied in healthcare, environmental measurements and the biomedical field. However, the low and fluctuant oxygen levels in solution and the high anodic detection potentially restrict the assay accuracy. To address these problems, in this work, we constructed a three-phase interface enzyme electrode by sequentially immobilizing H2O2 electrocatalysts and an oxidase layer on a superhydrophobic laser-induced graphene (LIG) array substrate. The LIG-based enzyme electrode possesses a solid-liquid-air three-phase interface where constant and sufficient oxygen can be supplied from the air phase to the enzymatic reaction zone, which enhances and stabilizes the oxidase kinetics. We discovered that the enzymatic reaction rate is 21.2-fold improved over that of a solid-liquid diphase system where oxygen is supplied from the liquid phase, leading to a 60-times wider linear detection range. Moreover, the three-phase enzyme electrode can employ a cathodic measuring principle for oxidase catalytic product H2O2 detection, which could minimize interferences arising from oxidizable molecules in biofluids and increase the detection selectivity. This work provides a simple and promising approach to the design and construction of high-performance bioassay systems.

High-Performance Photoelectrochemical Enzymatic Bioanalysis Based on a 3D Porous CuxO@TiO2 Film with a Solid-Liquid-Air Triphase Interface.

The accurate detection of H2O2 is crucial in oxidase-based cathodic photoelectrochemical enzymatic bioanalysis but will be easily compromised in the conventional photoelectrode-electrolyte diphase system due to the fluctuation of oxygen levels and the similar reduction potential between oxygen and H2O2. Herein, a solid-liquid-air triphase bio-photocathode based on a superhydrophobic three-dimensional (3D) porous micro-nano-hierarchical structured CuxO@TiO2 film that was constructed by controlling the wettability of the electrode surface is reported. The triphase photoelectrochemical system ensures an oxygen-rich interface microenvironment with constant and sufficiently high oxygen concentration. Moreover, the 3D porous micro-nano-hierarchical structures possess abundant active catalytic sites and a multidimensional electron transport pathway. The synergistic effect of the improved oxygen supply and the photoelectrode architecture greatly stabilizes and enhances the kinetics of the enzymatic reaction and H2O2 cathodic reaction, resulting in a 60-fold broader linear detection range and a higher accuracy compared with the conventional solid-liquid diphase system.

Predictive value of anti-Mullerian hormone for pregnancy outcomes following assisted reproductive techniques (ART) in Southwest China.

BACKGROUND: Anti-Müllerian hormone (AMH) is secreted by granulosa cells in preantral follicles and small antral follicles. There is limited information about whether serum AMH levels are related to pregnancy outcomes during in vitro fertilization and embryo transfer (IVF-ET). The aim of this study was to provide a theoretical basis for improving pregnancy outcomes. METHODS: A retrospective cohort study was conducted on infertile women who were treated at the Reproductive Centre of the Affiliated Hospital of Southwest Medical University between September 2018 and September 2019. The sample included 518 participants from Southwest China. The participants were divided into 2 groups according to their AMH level. Their data were retrieved from the medical records: days and dosage of gonadotropin (Gn) (one bottle equals 75 IU), the number of oocytes obtained, the number of oocytes in metaphase II (MII) and the number of high-quality embryos. The pregnancy outcomes were followed up and divided into two groups according to whether they were pregnant or not, with statistical analysis of the parameters related to the in vitro fertilization process performed separately. RESULTS: Compared to a lower AMH level (AMH ≤ 1.1), a higher AMH level (AMH > 1.1) resulted in less total Gn (bottle) (P = 0.00 < 0.05) and a lower starting Gn (IU) (P = 0.00 < 0.05), while the number of oocytes obtained,MII,cleavages and high-quality embryos were higher (P = 0.00 < 0.05). The participants' pregnancy outcomes (ectopic pregnancy, miscarriage, singleton, twin, multiple births) were found to not be predictable by AMH through ROC curves (P = 0.980, 0.093, 0.447, 0.146, 0.526, and 0.868 > 0.05). For participants in the pregnancy group, although AMH was lower in the nonpregnant participants(P = 0.868 > 0.05), the difference was not statistically significant, and the correlation coefficients between the two groups suggested no differences in the IVF process, except for the starting Gn (IU) (P = 0.038 < 0.05). CONCLUSION: AMH has clinical application value in predicting ovarian reserve function, providing guidance and suggestions for the specific formulation of ovulation promotion programs with assisted reproductive technology, but it cannot effectively predict the outcome of clinical pregnancy.

Three-Phases Interface Induced Local Alkalinity Generation Enables Electrocatalytic Glucose Oxidation in Neutral Electrolyte.

Electrocatalytic glucose oxidation is crucial to the development of non-enzymatic sensors, an attractive alternative for enzymatic biosensors. However, due to OH- consumption during the catalytic process, non-enzymatic detection generally requires electrolytes having an alkaline pH value, limiting its practical application since biofluids are neutral. Herein, via interfacial microenvironment design, we addressed this limitation by developing a non-enzymatic sensor with an air-solid-liquid triphase interface electrodes that synergistically integrates the functions of local alkalinity generation and electrocatalytic glucose oxidation. A sufficiently high local pH value was achieved via oxygen reduction reaction at the triphase interface, which consequently enabled the electrochemical oxidation (detection) of glucose in neutral solution. Moreover, we found that the linear detection range and sensitivity of triphase non-enzymatic sensor can be tuned by changing the electrocatalysts of the detection electrode. The triphase electrode architecture provides a new platform for further exploration and promotes practical application of non-enzymatic sensors.

Partial restoration of spinal cord neural continuity via vascular pedicle hemisected spinal cord transplantation using spinal cord fusion technique.

AIMS: Our team tested spinal cord fusion (SCF) using the neuroprotective agent polyethylene glycol (PEG) in different animal (mice, rats, and beagles) models with complete spinal cord transection. To further explore the application of SCF for the treatment of paraplegic patients, we developed a new clinical procedure for SCF called vascular pedicle hemisected spinal cord transplantation (vSCT) and tested this procedure in eight paraplegic participants. METHODS: Eight paraplegic participants (American Spinal Injury Association, ASIA: A) were enrolled and treated with vSCT (PEG was applied to the sites of spinal cord transplantation). Pre- and postoperative pain intensities, neurologic assessments, electrophysiologic monitoring, and neuroimaging examinations were recorded. RESULTS: Of the eight paraplegic participants who completed vSCT, objective improvements occurred in motor function for one participant, in electrophysiologic motor-evoked potentials for another participant, in re-establishment of white matter continuity in three participants, in autonomic nerve function in seven participants, and in symptoms of cord central pain for seven participants. CONCLUSIONS: The postoperative recovery of paraplegic participants demonstrated the clinical feasibility and efficacy of vSCT in re-establishing the continuity of spinal nerve fibers. vSCT could provide the anatomic, morphologic, and histologic foundations to potentially restore the motor, sensory, and autonomic nervous functions in paraplegic patients. More future clinical trials are warranted.

Partial Restoration of Spinal Cord Neural Continuity via Sural Nerve Transplantation Using a Technique of Spinal Cord Fusion.

BACKGROUND: Spinal cord injury (SCI) can cause paralysis and serious chronic morbidity, and there is no effective treatment. Based on our previous experimental results of spinal cord fusion (SCF) in mice, rats, beagles, and monkeys, we developed a surgical protocol of SCF for paraplegic human patients. We designed a novel surgical procedure of SCF, called sural nerve transplantation (SNT), for human patients with lower thoracic SCI and distal cord dysfunction. METHODS: We conducted a clinical trial (ChiCTR2000030788) and performed SNT in 12 fully paraplegic patients due to SCI between T1 and T12. We assessed pre- and postoperative central nerve pain, motor function, sensory function, and autonomic nerve function. Conduction of action potentials across the sural nerve transplant was evaluated. Neural continuity was also examined by diffusion tensor imaging (DTI). RESULTS: Among the 12 paraplegic patients enrolled in this clinical trial, seven patients demonstrated improved autonomic nerve functions. Seven patients had clinically significant relief of their symptoms of cord central pain. One patient, however, developed postoperative cord central pain (VAS: 4). Five patients had varying degrees of recovered sensory and/or motor functions below the single neurologic level 1 month after surgery. One patient showed recovery of electrophysiologic, motor-evoked potentials 6 months after the operation. At 6 months after surgery, DTI indicated fusion and nerve connections of white cord and sural nerves in seven patients. CONCLUSION: SNT was able to fuse the axonal stumps of white cord and sural nerve and at least partially improve the cord central pain in most patients. Although SNT did not restore the spinal cord continuity in white matter in some patients, SNT could restore spinal cord continuity in the cortico-trunco-reticulo-propriospinal pathway, thereby restoring in part some motor and sensory functions. SNT may therefore be a safe, feasible, and effective method to treat paraplegic patients with SCI. Future clinical trials should be performed to optimize the type/technique of nerve transplantation, reduce surgical damage, and minimize postoperative scar formation and adhesion, to avoid postoperative cord central pain. CLINICAL TRIAL REGISTRATION: [http://www.chictr.org.cn/showproj.aspx?proj=50526], identifier [ChiCTR2000030788].

Flexible triphase enzyme electrode based on hydrophobic porous PVDF membrane for high-performance bioassays.

Flexible bioassays based on oxidase-catalyzed and electrocatalytic cascade reactions have been widely reported. However, the fluctuant oxygen level and high anodic potential restricts the detection accuracy. To overcome these challenges, we report here a flexible triphase enzyme electrode by assembling an oxidase enzyme layer and Pt electrocatalysts onto a carbon nanotube film/porous polyvinylidene fluoride hydrophobic substrate. Such a flexible enzyme electrode has an air-liquid-solid triphase reaction zone where oxygen level is air phase dependent (constant and sufficient high), which stabilized the oxidase kinetics and enabled the cathodic measurement of enzymatic product H2O2 with minimum interferents caused from oxygen level fluctuation and many oxidizable species in analyte solution. Furthermore, the flexible triphase enzyme electrode exhibited good mechanical stability even after being bent over 600 times and an excellent air permeability, which are crucial to wearable devices that require long-term skin contact.

Decoupling hydrogen production from water oxidation by integrating a triphase interfacial bioelectrochemical cascade reaction.

Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel. However, the sluggish-kinetics and low value-added anodic oxygen evolution reaction (OER) restricts the overall energy conversion efficiency. Herein we report a strategy of boosting H2 production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode. In the presence of oxygen, oxidase enzymes can convert biomass into valuable products, and concurrently generate H2O2 that can be further electrooxidized at the bioanode. Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H2O2 oxidation than that of OER, the cell voltage and energy consumption are reduced by ~0.70 V and ~36%, respectively, relative to regular water electrolysis. This leads to an efficient H2 production at the cathode and valuable product generation at the bioanode. Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.

Antinociceptive Effects of Shenling Baizhu through PI3K-Akt-mTOR Signaling Pathway in a Mouse Model of Bone Metastasis with Small-Cell Lung Cancer.

Shenling Baizhu additive powder (SLBZ-AP), a formulation of a variety of natural medicinal plants, has clinical efficacy in treating cancers in previous studies. We explored the effect of SLBZ-AP in bone metastasis of lung cancer (BMLC) mice, and the possible mechanism involved was further investigated in the present study. Mice model of BMLC was made and treated with SLBZ-AP. Pain behavioral tests were performed to explore the effect on BMLC-induced pain in mice. TUNEL staining was used to investigate apoptosis. The mRNA expression of markers in the PI3K/Akt/mTOR pathway was measured by qPCR, and protein expression was detected by western blotting and immunohistochemistry analysis. SLBZ-AP relieved BMLC-induced pain and prolonged animals' survival, promoted cell apoptosis in the marrow from the tibia of BMLC mice, and inhibited mRNA and protein expression of AKT, mTOR, P70S6, and VEGF, as well as protein expression of p-AKT, p-mTOR, p-P70S6, and VEGF upregulation in the marrow of tibia induced by BMLC, an effect which was similar to rapamycin. Our results suggested that SLBZ-AP may have antinociceptive effect and prolong survival of BMLC mice at least partially by inhibiting cell proliferation and promoting apoptosis through the PI3K/Akt/mTOR signaling pathway. SLBZ-AP may be a potential candidate for BMLC therapy.

Increasing the Efficiency of Photocatalytic Reactions via Surface Microenvironment Engineering.

The use of photocatalysis for water purification and environmental protection is of key interest. However, the reaction kinetics can be limited by the restricted accessibility of electron acceptor oxygen and the low adsorption of organic compounds-crucial factors underlying photocatalytic performance. Here we simultaneously alleviate these constraints via reaction interface microenvironment design using superhydrophobic (SHB) TiO2 nanoarrays as a model photocatalyst. The low surface energy and rough surface microstructure features of the SHB nanoarrays give the photocatalytic system long-range hydrophobic force and an air-water-solid triphase reaction interface. This simultaneously changes the adsorption model of organic compounds and the access pathway of oxygen, leading to a markedly enhanced adsorption capacity and higher interfacial oxygen levels. These synergistic qualities result in over 30-fold higher reaction kinetics versus a normal diphase system. In addition, this photocatalytic system is stable via repeated cycling. Our findings highlight the importance of reaction interface microenvironment design and reveal an effective path for the development of efficient photocatalysis systems.

Enhanced catalytic reaction at an air-liquid-solid triphase interface.

Gaseous reactant involved heterogeneous catalysis is critical to the development of clean energy, environmental management, health monitoring, and chemical synthesis. However, in traditional heterogeneous catalysis with liquid-solid diphase reaction interfaces, the low solubility and slow transport of gaseous reactants strongly restrict the reaction efficiency. In this minireview, we summarize recent advances in tackling these drawbacks by designing catalytic systems with an air-liquid-solid triphase joint interface. At the triphase interface, abundant gaseous reactants can directly transport from the air phase to the reaction centre to overcome the limitations of low solubility and slow transport of the dissolved gas in liquid-solid diphase reaction systems. By constructing a triphase interface, the efficiency and/or selectivity of photocatalytic reactions, enzymatic reactions, and (photo)electrochemical reactions with consumption of gaseous reactants oxygen, carbon dioxide, and nitrogen are significantly improved.

Green Approach for Metal Oxide Deposition at an Air-Liquid-Solid Triphase Interface with Enhanced Photocatalytic Activity.

Bioinspired superhydrophobic substrates have been used in many scientific and technological areas. These substrates can trap atmosphere-linked air pockets at the solid-liquid interface, offering an opportunity to address the oxygen-deficit problem in many reaction systems. Herein, we addressed the oxygen-deficit problem in metal oxide electrochemical deposition by using a triphase electrode possessing an air-liquid-solid joint interface. Oxygen in the interface is directly available from the air phase for sufficient OH- production via oxygen cathodic reaction, thereby offering us a green approach to fabricate two-dimensional mesoporous ZnO nanoarrays over a wide range of current densities. Further, because metal oxides are deposited at the triphase interface, sufficient O2, a natural electron scavenger required in photocatalytic reaction to suppress the recombination of photogenerated electron-hole pairs, can be directly supplied, and we demonstrated their enhanced photocatalytic reaction kinetics in water remediation. The present work highlights a powerful interface-engineering strategy for fabricating metal oxides with unprecedented photocatalytic ability.

Oxygen-Tolerant Hydrogen Peroxide Reduction Catalysts for Reliable Noninvasive Bioassays.

Noninvasive bioassays based on the principle of a hydrogen peroxide (H2 O2 ) cathodic reaction are highly desirable for low concentration analyte detection within biofluids since the reaction is immune to interference from oxidizable species. However, the inability to selectively reduce H2 O2 over O2 for commonly used stable catalysts (carbon or noble metals) is one of the key factors limiting their development and practical applications. Herein, catalysts that enable selective H2 O2 reduction in the presence of oxygen with fluctuating concentrations are reported. These catalysts consist of noble metal nanoparticles underneath an amorphous chromium oxide nanolayer, which inhibits O2 diffusion to the metal/oxide interface and suppresses its reduction reaction. Using these catalysts, analytes of low concentration in biofluids, including but not limited to glucose and lactate, are detected within the presence of various interferents. This work enables wide application of the cathodic detection principle and the development of reliable noninvasive bioassays.