Electrosynthesis of Transition Metal Coordinated Polymers for Active and Stable Oxygen Evolution.

Transition metal coordination polymers (TM-CP) are promising inexpensive and flexible electrocatalysts for oxygen evolution reaction in water electrolysis, while their facile synthesis and controllable regulation remain challenging. Here we report an anodic oxidation-electrodeposition strategy for the growth of TM-CP (TM = Fe, Co, Ni, Cr, Mn; CP = polyaniline, polypyrrole) films on a variety of metal substrates that act as both catalyst supports and metal ion sources. An exemplified bimetallic NiFe-polypyrrole (NiFe-PPy) features superior mechanical stability in friction and exhibits high activity with long-term durability in alkaline seawater (over 2000 h) and anion exchange membrane electrolyzer devices at current density of 500 mA cm-2. Spectroscopic and microscopic analysis unravels the configurations with atomically distributed metal sites induced by d-π conjugation, which transforms into a mosaic structure with NiFe (oxy)hydroxides embedded in PPy matrix during oxygen evolution. The superior catalytic performance is ascribed to the anchoring effect of PPy that inhibits the metal dissolution, the strong substrate-to-catalyst interaction that ensures good adhesion, and the Fe/Ni-N coordination that modulates the electronic structures to facilitate the deprotonation of *OOH intermediate. This work provides a general strategy and mechanistic insight into building robust inorganic/polymer composite electrodes for oxygen electrocatalysis.

Sequentially Regulating Potential-Determining Step for Lowering CO2 Electroreduction Overpotential over Te-Doped Bi Nanotips.

Electrocatalytic conversion of CO2 into formate is recognized an economically-viable route to upgrade CO2, but requires high overpotential to realize the high selectivity owing to high energy barrier for driving the involved proton-coupled electron transfer (PCET) processes and serious ignorance of the second PCET. Herein, we surmount the challenge through sequential regulation of the potential-determining step (PDS) over Te-doped Bi (TeBi) nanotips. Computational studies unravel the incorporation of Te heteroatoms alters the PDS from the first PCET to the second one by substantially lowering the formation barrier for *OCHO intermediate, and the high-curvature nanotips induce enhanced electric field that can steer the formation of asymmetric *HCOOH. In this scenario, the thermodynamic barrier for *OCHO and *HCOOH can be sequentially decreased, thus enabling a high formate selectivity at low overpotential. Experimentally, distinct TeBi nanostructures are obtained via controlling Te content in the precursor and TeBi nanotips achieve >90% of Faradaic efficiency for formate production over a comparatively positive potential window (-0.57 V to -1.08 V). The strong Bi-Te covalent bonds also afford a robust stability. In an optimized membrane electrode assembly device, the formate production rate at 3.2 V reaches 10.1 mmol h-1 cm-2, demonstrating great potential for practical application.

The improvement of pain symptoms in patients with burning mouth syndrome through combined laser and medication therapy.

BACKGROUND: The etiology of Burning Mouth Syndrome (BMS) remains unclear. OBJECTIVE: To explore the differences in the therapeutic efficacy of pain improvement between medication therapy and laser therapy in patients with BMS. METHODS: 45 BMS patients were randomly divided into three groups: The Combination therapy group (Group A, n= 15), The Medication therapy group (Group B, n= 15), and the Laser therapy group (Group C, n= 15). The pain condition of the patients was evaluated using the Numeric Rating Scale (NRS), and the improvement in pain before and after treatment was compared among the three groups. RESULTS: All three groups (A, B, and C) showed a significant reduction in NRS scores after treatment, with statistically significant differences observed among the different groups. Group A exhibited the most significant improvement, with a statistically significant difference before and after treatment. CONCLUSION: Laser and medication therapy are effective methods for reducing oral burning pain * symptoms, and their combined use yields more significant therapeutic effects.

The improvement of pain symptoms in patients with burning mouth syndrome through combined laser and medication therapy.

BACKGROUND: The etiology of Burning Mouth Syndrome (BMS) remains unclear. OBJECTIVE: To explore the differences in the therapeutic efficacy of pain improvement between medication therapy and laser therapy in patients with BMS. METHODS: 45 BMS patients were randomly divided into three groups: The Combination therapy group (Group A, n= 15), The Medication therapy group (Group B, n= 15), and the Laser therapy group (Group C, n= 15). The pain condition of the patients was evaluated using the Numeric Rating Scale (NRS), and the improvement in pain before and after treatment was compared among the three groups. RESULTS: All three groups (A, B, and C) showed a significant reduction in NRS scores after treatment, with statistically significant differences observed among the different groups. Group A exhibited the most significant improvement, with a statistically significant difference before and after treatment. CONCLUSION: Laser and medication therapy are effective methods for reducing oral burning pain * symptoms, and their combined use yields more significant therapeutic effects.

Integrated metabolomic and transcriptomic dynamic profiles of endopleura coloration during fruit maturation in three walnut cultivars.

BACKGROUND: The color of endopleura is a vital factor in determining the economic value and aesthetics appeal of nut. Walnuts (Juglans) are a key source of edible nuts, high in proteins, amino acids, lipids, carbohydrates. Walnut had a variety endopleura color as yellow, red, and purple. However, the regulation of walnut endopleura color remains little known. RESULTS: To understand the process of coloration in endopleura, we performed the integrative analysis of transcriptomes and metabolomes at two developmental stages of walnut endopleura. We obtained total of 4,950 differentially expressed genes (DEGs) and 794 metabolites from walnut endopleura, which are involved in flavonoid and phenolic biosynthesis pathways. The enrichment analysis revealed that the cinnamic acid, coniferyl alcohol, naringenin, and naringenin-7-O-glucoside were important metabolites in the development process of walnut endopleura. Transcriptome and metabolome analyses revealed that the DEGs and differentially regulated metabolites (DRMs) were significantly enriched in flavonoid biosynthesis and phenolic metabolic pathways. Through co-expression analysis, CHS (chalcone synthase), CHI (chalcone isomerase), CCR (cinnamoyl CoA reductase), CAD (cinnamyl alcohol dehydrogenase), COMT (catechol-Omethyl transferase), and 4CL (4-coumaroyl: CoA-ligase) may be the key genes that potentially regulate walnut endopleura color in flavonoid biosynthesis and phenolic metabolic pathways. CONCLUSIONS: This study illuminates the metabolic pathways and candidate genes that underlie the endopleura coloration in walnuts, lay the foundation for further study and provides insights into controlling nut's colour.

Favoring CO Intermediate Stabilization and Protonation by Crown Ether for CO2 Electromethanation in Acidic Media.

The large-scale deployment of CO2 electroreduction is hampered by deficient carbon utilization in neutral and alkaline electrolytes due to CO2 loss into (bi)carbonates. Switching to acidic media mitigates carbonation, but suffers from low product selectivity because of hydrogen evolution. Here we report a crown ether decoration strategy on a Cu catalyst to enhance carbon utilization and selectivity of CO2 methanation under acidic conditions. Macrocyclic 18-Crown-6 is found to enrich potassium cations near the Cu electrode surface, simultaneously enhancing the interfacial electric field to stabilize the *CO intermediate and accelerate water dissociation to boost *CO protonation. Remarkably, the mixture of 18-Crown-6 and Cu nanoparticles affords a CH4 Faradaic efficiency of 51.2 % and a single pass carbon efficiency of 43.0 % toward CO2 electroreduction in electrolyte with pH=2. This study provides a facile strategy to promote CH4 selectivity and carbon utilization by modifying Cu catalysts with supramolecules.

Hollow Hierarchical Cu2 O-Derived Electrocatalysts Steering CO2 Reduction to Multi-Carbon Chemicals at Low Overpotentials.

The electrochemical reduction of carbon dioxide into multi-carbon products (C2+ ) using renewably generated electricity provides a promising pathway for energy and environmental sustainability. Various oxide-derived copper (OD-Cu) catalysts have been showcased, but still require high overpotential to drive C2+ production owing to sluggish carbon-carbon bond formation and low CO intermediate (*CO) coverage. Here, the dilemma is circumvented by elaborately devising the OD-Cu morphology. First, computational studies propose a hollow and hierarchical OD-Cu microstructure that can generate a core-shell microenvironment to inhibit CO evolution and accelerate *CO dimerization via intermediate confinement and electric field enhancement, thereby boosting C2+ generation. Experimentally, the designed nanoarchitectures are synthesized through a heteroseed-induced approach followed by electrochemical activation. In situ spectroscopic studies further elaborate correlation between *CO dimerization and designed architectures. Remarkably, the hierarchical OD-Cu manifests morphology-dependent selectivity of CO2 reduction, giving a C2+ Faradaic efficiency of 75.6% at a considerably positive potential of -0.55 V versus reversible hydrogen electrode.

Boosting the Kinetics and Stability of Zn Anodes in Aqueous Electrolytes with Supramolecular Cyclodextrin Additives.

The hydrophobic internal cavity and hydrophilic external surface of cyclodextrins (CDs) render promising electrochemical applications. Here, we report a comparative and mechanistic study on the use of CD molecules (α-, ß-, and γ-CD) as electrolyte additives for rechargeable Zn batteries. The addition of α-CD in aqueous ZnSO4 solution reduces nucleation overpotential and activation energy of Zn plating and suppresses H2 generation. Computational, spectroscopic, and electrochemical studies reveal that α-CD preferentially adsorbs in parallel on the Zn surface via secondary hydroxyl groups, suppressing water-induced side reactions of hydrogen evolution and hydroxide sulfate formation. Additionally, the hydrophilic exterior surface of α-CD with intense electron density simultaneously facilitates Zn2+ deposition and alleviates Zn dendrite formation. A formulated 3 M ZnSO4 + 10 mM α-CD electrolyte enables homogenous Zn plating/stripping (average Coulombic efficiency ∼ 99.90%) at 1 mA cm-2 in Zn|Cu cells and a considerable capacity retention of 84.20% after 800 cycles in Zn|V2O5 full batteries. This study provides insight into the use of supramolecular macrocycles to modulate and enhance the interface stability and kinetics of metallic anodes for aqueous battery chemistry.

Efficient Axillary Lymph Node Detection Via Two-stage Spatial-information-fusion-based CNN.

BACKGROUND AND OBJECTIVE: Preoperative imaging diagnosis of axillary lymph node (ALN) metastasis is particularly important for breast cancer patients. This paper focuses on developing non-invasive and automatic schemes for accurate localization and classification (metastasis prediction) of ALN via contrast-enhanced computed tomography (CECT) image and deep learning models. METHODS: Based on a two-stage strategy, a novel detection neural network is proposed, where the convolutional block attention module is utilized to extract spacial information and the bottleneck feature fusion module is designed for feature fusion in different scales. RESULTS: Owing to the two embedded modules, the proposed convolutional neural network (CNN) model outperforms Faster R-CNN, YOLOv3, and EfficientDet in the sense that the achieved mAP is 0.454, higher than 0.247, 0.335, and 0.329, respectively. In particular, considering the function of classification only, the proposed model reaches the best performance on most indices (accuracy of 0.968, positive predictive value of 0.972, negative predictive value of 0.966, specificity of 0.983), compared with the methods that have been frequently adopted to predict ALN. In addition, the proposed CNN model has the function of locating ALN, which is lacking in existing models. CONCLUSIONS: In this paper, a supervised deep learning method is proposed to detect ALN in CECT images. The positive effect of new added modules are verified, and the benefits of spatial information in ALN detection are confirmed. Further, the two subtasks called localization and classification are evaluated separately, where the proposed model achieves the best performance on most indices. The source code mentioned in this article will be released later.

Nanoporous NiSb to Enhance Nitrogen Electroreduction via Tailoring Competitive Adsorption Sites.

Ambient nitrogen reduction reaction (NRR) is attracting extensive interest but still suffers from sluggish kinetics owing to competitive rapid hydrogen evolution and difficult nitrogen activation. Herein, nanoporous NiSb alloy is reported as an efficient electrocatalyst for N2 fixation, achieving a high ammonia yield rate of 56.9 µg h-1 mg-1 with a Faradaic efficiency of 48.0%. Density functional theory calculations reveal that in NiSb alloy, Ni favors N2 hydrogenation while the neighboring Sb separates active sites for proton and N2 adsorption, which optimizes the adsorption/desorption of intermediates and enables an energetically favorable NRR pathway. This work indicates promising electrocatalytic application of the alloys of 3d and p block metals toward the NRR and provides an intriguing strategy to enhance the reduction of inert molecules by restraining the competitive hydrogen adsorption.

Optimal fermentation time for Nigrospora-fermented tea rich in bostrycin.

BACKGROUND: Bostrycin has many biological functions, such as anticancer activity, and is becoming increasingly popular. Nigrospora sphaerica HCH285, which has the ability to produce high levels of bostrycin, can be used to ferment sun-dried green tea of Camellia sinensis through acclimation, resulting in the development of a Nigrospora-fermented tea. The effects of fermentation time on the production of bostrycin by the HCH285 strain were investigated. RESULTS: After 45 days of fermentation, the bostrycin content reached 3.18 g kg-1 , which is the highest level during the whole fermentation. At 50 days, the tea liquor was red, had a strong mushroom odour and a sweet taste, and presented optimal quality. The contents of free amino acids, tea polyphenols and soluble sugars in the fermented tea decreased generally during the fermentation, although the content of water-soluble substances increased. Additionally, the results of a 14-day acute oral toxicity test showed that Nigrospora-fermented tea was nontoxic. CONCLUSION: The optimum fermentation time of Nigrospora-fermented tea was concluded to be 45-50 days. These results provide insights with respect to the development of tea biotechnology and new tea products with active ingredients. © 2020 Society of Chemical Industry.

Nanoporous Palladium Hydride for Electrocatalytic N2 Reduction under Ambient Conditions.

The electrocatalytic nitrogen reduction reaction (NRR) is an alternative eco-friendly strategy for sustainable N2 fixation with renewable energy. However, NRR suffers from sluggish kinetics owing to difficult N2 adsorption and N≡N cleavage. Now, nanoporous palladium hydride is reported as electrocatalyst for electrochemical N2 reduction under ambient conditions, achieving a high ammonia yield rate of 20.4 µg h-1 mg-1 with a Faradaic efficiency of 43.6 % at low overpotential of 150 mV. Isotopic hydrogen labeling studies suggest the involvement of lattice hydrogen atoms in the hydride as active hydrogen source. In situ Raman analysis and density functional theory (DFT) calculations further reveal the reduction of energy barrier for the rate-limiting *N2 H formation step. The unique protonation mode of palladium hydride would provide a new insight on designing efficient and robust electrocatalysts for nitrogen fixation.

Electrodeposition of Pt-Decorated Ni(OH)2/CeO2 Hybrid as Superior Bifunctional Electrocatalyst for Water Splitting.

The facile synthesis of highly active and stable bifunctional electrocatalysts to catalyze water splitting is attractive but challenging. Herein, we report the electrodeposition of Pt-decorated Ni(OH)2/CeO2 (PNC) hybrid as an efficient and robust bifunctional electrocatalyst. The graphite-supported PNC catalyst delivers superior hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activities over the benchmark Pt/C and RuO2, respectively. For overall water electrolysis, the PNC hybrid only requires a cell voltage of 1.45 V at 10 mA cm-2 and sustains over 85 h at 1000 mA cm-2. The remarkable HER/OER performances are attributed to the superhydrophilicity and multiple effects of PNC, in which Ni(OH)2 and CeO2 accelerate HER on Pt due to promoted water dissociation and strong electronic interaction, while the electron-pulling Ce cations facilitate the generation of high-valence Ni OER-active species. These results suggest the promising application of PNC for H2 production from water electrolysis.

Extending the depth of focus of fiber-optic optical coherence tomography using a chromatic dual-focus design.

We report a dual-focus fiber-optic probe designed to extend depth of focus (DOF) in high-resolution endoscopic optical coherence tomography. We exploited the broad spectral bandwidth of a supercontinuum source and, in the fiber probe, the foci of the 750-1000 nm and 1100-1450 nm inputs were axially chromatically shifted. The interference signals from the two spectral bands were measured with a Si camera-based spectrometer and an InGaAs camera-based spectrometer, respectively. We verified the feasibility of the design using a phantom composed of microparticles and swine small intestine tissue ex vivo. The results showed that a transverse resolution below 5 µm over 300 µm could be maintained, and that the extended DOF was 2 times larger than that of the single focus probe via the use of dual spectral band inputs and a chromatic focal shift.

Transient transmembrane secretion of H2O2: a mechanism for the citral-caused inhibition of aflatoxin production from Aspergillus flavus.

A polydopamine-Fe3O4 nanocomposite-based H2O2 electrochemical sensor is fabricated to real-time monitor the transmembrane release of reactive oxygen species from citral-treated Aspergillus flavus, revealing a mechanism involving transient transmembrane secretion of H2O2 for the citral-caused inhibition of aflatoxin production from a fungus for the first time.

Aflatoxin B1 degradation by a Pseudomonas strain.

Aflatoxin B1 (AFB1), one of the most potent naturally occurring mutagens and carcinogens, causes significant threats to the food industry and animal production. In this study, 25 bacteria isolates were collected from grain kernels and soils displaying AFB1 reduction activity. Based on its degradation effectiveness, isolate N17-1 was selected for further characterization and identified as Pseudomonas aeruginosa. P. aeruginosa N17-1 could degrade AFB1, AFB2 and AFM1 by 82.8%, 46.8% and 31.9% after incubation in Nutrient Broth (NB) medium at 37 °C for 72 h, respectively. The culture supernatant of isolate N17-1 degraded AFB1 effectively, whereas the viable cells and intra cell extracts were far less effective. Factors influencing AFB1 degradation by the culture supernatant were investigated. Maximum degradation was observed at 55 °C. Ions Mn²âº and Cu²âº were activators for AFB1 degradation, however, ions Mg²âº, Li⁺, Zn²âº, Se²âº, Fe³âº were strong inhibitors. Treatments with proteinase K and proteinase K plus SDS significantly reduced the degradation activity of the culture supernatant. No degradation products were observed based on preliminary LC-QTOF/MS analysis, indicating AFB1 was metabolized to degradation products with chemical properties different from that of AFB1. The results indicated that the degradation of AFB1 by P. aeruginosa N17-1 was enzymatic and could have a great potential in industrial applications. This is the first report indicating that the isolate of P. aeruginosa possesses the ability to degrade aflatoxin.

[A clinical comparative study on Traditional Chinese Medicine serving as consolidation treatment in patients with advanced non-small cell lung cancer].

BACKGROUND: The role of Traditional Chinese Medicine(TCM) is recognized in treatment of non-small cell lung cancer.The aim of this study is to evaluate the efficacy of TCM serving as consolidation treatment in patients with advanced non-small cell lung cancer. METHODS: One hundred and sixty-two patients with advanced non-small cell lung cancer were divided into two arms.Arm A(observation arm):81 cases,TCM serving as consolidation treatment after conventional treatment;Arm B(control arm):81 cases,only conventional treatment,no TCM serving as consolidation treatment.The TCM was given according mainly to the syndrome differentiation.Four types were found in the arm A:lung and spleen-qi deficiency type,the lung heat and phlegm-dampness type,the lung-yin and stomach-yin deficiency type,and the qi stagnation with blood stasis type. RESULTS: 1-,2-,3-and 5-year survival rate accounted for 70.3%,37.0%,20.9% and 8.6% in arm A,and 61.7%,20.9%,8.6% and 3.7% in arm B,respectively.Median survival time was 18 months in arm A and 12 months in arm B,respectively.Statistically,2-and 3-year survival rate of arm A and arm B had significant difference(P < 0.05). CONCLUSIONS: TCM serving as consolidation treatment in patients with advanced non-small cell lung cancer might be closely related to 2-and 3-year survival rate and median survival time improvement,but not to 5-year survival rate.

[Evaluation on survival in locally advanced non-small cell lung cancer (NSCLC) for multimodality treatment with or without operation].

BACKGROUND: It is uncertain that the effect of multimodality treatment with operation on survival for locally advanced non-small cell lung cancer (NSCLC). The aim of this study is to evaluate the effect of multimodality treatment with or without operation on survival for locally advanced NSCLC. METHODS: From May 1992 to May 1999, 114 patients with locally advanced NSCLC were divided into two arms. Arm A (n=56): 39 cases were at stage IIIA, and 17 at stage IIIB; Median KPS was 80 (range from 70 to 90 ); Multimodality treatment program included operation, chemotherapy, radiotherapy and traditional Chinese herb medicine. Of them, lobectomy plus mediastinal systematic lymph node dissection or lymph node sampling accounted for 49 cases, sleeve lobectomy plus mediastinal lymph node dissection for 5 cases, and pneumonectomy for 2 cases. Preoperative or adjuvant chemotherapy regimens included MVP (mitomycin C, vindesine, cisplatin), NP (vinorelbine, cisplatin), TC (paclitaxel, carboplatin), GP (gemcitabine, cisplatin), which were repeated every 4 weeks for 4-6 cycles. Total dose of radiotherapy for lesions in the lung or mediastinal field was 5000-6000cGy. Arm B (n=58): 23 cases were at stage IIIA, and 35 at stage IIIB; Median KPS was 70 (range from 60 to 90); Treatment program was the same approximately as arm A except for no operation. RESULTS: Arm A: (1) Metastatic locations in follow-up, in turn, showed as: lymph node, pleural-lung, bone, brain, liver, pericardium, skin and adrenal; (2) Median survival was 27 months, and 1-, 2- and 5-year survival rate was 82.1%, 60.7% and 25.0% respectively. Arm B: (1) Metastatic locations in follow-up, in turn, showed as: lymph node, pleural-lung, bone, brain, liver, pericardium, skin, adrenal, pancreatic and esophageal metastasis; (2) Median survival was 13 months, and 1-, 2- and 5-year survival rate was 53.4%, 31.0% and 1.7% respectively. Median survival duration of Arm A was significantly superior to Arm B (P=0.0001). There were significant differences in 1-, 2- and 5-year survival rate between the two groups (Chi-Square=9.4, P < 0.01; Chi-Square=8.9, P < 0.01;Chi-Square=11.5, P < 0.01). CONCLUSIONS: Compared with non-operative multimodality treatment, operative multimodality treatment including lobectomy or pneumonectomy with mediastinal lymph node dissection can remarkably improve the survival in patients with locally advanced NSCLC.

[Diagnostic value of multiple tumor marker protein biochip detective system for lung cancer].

BACKGROUND: To evaluate the diagnostic values of multiple tumor marker protein biochip detective system for lung cancer. METHODS: The serum levels of 12 tumor markers, including CA199, NSE, CEA, CA242, CA125, CA153, AFP, ferritin, free-PSA, PSA, ß-HCG and HGH, were measured in 108 lung cancer patients, 48 patients with benign pulmonary lesion and 145 healthy by the detective system. RESULTS: The positive rates were 83.33% (90/108), 52.08% (25/48) and 28.97% (42/145) in lung cancer, benign pulmonary lesion and healthy groups, respectively. The lung cancer group had significantly higher positive rate than that of the controls (Chi-Square=16.75 and 73.32, both P < 0.001); There was significant difference of positive rate in various clinical stages of lung cancer (Chi-Square=7.89, P=0.048), but not in different pathologic classification. Serum CA199, CEA and CA242 levels were closely correlated with clinical staging (F=2.84, P=0.041; F= 3.49, P=0.018; F =5.22, P=0.002). The positive rate of CEA in adenocarcinoma was higher, but no significant difference was observed (Chi-Square=0.71, P=0.07). NSE in small cell lung cancer had the highest positive rate (Chi-Square=19.03, P < 0.001). Combined measurement of the twelve markers had higher sensitivity (Chi-Square= 368.58, P < 0.001), but less specificity (Chi-Square= 369.87, P < 0.001). CONCLUSIONS: Combined measurement of various serum tumor markers using protein biochip can significantly increase the diagnostic sensitivity for lung cancer. Meanwhile, it is also significant for defining clinical stage, identificating pathologic classification, as well as monitoring therapeutic efficacy. As its specificity and positive predictive value are lower, it is more suitable to be used as a surveying tool for symptomless people, especially for high risk people for lung cancer.