Characterization of T cell receptor repertoire in penile cancer.

Tumor-infiltrating lymphocytes (TILs) play a key role in regulating the host immune response and shaping tumor microenvironment. It has been previously shown that T cell infiltration in penile tumors was associated with clinical outcomes. However, few studies have reported the T cell receptor (TCR) repertoire in patients with penile cancer. In the present study, we evaluated the TCR repertoires in tumor and adjacent normal tissues from 22 patients with penile squamous cell carcinoma (PSCC). Analysis of the T cell receptor beta-variable (TRBV) and joining (TRBJ) genes usage and analysis of complementarity determining region 3 (CDR3) length distribution did not show significant differences between tumor and matched normal tissues. Moreover, analysis of the median Jaccard index indicated a limited overlap of TCR repertoire between these groups. Compared with normal tissues, a significantly lower diversity and higher clonality of TCR repertoire was observed in tumor samples, which was associated with clinical characteristics. Further analysis of transcriptional profiles demonstrated that tumor samples with high clonality showed increased expression of genes associated with CD8 + T cells. In addition, we analyzed the TCR repertoire of CD4 + T cells and CD8 + T cells isolated from tumor tissues. We identified that expanded clonotypes were predominantly in the CD8 + T cell compartment, which presented with an exhausted phenotype. Overall, we comprehensively compared TCR repertoire between penile tumor and normal tissues and demonstrated the presence of distinct T cell immune microenvironments in patients with PSCC.

Maternal rheumatoid arthritis and risk of autism in the offspring.

BACKGROUND: Maternal Rheumatoid Arthritis (RA) is suggested to increase the risk of Autism Spectrum Disorder (ASD) in the offspring, mainly through inflammation/autoimmunity, but the association is unclear. A prospective population-based cohort study was implemented to examine the association between maternal RA and offspring ASD. METHODS: We included all children born alive in Sweden from 1995 to 2015, followed up through 2017. Diagnoses of ASD and RA were clinically ascertained from National Patient Register. We quantified the association by hazard ratios (HR) and two-sided 95% confidence intervals (CI), from Cox regression after detailed adjustment for potential confounders. We examined RA serostatus, etiological subgroups and the timing of exposure. To closer examine the underlying mechanism for the association, we included a negative control group for RA, arthralgia, with similar symptomology as RA but free from inflammation/autoimmunity. RESULTS: Of 3629 children born to mothers with RA, 70 (1.94%) were diagnosed with ASD, compared to 28 892 (1.92%) of 1 503 908 children born to mothers without RA. Maternal RA before delivery was associated with an increased risk of offspring ASD (HR = 1.43, 95% CI 1.11-1.84), especially for seronegative RA (HR = 1.61, 95% CI 1.12-2.30). No similar association was observed for paternal RA, maternal sisters with RA, or RA diagnosed after delivery. Maternal arthralgia displayed as high risks for offspring ASD as did maternal RA (HR = 1.41, 95% CI 1.24-1.60). CONCLUSIONS: In Sweden, maternal RA before delivery was associated with an increased risk of offspring ASD. The comparable association between maternal arthralgia and ASD risk suggests other pathways of risk than autoimmunity/inflammation, acting jointly or independently of RA.

Comparative Analysis of Chemical Constituents of Moringa oleifera Leaves from China and India by Ultra-Performance Liquid Chromatography Coupled with Quadrupole-Time-Of-Flight Mass Spectrometry.

With the aim to discuss the similarities and differences of phytochemicals in Moringa oleifera leaves collected from China (CML) and India (IML) in mind, comparative ultra-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry (UPLC-QTOF-MS) analysis was performed in this study. A screening analysis based on a UNIFI platform was first carried out to discuss the similarities. Next, untargeted metabolomic analysis based on multivariate statistical analysis was performed to discover the differences. As a result, a total of 122 components, containing 118 shared constituents, were characterized from CML and IML. The structure types included flavonoids, alkaloids, glyosides, organic acids and organic acid esters, iridoids, lignans, and steroids, etc. For CML, 121 compounds were characterized; among these, 18 potential biomarkers with higher contents enabled differentiation from IML. For IML, 119 compounds were characterized; among these, 12 potential biomarkers with higher contents enabled differentiation from CML. It could be concluded that both CML and IML are rich in phytochemicals and that CML is similar to IML in the kinds of the compounds it contains, except for the significant differences in the contents of some compounds. This comprehensive phytochemical profile study provides a basis for explaining the effect of different growth environments on secondary metabolites and exists as a reference for further research into or applications of CML in China.

Non-Targeted Metabolomic Analysis of Methanolic Extracts of Wild-Simulated and Field-Grown American Ginseng.

Aiming at revealing the structural diversity of secondary metabolites and the different patterns in wild-simulated American ginseng (WsAG) and field-grown American ginseng (FgAG), a comprehensive and unique phytochemical profile study was carried out. In the screening analysis, a total of 121 shared compounds were characterized in FgAG and WsAG, respectively. The results showed that both of these two kinds of American ginseng were rich in natural components, and were similar in terms of the kinds of compound they contained. Furthermore, in non-targeted metabolomic analysis, when taking the contents of the constituents into account, it was found that there indeed existed quite a difference between FgAG and WsAG, and 22 robust known biomarkers enabling the differentiation were discovered. For WsAG, there were 12 potential biomarkers including two ocotillol-type saponins, two steroids, six damarane-type saponins, one oleanane-type saponins and one other compound. On the other hand, for FgAG, there were 10 potential biomarkers including two organic acids, six damarane-type saponins, one oleanane-type saponin, and one ursane. In a word, this study illustrated the similarities and differences between FgAG and WsAG, and provides a basis for explaining the effect of different growth environments on secondary metabolites.

Pharmacokinetic and Metabolism Studies of 12-Riboside-Pseudoginsengenin DQ by UPLC-MS/MS and UPLC-QTOF-MSE.

Pharmacokinetic and metabolism studies of 12-riboside-pseudoginsengenin DQ (RPDQ), a novel ginsenoside with an anti-cancer effect, were carried out, aiming at discussing the characteristics of the ginsenoside with glycosylation site at C-12. In the pharmacokinetic analysis, we developed and validated a method by UPLC-MS to quantify RPDQ in rat plasma. In the range of 5⁻1000 ng/mL, the assay was linear (R² > 0.9966), with the LLOQ (lower limit of quantification) being 5 ng/mL. The LOD (limit of detection) was 1.5 ng/mL. The deviations of intra-day and inter-day, expressed as relative standard deviation (RSD), were ≤ 3.51% and ≤ 5.41% respectively. The accuracy, expressed as relative error (RE), was in the range ⁻8.82~3.47% and ⁻5.61~2.87%, respectively. The recoveries were in the range 85.66~92.90%. The method was then applied to a pharmacokinetic study in rats intragastrically administrated with 6, 12, and 24 mg/kg RPDQ. The results showed that RPDQ exhibited slow oral absorption (Tmax = 7.0 h, 7.5 h, and 7.0 h, respectively), low elimination (t1/2 = 12.59 h, 12.83 h, and 13.74 h, respectively) and poor absolute bioavailability (5.55, 5.15, and 6.08%, respectively). Moreover, the investigation of metabolites were carried out by UPLC-QTOF-MS. Thirteen metabolites of RPDQ were characterized from plasma, bile, urine, and feces of rats. Some metabolic pathways, including oxidation, acetylation, hydration, reduction, hydroxylation, glycine conjugation, sulfation, phosphorylation, glucuronidation, glutathione conjugation, and deglycosylation, were profiled. In general, both the rapid quantitative method and a good understanding of the characteristics of RPDQ in vivo were provided in this study.

UPLC-QTOF/MS-Based Nontargeted Metabolomic Analysis of Mountain- and Garden-Cultivated Ginseng of Different Ages in Northeast China.

Aiming at further systematically comparing the similarities and differences of the chemical components in ginseng of different ages, especially comparing the younger or the older and mountain-cultivated ginseng (MCG), 4, 5, 6-year-old cultivated ginseng (CG) and 12, 20-year-old MCG were chosen as the analytical samples in the present study. The combination of UPLC-QTOF-MSE, UNIFI platform and multivariate statistical analysis were developed to profile CGs and MCGs. By the screening analysis based on UNIFI, 126 chemical components with various structural types were characterized or tentatively identified from all the CG and MCG samples for the first time. The results showed that all the CG and MCG samples had the similar chemical composition, but there were significant differences in the contents of markers. By the metabolomic analysis based on multivariate statistical analysis, it was shown that CG4⁻6 years, MCG12 years and MCG20 years samples were obviously divided into three different groups, and a total of 17 potential age-dependent markers enabling differentiation among the three groups of samples were discovered. For differentiation from other two kinds of samples, there were four robust makers such as α-linolenic acid, 9-octadecenoic acid, linoleic acid and panaxydol for CG4⁻6 years, five robust makers including ginsenoside Re1, -Re2, -Rs1, malonylginsenoside Rb2 and isomer of malonylginsenoside Rb1 for MCG20 years, and two robust makers, 24-hydroxyoleanolic acid and palmitoleic acid, for MCG12 years were discovered, respectively. The proposed approach could be applied to directly distinguish MCG root ages, which is an important criterion for evaluating the quality of MCG. The results will provide the data for the further study on the chemical constituents of MCG.

Pharmacokinetic and Metabolism Studies of Curculigoside C by UPLC-MS/MS and UPLC-QTOF-MS.

Pharmacokinetic and metabolism studies were carried out on curculigoside C (CC), a natural product with good antioxidant and neuroprotective effects, with the purpose of investigating the effects of the hydroxyl group at C-3' in curculigoside. A rapid and sensitive method with UPLC-MS was developed and fully validated for the first time in the pharmacokinetic analysis for quantification of CC in rat plasma. The assay was linear (R² > 0.9984) over the concentration range of 1⁻2500 ng/mL, with the lower limit of quantification (LLOQ) being 1 ng/mL. The intra-day and inter-day precision (expressed as relative standard deviation, RSD) ranged from 4.10% to 5.51% and 5.24% to 6.81%, respectively. The accuracy (relative error, RE) ranged from -3.28% to 0.56% and -5.83% to -1.44%, respectively. The recoveries ranged from 92.14% to 95.22%. This method was then applied to a pharmacokinetic study of rats after intragastric administration of 15, 30 and 60 mg/kg CC. The results revealed that CC exhibited rapid oral absorption (Tmax = 0.106 h, 0.111 h, and 0.111 h, respectively), high elimination (t1/2 = 2.022 h, 2.061 h, and 2.048 h, respectively) and low absolute bioavailability (2.01, 2.13, and 2.39%, respectively). Furthermore, an investigation on the metabolism of CC was performed by UPLC-QTOF-MSE. Twelve metabolites of CC from plasma, bile, urine and faeces of rats were confirmed. The main metabolic pathways of CC, which involve dehydration, glucosylation, desaturation, formylation, cysteine conjugation, demethylation and sulfonation, were profiled. In conclusion, this research has developed a sensitive quantitative method and demonstrated the metabolism of CC in vivo.

Comprehensive Metabolomics Analysis of Xueshuan Xinmaining Tablet in Blood Stasis Model Rats Using UPLC-Q/TOF-MS.

Blood stasis syndrome (BSS) is one of the most common Chinese medicine patterns in coronary heart disease. Our previous work proved that Xueshuan Xinmaining Tablet (XXT) could treat blood stasis through regulating the expression of F13a1, Car1 and Tbxa2r. In the current study, the effect and mechanism of XXT on BSS was comprehensively and holistically investigated based on a metabolomics approach. Urine and plasma samples of 10 BBS rats treated with XXT (XT), 9 BSS model rats (BM) and 11 normal control (NC) rats were collected and then determined by UPLC-Q/TOP-MS. Multivariate analyses were applied to distinguish differentiate urinary and plasma metabolite patterns between three groups. Results showed that a clear separation of three groups was achieved. XT group was located between BM group and NC group, and showing a tendency of recovering to NC group, which was consistent with the results of hemorheological studies. Some significantly changed metabolites like cortexolone, 3α,21-dihydroxy-5ß-pregnane-11,20-dione and 19S-hete and leukotriene A4, chiefly involved in steroid hormone biosynthesis, arachidonic acid metabolism and lipid metabolism, were found and identified to explain the mechanism. These potential markers and their corresponding pathways will help explain the mechanism of BSS and XXT treatment. This work also proves that metabolomics is effective in traditional Chinese medicinal research.

Synthesis of 2H-Chromenones from Salicylaldehydes and Arylacetonitriles.

An efficient and convenient protocol for the synthesis of 2H-chromenones has been developed. In the presence of tBuOK in DMF, good to excellent yields of various chromenones were obtained from the corresponding salicylaldehydes and arylacetonitriles. No protection of inert gas atmosphere is required here.

Nontargeted Metabolomic Analysis of Four Different Parts of Platycodon grandiflorum Grown in Northeast China.

Platycodonis radix is extensively used for treating cough, excessive phlegm, sore throat, bronchitis and asthma in the clinic. Meanwhile, the stems, leaves and seeds of Platycodon grandiflorum (PG) have some pharmaceutical activities such as anti-inflammation and anti-oxidation effects, etc. These effects must be caused by the different metabolites in various parts of herb. In order to profile the different parts of PG, the ultra-high performance liquid chromatography combined with quadrupole time-of- flight mass spectrometry (UPLC-QTOF-MSE) coupled with UNIFI platform and multivariate statistical analyses was used in this study. Consequently, for the constituent screening, 73, 42, 35, 44 compounds were characterized from the root, stem, leaf and seed, respectively. The stem, leaf and seed contain more flavonoids but few saponins that can be easily discriminated in the root. For the metabolomic analysis, 15, 5, 7, 11 robust biomarkers enabling the differentiation among root, stem, leaf and seed, were discovered. These biomarkers can be used for rapid identification of four different parts of PG grown in northeast China.

Fabrication of homogenous multilayered W films by multi-step sputtering deposition: a novel grain boundary enrichment strategy.

Using a multi-step deposition approach, we develop a strategy of homogeneous multilayered (HM) structure to enrich the grain boundary (GB) of sputtered W films. In comparison with the single-layered film, the HM W film is easily controllable for the film GB density. When decreasing the film modulation period t m from 160 nm to 7 nm, the GB density gradually increased from 0.065 nm(-1) to 0.275 nm(-1) without changing the phase structure of the films. Accordingly, the film's electrical resistivity and mechanical hardness, which are related to the GBs, changed from 40.1 µΩ · cm to 75.3 µΩ · cm and from 12.1 GPa to 16.2 GPa, respectively. Detailed analysis showed that the formation of an HM structure is related to the temperature evolution of the film growing surface during the multi-step sputtering process. This study could provide a general engineering approach to enrich film interfaces and allows for the development of thin films with novel microstructures.

Physicochemical, structural and functional properties of low methoxyl pectin­iron (III) complex and its effect on rats with iron deficiency anemia.

Iron deficiency anemia (IDA) is the most common nutritional disease worldwide. In this study, a low methoxyl pectin (LMP)­iron(III) complex was prepared. The physicochemical and structural properties were characterized by HPSEC, HPIC, CV, FTIR, 1H NMR, XRD, SEM and CD. The results showed that iron increased the molecular weight of the LMP­iron(III) from 11.50 ± 0.32 to 12.70 ± 0.45 kDa and improved its crystallinity. Moreover, the findings demonstrated that -OH and -COOH groups in LMP coordinate with Fe3+ to form ß-FeOOH. The water-holding capacity, emulsion stability, and antioxidant activities of the LMP­iron(III) were lower than those of LMP. Furthermore, the therapeutic effects of LMP­iron(III) on IDA were investigated in rats. Following LMP­iron(III) supplementation, compared with the model group, the administration of LMP­iron(III) significantly increased the body weight, hemoglobin concentration, and serum iron concentration as well as decreased free erythrocyte protoporphyrin concentration. Therefore, the LMP­iron(III) can potentially treat IDA in rats experiments, providing a theoretical basis for the development of a promising iron supplement.

Integrated non-targeted metabolomics and network pharmacology to reveal the mechanisms of berberine in the long-term treatment of PTZ-induced epilepsy.

AIMS: The increasing resistance to anti-seizure medications (ASMs) and the ambiguous mechanisms of epilepsy highlight the pressing demand for the discovery of pioneering lead compounds. Berberine (BBR) has received significant attention in recent years within the field of chronic metabolic disorders. However, the reports on the treatment of epilepsy with BBR are not systematic and the mechanism remains unclear. MAIN METHODS: In this study, the seizure behaviors of mice were recorded following subcutaneous injection of pentetrazol (PTZ). Non-targeted metabolomics was used to analyze the serum metabolites based on ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). Meanwhile, multivariate statistical methods were used for metabolite identification and pathway analysis. Furthermore, network pharmacology, molecular docking, and quantitative real-time PCR assay were used for the target identification. KEY FINDINGS: BBR had anti-seizure effects on PTZ-induced seizure mice after long-term treatment. Tryptophan metabolism and phenylalanine metabolism were involved in regulating the therapeutic effects of BBR. SIGNIFICANCE: This study reveals the potential mechanism of BBR for epilepsy treatment based on non-targeted metabolomics and network pharmacology, which provides evidence for uncovering the pathogenesis of epilepsy, suggesting that BBR is a potential lead compound for anti-epileptic treatment.

Chitosan-Based Hydrogel-Incorporated Trp-CDs with Antibacterial Properties and pH-Mediated Fluorescence Response as a Smart Food Preservation Material.

The great problem of food spoilage is causing food waste worldwide. However, prolonging the shelf life of food and responding to spoilage are good strategies for dealing with this problem. Herein, we present the design of multifunctional chitosan-based hydrogel-incorporated tryptophan carbon quantum dots (Trp-CDs) with antibacterial properties and pH-mediated fluorescence response (pH = 1-13). This chitosan (CS)/tannic acid (TA)/Trp-CDs hydrogel (CTTC hydrogel) was rapidly formed by a high density of hydrogen bonds and has the advantages of good mechanical properties (1628.55 kPa, 280%), washability (5-10 min), antioxidant activity (95.83%), and antibacterial properties. In practical application with fruits, the hydrogel significantly prolonged the shelf life of strawberries by at least 5 days and oranges by 20 days under ambient conditions. In particular, the hydrogel has good pH-mediated fluorescence responsiveness and reversibility due to doping with Trp-CDs, laying a foundation for its application in response to food spoilage.

Fabrication of Anatase TiO2/PVDF Composite Membrane for Oil-in-Water Emulsion Separation and Dye Photocatalytic Degradation.

At present, the types of pollutants in wastewater are more and more complicated, however, the multifunctional membrane materials are in short supply. To prepare a membrane with both high efficient oil-in-water emulsion separation performance and photocatalytic degradation performance of organic dyes, the bifunctional separation membrane was successfully prepared by electrostatic spinning technology of PVDF/PEMA and in situ deposition of anatase TiO2 nanoparticles containing Ti3+ and oxygen vacancies (Ov). The prepared composite membrane has excellent hydrophilic properties (WCA = 15.65), underwater oleophobic properties (UOCA = 156.69), and photocatalytic performance. These composite membranes have high separation efficiency and outstanding anti-fouling performance, the oil removal efficiency reaches 98.95%, and the flux recovery rate (FRR) reaches 99.19% for soybean oil-in-water emulsion. In addition, the composite membrane has outstanding photocatalytic degradation performance, with 97% and 90.2% degradation of RhB and AG-25 under UV conditions, respectively. Several oil-in-water separation and dye degradation experiments show that the PVDF composite membrane has excellent reuse performance. Based on these results, this study opens new avenues for the preparation of multifunctional reusable membranes for the water treatment field.

High-Efficiency Corrosion Inhibitor of Biomass-Derived High-Yield Carbon Quantum Dots for Q235 Carbon Steel in 1 M HCl Solution.

Eco-friendly self-doped carbon quantum dots (ZCQDs) with excellent corrosion inhibition ability were prepared via solid-phase pyrolysis only using Zanthoxylum bungeanum leaves as the raw material. Compared with the relevant research, a simpler and higher yield (25%) preparation process for carbon quantum dots was proposed. ZCQDs were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy, and the average size of ZCQDs with multitudes of O- and N-containing functional groups was about 2.53 nm. The prepared ZCQDs were used to inhibit the corrosion of Q235 steel in HCl solution, and the inhibition behavior was investigated through weight loss, electrochemical test, surface analysis, and adsorption thermodynamic analyses. The results showed that the ZCQDs, acted as a mixed corrosion inhibitor, have an effective corrosion inhibition for Q235, the corrosion inhibition efficiency reached 95.98% at 200 mg/L, and at this concentration, effective protection of at least 132h (IE > 90%) is provided. Moreover, the adsorption mechanism of ZCQDs was consistent with that of Redlich-Peterson adsorption, including chemisorption and physisorption. A new corrosion inhibition mechanism of ZCQDs has been thoroughly studied and proposed; ZCQDs have functional groups containing O and N, which can form a protective barrier through physical adsorption and chemisorption, but the coverage of the protective film is low at low concentrations. With the increase of concentration, the protective film formed by ZCQDs on the metal surface will first increase the coverage and then adsorb more ZCQDs on the protective film to form a thicker and denser protective film to protect the metal. The carbon quantum dots prepared in this paper have advantages including a green, renewable precursor, a fast method, high yield, and excellent corrosion inhibition. Therefore, this work can inspire and facilitate, to a certain extent, the future application of doped carbon quantum dots as efficient corrosion inhibitors in HCl solutions.

The effect of grape seed procyanidins extract on cognitive function in elderly people with mild cognitive impairment: A randomized, double-blind, placebo-controlled clinical trial.

Background: Procyanidins have antioxidative properties that may protect against age-related brain oxidative stress. Previous studies indicated that procyanidin-rich foods could improve cognitive function and prevent neurodegenerative diseases. This study hypothesized that grape seed procyanidins extract (GSPE) would have a favorable effect on cognitive function in elderly people with mild cognitive impairment (MCI). Methods: A community-based, randomized, double-blind, placebo-controlled trial was conducted. Participants aged 60 years or older with MCI were randomly assigned into the GSPE group (n = 35, 320 mg/d) or placebo group (n = 36), and received capsules for 6 months. Cognitive function was assessed using the Montreal Cognitive Assessment Scale (MoCA). The change in MoCA scores between groups were tested by the time ✕ treatment interaction in mixed-design ANOVA. Results: After 6 months of intervention, the MoCA score was higher than the baseline both in the intervention group and placebo control group, while the there was no significant difference for mean change in MoCA score from baseline between the intervention group and the placebo group (2.35 ± 3.20 vs. 1.28 ± 2.93, P = 0.192). Conclusions: Present study showed that 6-month supplementation with GSPE did not significantly improve cognitive function in subjects with MCI. Further investigations regarding the longer-term intervention effect of procyanidins extract on mild or moderate cognitive disorders are needed.

Development and validation of an integrated nomogram to predict personalized new baseline functional outcomes after partial nephrectomy.

BACKGROUND: The prediction of new baseline renal function after partial nephrectomy (PN) has important clinical implications. This study aimed to establish a precise personalized nomogram integrating pre-, intra- and post-operative variables to predict new baseline function after PN. METHODS: This nomogram was constructed based on 213 consecutive PN cases at a large-volume institution from 2014 to 2017 and externally validated by a prospective cohort from January to December 2018 at the same institution. Multivariate cox regression and logistic least absolute shrinkage and selection operator (LASSO) regression were used to select predictors. The performance of the nomogram was assessed by the concordance index (C-index), calibration plot, decision curve analysis and Kaplan-Meier plot. RESULTS: The average drop percent of the estimated glomerular filtration rate (eGFR) was -8.6% (-12.3%, -7.2%). Multivariate Cox regression analysis and LASSO regression revealed that age, baseline eGFR, RENAL nephrometry score, ischemia time, and AKI were independent predictive factors. These five factors were subsequently incorporated to establish an integrated nomogram, with a C-index of 0.910, excellent calibration plot and net clinical benefit. An external validation of 67 patients showed a C-index of 0.801, excellent calibration and clinical net benefit. CONCLUSIONS: Our proposed nomogram based on pre-, intra- and post-operative outcomes accurately predicts personalized new baseline eGFR after PN. The successful personalized prediction of at-risk individuals at an early stage can provide multi-professional consideration and timely management.

Visible-Light-Driven Zr-MOF/BiOBr Heterojunction for the Efficient Synchronous Removal of Hexavalent Chromium and Rhodamine B from Wastewater.

With the rapid industrial development, the coexistence of multiple pollutants in wastewater has become a common phenomenon. Thus, developing highly efficient decontamination methods is imperative. In this work, a string of UiO-66-NH2/BiOBr heterojunctions with varying ratios of BiOBr were prepared and applied to remove hexavalent chromium Cr(VI) and rhodamine B (RhB). The possible growth process of BiOBr nanosheets on UiO-66-NH2, removal activity of contaminants, and photocatalysis mechanism were investigated. When the mass ratio of UiO-66-NH2 to BiOBr reaches 1:0.75, the heterojunction (NB-75) shows optimal photocatalytic activity. After 30 min of adsorption, the total removal rates of Cr(VI) (50 mg/L) and RhB (10 mg/L) over NB-75 (0.25 g/L) reaches 96.7% within 120 min of illumination and 98.9% within 80 min of illumination, respectively. For the removal process, there are two factors. The first is the high adsorption capacity for RhB and Cr(VI) owing to the high porosity of UiO-66-NH2 and interlayer surface positive charge of BiOBr. The second is the improved visible-light photocatalytic performance of the UiO-66-NH2/BiOBr heterojunction via rapid separation of photoinduced carriers. In addition, the active species capture study reveals that the electrons (e-) and the superoxide radicals (•O2 -) play key roles in Cr(VI) reduction, while the holes (h+) are major reactive groups participating in the degradation of RhB. This work demonstrated a kind of promising MOF-based photocatalysis material for eliminating Cr(VI) and RhB simultaneously.

Fabrication of photo-Fenton self-cleaning PVDF composite membrane for highly efficient oil-in-water emulsion separation.

The anti-fouling performance of membranes is an important performance in the separation of oil/water. However, the membrane with anti-fouling performance will also have surface scaling phenomenon when it runs for a long time. Therefore, there is still a great demand for stain-resistant membranes with good self-cleaning ability and high flux recovery rate. Based on this, this paper firstly prepared a hydrophilic membrane with carboxyl group and carboxyl ion by blending poly(ethylene-alt-maleic anhydride) (PEMA) and polyvinylidene fluoride (PVDF), and then prepared a self-cleaning composite membrane by in situ mineralization of ß-FeOOH particles on the surface of the membrane for efficient oil-in-water emulsion separation. A large number of -COOH/COO- and ß-FeOOH particles on the membrane surface make the composite membrane have strong hydrophilic properties (WCA = 20.34°) and underwater superoleophobicity (UOCA = 155.10°). These composite membranes have high separation efficiency (98.8%) and high flux (694.56 L m-2 h-1 bar-1) for soybean oil-in-water emulsion. Importantly, the as-prepared membrane shows excellent flux recovery rate (over 99.93%) attributed to the robust photo-Fenton catalytic activity of ß-FeOOH, and the ß-FeOOH is chemically bonded to the as-prepared membrane, which makes the as-prepared membrane have good reusability. This work provides hope for the application of self-cleaning membranes in the construction of anti-fouling membranes for wastewater remediation.