Efficient and Sustainable in†situ Photo-Fenton Reaction to Remove Phenolic Pollutants by NH2 -MIL-101(Fe)/Ti3 C2 Tx Schottky-Heterojunctions.

Metal-organic frameworks (MOFs) with abundant active sites, a class of materials composed of metal nodes and organic ligands, is widely used for photocatalytic degradation of pollutants. However, the rapid recombination of photoinduced carriers of MOFs limits its photocatalytic degradation performance. Herein, Ti3 C2 Tx nanosheets-based NH2 -MIL-101(Fe) hybrids with Schottky-heterojunctions were fabricated by in situ hydrothermal assembly for improved photocatalytic activity. The photodegradation efficiencies of the NH2 -MIL-101(Fe)/Ti3 C2 Tx (N-M/T) hybrids for phenol and chlorophenol were 96.36 % and 99.83 % within 60 minutes, respectively. The N-M/T Schottky-heterojunction duly transferred electrons to the Ti3 C2 Tx nanosheets surface via built-in electric fields, effectively suppressing the recombination of photogenerated carriers, thereby improving the photocatalytic performance of NH2 -MIL-101(Fe). Moreover, the Fe-mixed-valence in the N-M/T led to improvement in the efficiency of the in situ generated photo-Fenton reactions, further enhancing the photocatalytic activity with more generated reactive oxygen species (ROS). The study proposes a highly effective removal of phenolic pollutants in wastewater.

A catalyst-free co-reaction system of long-lasting and intensive chemiluminescence applied to the detection of alkaline phosphatase.

A catalyst-free co-reaction luminol-H2O2-K2S2O8 chemiluminescence (CL) system was developed, with long-life and high-intensity emission, and CL emission lasting for 6 h. A possible mechanism of persistent and intense emission in this CL system was discussed in the context of CL spectra, cyclic voltammetry, electron spin resonance (ESR), and the effects of radical scavengers on luminol-H2O2-K2S2O8 system. H2O2 and K2S2O8 co-reactants can promote each other to continuously generate corresponding radicals (OH•, 1O2, O2•-, SO4•-) that trigger the CL emission of luminol. H2O2 can also be constantly produced by the reaction of K2S2O8 and H2O to further extend the persistence of this CL system. CL emission can be quenched via ascorbic acid (AA), which can be generated through hydrolysis reaction of L-ascorbic acid 2-phosphate trisodium salt (AAP) and alkaline phosphatase (ALP). Next, a CL-based method was established for the detection of ALP with good linearity from 0.08 to 5 U·L-1 and a limit of detection of 0.049 U·L-1. The proposed method was used to detect ALP in human serum samples.

The role of band structure in Co- and Fe-co-doped Ba0.5Sr0.5Zr0.1Y0.1O3-δ perovskite semiconductor to design an electrochemical aptasensing platform: application in label-free detection of ochratoxin A using voltammetry.

Nanocomposites can offer a platform to conjugate biorecognition features of aptamer with unique size-dependent properties of a given material, which can autoprobe the binding event based on their electroactive characteristics. Herein, we design electroactive switchable aptamer probes based on co-doped single-phase semiconducting materials employing the cyclic voltammetry method to record the current signal at each step of electrochemical characterization. To do so, we utilized a facile hydrothermal method assisted by co-precipitation method such as Co-Fe-co-doped Ba0.5Sr0.5Zr0.1Y0.1O3-δ (CF-BSZY) and tuned the alignment of the energy band structure of the material to amplify the output of the electrochemical signal. At various steps, changes occurred in the electrochemical properties at the surface of CF-BSZY. The binding of the ssDNA with prepared materials enhances the current signal by the interaction with the target (ochratoxin A (OTA)) depressing the current signal and facilitating the construction of a novel design of electrochemical aptasensor. As a proof of concept, an electrochemical aptasensor for the detection of ochratoxin A (OTA) in rice samples has been developed. The electrochemical aptasensor provides a limit of detection (LOD) of 0.00012 µM (0.12 nM), with a linear range from 0.000247 to 0.74 µM and sound OTA recovery in real samples. The developed aptasensor is simply designed and is free of oligonucleotide labeling or decorative nanoparticle modifications. The proposed mechanism is generic in principle with the potential to translate any type of aptamer and target binding event into a detectable signal; hence, it can be largely applied to various bioreceptor recognition phenomena for subsequent applications.

Visual identification of 1O2-induced crystal structure transformation of single Zr-MOF by dark-field microscopy.

Understanding the structural transformation of photocatalysts under illumination provides detailed insights to solve the poisoning of photocatalysts. In this study, the 1O2-induced transformation of crystalline structure in nanosized Zr-porphyrin metal organic frames (ZrTCPP MOFs) is confirmed by a dark-field microscopy (DFM) system. Under continuous illumination, the energy of excited ZrTCPP transfers to oxygen in the surroundings and generates 1O2, which causes the nanosized crystal ZrTCPP to change into the amorphous state The crystalline structure of ZrTCPP corresponds to the multiple resonance peaks of the scattering spectra, and the amorphous structure corresponds to the single scattering peak. Therefore, the crystalline change is characterized by characteristic peaks changes in the scattering spectra under DFM, showing that a real-time and in situ DFM imaging method is a good platform for monitoring the crystal structure transformation at the single particle level.

[Expression of multiple tumor suppressor gene p16 and its relationship with prognosis of gastric cancer patients].

OBJECTIVE: To investigate the relationship between p16 expression and cell proliferation and prognosis in gastric cancer patients. METHODS: Gastric cancer cell lines SGC-7901, MKN45, MKN28, human embryonic kidney cell line HEK293, human fibroblast cell line MRC-5, and surgical specimens of gastric carcinoma and adjacent normal gastric mucosa from 65 patients were included in this study. RT-PCR, MTT and FCM assays were used to detect p16 expression in gastric cancer cell lines and surgical specimens of gastric cancer. MTT assay was used to determine cancer cell viability and FCM to detect cell cycle. Kaplan-Meier survival curve and Log-Rank statistics were used to analyze the relationship between p16 expression and survival of petients with gastric cancer. RESULTS: Gastric cancer cell lines were mostly negative for p16 expression, and p16 was re-expressed after the cells transfected with p16 gene by adenovirus AdCMV-p16. p16 re-expression resulted in the decrease of cancer cell viability and cancer cell cycle arrest with increased G(1) phase and decreased S phase. p16 expression in cancer specimens was 32.3% (21/65), significantly lower than the 81.5% (53/65) in normal mucosa (χ(2) = 32.124, P < 0.001). The disease-free survival was significantly shorter in p16-negative patients than that in p16-positive patients (P < 0.01), but not the overall survival (P > 0.05). p16 expression was significantly correlated with differentiation and lymph node metastasis, but not significantly correlated with sex, age, tumor size or invasion depth of the gastric cancer. CONCLUSIONS: p16 gene is important for cancer cell proliferation. The inactivation gives cancer cells a high activity for proliferation and metastasis, and then influences the disease-free survival of gastric cancer patients.

Facile synthesis of porphyrin-MOFs with high photo-Fenton activity to efficiently degrade ciprofloxacin.

The slow conversion of Fe(Ⅱ)/Fe(III) cycle was largely limited the degradation efficiency of many photo-Fenton systems. Herein, four Fe-MOFs nanorods (namely Fe-TCPP-1, Fe-TCPP-2, Fe-TCPP-3, Fe-TCPP-4) with decreasing length-diameter ratios were synthesized in a household microwave oven, using photosensitizer porphyrin and iron ions with Fenton activity as building blocks. Among them, the Fe-TCPP-3 exhibited high photogenerated electron-hole (e--h+) separation efficiency and largest pore structure, endowing Fe-TCPP-3 with superior photo-Fenton property. In addition, Fe-TCPP-3 based photo-Fenton system was applied to efficiently degrade antibiotic ciprofloxacin (CIP) under neutral condition, due to the continuously generated reactive species (h+, e-, OH·, O2·-, 1O2) in Fe-TCPP-3 under visible-light irradiation. With irradiation for 30 min, the degradation efficiency of the system could reach about 73 %, which was about 26-fold towards the system without light irradiation. This study paved a way to modulating the photo-Fenton activity of MOF-based catalysts.

Continuous singlet oxygen generation for persistent chemiluminescence in Cu-MOFs-based catalytic system.

Due to the ultra-weak and instantaneous chemiluminescence (CL) of luminol-H2O2 system, developing new catalysts to dramatically enhance and produce persistent CL emission is crucial. In this study, the Cu-metal-organic frameworks (Cu-MOFs) with flower morphology converted from Cu-based metal-organic gels (Cu-MOGs) could catalyze luminol-H2O2 system, exhibiting persistent CL. The possible mechanism of this persistent emission of luminol was attributed to the gradual generation of OH˙, O2˙- and 1O2 in Cu-MOFs-catalyzed luminol-H2O2 system. In addition, OH˙ and O2˙- were continuously recombined into singlet oxygen on the surface of Cu-MOFs which further prolonged the duration time of the CL leading to the persistent emission, due to the longer lifetime of 1O2 compared to OH˙ and O2˙-. Furthermore, based on the high-intensity emission of Cu-MOFs-catalyzed luminol-H2O2 system, the strategy for sensitive response to quercetin was established with good linearity within the range of 0.05-1.2 µM and a detection limit of 49.7 nM. This study provides a new idea for developing persistent CL catalysts.

Cu vacancies enhanced photoelectrochemical activity of metal-organic gel-derived CuO for the detection of l-cysteine.

Defect engineering in the photoelectrochemical (PEC) process of photoelectrodes has been extensively studied. But insufficient attention has been received about the impact of metal vacancies (VM) in PEC process. Herein, the influence of Cu vacancies (VCu) on PEC performance of copper oxide (CuO) derived from Cu-based metal-organic gel (Cu-MOG) precursor was reported. It can be found that the presence of more VCu can improve the PEC activity of CuO photocathode by facilitating the charge separation and transfer. Moreover, the as-prepared CuO was presented as a new PEC sensor to detect l-cysteine (L-Cys) on the basis of the excellent PEC performance, which showed high sensitivity and selectivity. Good linear response of L-Cys within the range of 0.1-6 µM was performed with a detection limit of 0.04 µM. This work not only provides insights into the role of VM in the PEC process of photocathodes, but also proved the high potential applicability of CuO as a PEC device for biomolecule detection.

Heavy metal concentrations and associated health risks in edible tissues of marine nekton from the outer Pearl River Estuary, South China Sea.

Seven heavy metals including Hg, Cu, Pb, Cd, Zn, Cr, and As were examined in seventeen marine nekton species from the outer Pearl River Estuary (PRE), South China Sea. On the wet weight basis, the metal concentration ranges were 0.016-0.157 µg/g for Hg, 0.18-14.3 µg/g for Cu, 0.26-1.48 µg/g for Pb, 0.021-0.873 µg/g for Cd, 1.35-57.15 µg/g for Zn, 0.15-0.53 µg/g for Cr, and 0.42-7.83 µg/g for As, respectively. The levels of tested metals except for Pb in crustaceans were found to be higher than those in fish and cephalopods, suggesting that the diet and habitat played important roles on heavy metal accumulation ability of marine organism. Except for Cd in Champsodon capensis, Calappa lophos, and Portunus argentatus, all the left metal concentrations of investigated nekton species were below their permissible upper limits, indicating that consumption of examined marine nekton should be considered as safe for human health. The values of single target hazard quotient (THQ) and total THQ were all less than 1 and also suggested that there was no health risk for consumption. Even so, the local people should control their daily intake of crustacean foods from the outer PRE, since there might be potential As and Cd cumulative risks.

[Dominant species of cephalopods and their niche characteristics in offshore of northern South China Sea]. / å—æµ·åŒ—éƒ¨è¿‘æµ·å¤´è¶³ç±»ä¼˜åŠ¿ç§åŠå ¶ç”Ÿæ€ä½ç‰¹å¾.

To understand the relationships among dominant species of cephalopods in offshore nor-thern South China Sea, we examined the niche characteristics of these dominant species from both spatial and temporal dimensions using the index of relative importance (IRI), the niche breadth and overlap indices based on fishery resources data from the bottom-trawl survey for four seasons during 2014-2015. The results showed that five dominant species of cephalopods were recorded for four seasons, including Loligo edulis, L. chinensis, L. beka, Sepia esculenta, and L. duvaucelii. The first two species were shared by all seasons. Compared with historical data, the composition of dominant cephalopods species had changed. The cephalopods resource exhibited obvious temporal and spatial variations. Stock density was higher in the sea area extending from the southern Hainan Island to eastern Guangdong Province than that in Beibu Gulf. The seasonal variation was characte-rized by the largest in summer but the smallest in winter. The temporal and spatial niche analysis showed that there was inconsistent in the order between temporal and spatial niche breadths for domi-nant species. L. edulis (1.32) and L. chinensis (3.90) occupied the largest temporal and spatial niche breadths, respectively. The smallest of temporal and spatial niche breadths were shown for S. esculenta (0.98) and L. duvaucelii (2.04), respectively. Though the temporal niche overlap was numerically larger than the spatial niche overlap, both of them had higher values in interspecies among L. edulis, L. chinensis, L. beka, and the lower overlap for the species pairs between L. duvaucelii and other species. The result of correlation analysis suggested that niche breadth exhibited a significant negative correlation with variation in abundance on both temporal and spatial scales. The ecological niche could reflect the tempo-spatial changes of species resource, which enriched the traditional methods of fishery communities.

Occurrence of microplastics in gastrointestinal tracts and gills of fish from Beibu Gulf, South China Sea.

Microplastics are widespread across the global oceans, yet the potential risks of the ubiquitous environmental contaminant to marine organisms has been less known. Accumulation of microplastics and associated contaminants in marine fish, may pose adverse impacts to human health via seafood consumption. This study evaluated microplastic contamination in 24 fish species collected from Beibu Gulf, one of the world's largest fishing grounds in South China Sea. Microplastics were detected in 12 fish species at an abundance of 0.027-1.000 items individual-1 and found in fish stomach, intestines and gills with the count percentage of 57.7%, 34.6% and 7.7%, respectively. Transparent fibers were observed as the predominant microplastics, which might be ingested accidently by fish or transferred through other animals at lower trophic levels. Majority of microplastics were identified as polyester (44%) and nylon (38%), whereas polypropylene (6%), polyethylene (6%), and acrylics (6%) were also found. Relatively, higher microplastic abundances were found in demersal fish compared to the pelagic species. Overall, the abundance of microplastics was documented as relatively low in the commercial fish collected from the open water of Beibu Gulf, South China Sea.

Sealing of the cystic and appendix arteries with monopolar electrocautery during laparoscopic combined cholecystectomy and appendectomy.

The best method to ligate the arteries during laparoscopic cholecystectomy or appendectomy remains controversy. The aim of this study is to introduce a new approach during laparoscopic combined cholecystectomy and appendectomy using a monopolar electrocautery to seal the cystic and appendix arteries. We retrospectively reviewed data from 57 patients who underwent laparoscopic combined cholecystectomy and appendectomy between December 2006 and June 2016. Each laparoscopic combined cholecystectomy and appendectomy was performed by coagulating and sealing the cystic and appendix arteries. Absorbable clip or coils were then used to ligate the proximal of cystic duct and the stump of appendix. The other side of the cystic duct and appendix which subsequently were to be removed from abdomen were used titanium clips or silk ligature. Of the 57 patients, 3 patients (5.3%) were converted to open surgery due to severe abdominal adhesions or gallbladder perforation. The mean operative time was 56 minutes (range, 40-80 minutes). Mean blood loss was 12 mL (range, 5-120 mL), and the mean postoperative hospital stay was 3.0 days (range, 2-5 days). No postoperative bleeding, biliary leakage, infection, or mortality occurred. Monopolar electrocautery to seal the cystic and appendix arteries is a safe, effective, and economical surgical procedure during laparoscopic combined cholecystectomy and appendectomy. Further randomized controlled clinical trials are required to validate our findings.

Efficacy of electrocoagulation in sealing the cystic artery and cystic duct occluded with only one absorbable clip during laparoscopic cholecystectomy.

BACKGROUND: Even though laparoscopic cholecystectomy (LC) emerged over 20 years ago, controversies persist with regard to the best method to ligate the cystic duct and artery. We proposed to assess the effectiveness and safety of electrocoagulation to seal the cystic artery and cystic duct after their occlusion with only one absorbable clip. MATERIALS AND METHODS: We retrospectively compared the clinical data for 635 patients undergoing LC using electrocoagulation to seal the cystic artery and cystic duct that were occluded with only one absorbable clip (Group 1) and 728 patients undergoing LC using titanium clips (Group 2). In parallel, 30 rabbits randomized into six groups underwent cholecystectomy. After cystic duct ligation with absorbable or titanium clips, the animals were sacrificed 1, 3, or 6 months later, and intraabdominal adhesions were assessed after celiotomy. RESULTS: The mean operative time was significantly shorter (41.6 versus 58.9 minutes, P<.01) in Group 1 than in Group 2. No cystic duct leaks occurred in any patients from Group 1, compared with seven leaks among the 728 (0.96%) patients from Group 2 (P<.05). The morbidity was significantly higher in Group 2 than in Group 1 (3.43% versus 1.58%). Mean intraoperative blood loss and hospitalization length were not significantly different between the two groups, and no deaths occurred in either group. In animal experiments, adhesion was tighter for absorbable than for titanium clips, but fibrous tissue encapsulation was thinner at the site of titanium clips. CONCLUSIONS: Electrocoagulation of the cystic artery and cystic duct that were occluded with only one absorbable clip is safe and effective during LC. This approach is associated with shortened operative times and reduced leakage, compared with the standard method using metal clips.

RET proto-oncogene genetic screening of families with multiple endocrine neoplasia type 2 optimizes diagnostic and clinical management in China.

BACKGROUND: Genetic screening for germline mutations in the RET proto-oncogene has been extensively exploited worldwide to optimize the diagnostic and clinical management of multiple endocrine neoplasia type 2 (MEN2) patients and their relatives. However, a distinct lag period exists not only in the recognition but also in the medical treatment of patients with MEN2. Here we present a comprehensive genetic and clinical analysis of MEN2 among Chinese families followed from 1975 to 2011. Our series comprises 36 index cases and 134 relatives from 11 independent families. METHODS: Genetic diagnosis was performed in all participants by direct sequencing all relevant RET exons. Thyroidectomy was performed in 50 patients with varying cervical neck dissection procedures. Patients with pheochromocytoma (PHEO) underwent specific surgery. Demographic, clinical profiles, mutation types, tumor histopathologic features, and follow-up records were systematically analyzed. RESULTS: The RET mutations p.C634Y (n=34), p.C634R (n=6), p.C618S (n=13), p.V292M/R67H/R982C (n=7), p.L790F (n=2), and p.C634Y/V292M/R67H/R982C (n=1) were confirmed in 31 index cases and then identified in 32 at-risk relatives (mutation carriers), with MEN2A as the most common clinical subtype. The overall penetrance of PHEO in patients with MEN2A was 46.7%. A total of 50 patients underwent thyroidectomy, and there was a significant lowering of their mean age at thyroidectomy and the tumor diameter of the mutation carriers that were detected and operated on compared with the index cases (age at first surgery: 29.3 vs. 39.3 years, p<0.05; maximum size: 1.1 vs. 3.3 cm, p<0.001). There was also a decrease in the TNM staging and the proportion of patients who underwent inappropriate initial thyroid surgery (pN1: 31.6% vs. 100%, p<0.001; inappropriate surgery: 0% vs. 29%). Meanwhile, disease-free survival (DFS) increased (DFS: 100% vs. 58.1%, p<0.05). Both medullary thyroid carcinoma-specific (n=1) and PHEO-specific (n=5) deaths were reported during the study period. CONCLUSIONS: Our results further substantiate that gene scanning of all relevant RET exons is a powerful tool in the management of MEN2 patients, especially in asymptomatic carriers, and has led to earlier diagnosis and more complete initial treatment of patients with MEN2 in China.