A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide.

The design and synthesis of metal-organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive perylenediimides-based (PDI) carboxylate ligand N,N'-di(3',3",5',5"-tetrakis(4-carboxyphenyl))-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide (Cl-PDI-TA) and use it to successfully synthesize a novel Zr(IV)-based MOF 1 constructed from [Zr6 O8 (H2 O)8 ]8+ clusters bridged by Cl-PDI-TA ligands. Structural analysis revealed that Zr-MOF 1 manifests a 3D framework with (4,8)-connected csq topology and possesses triangular channels of ~17 Šand mesoporous hexagonal channels of ~26 Šalong c-axis. Moreover, the synthesized Zr-MOF 1 exhibits visible-light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor. When Zr-MOF 1 was used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light, it could afford the corresponding sulfoxides with high yield and selectivity. Experimental results demonstrated that the substrate sulfides could be fixed in the pores of 1 and directly transformed to the products sulfoxides in the solid state. Furthermore, the mechanism for the photocatalytic transformation was also investigated and the results revealed that the singlet oxygen (1 O2 ) and superoxide radical (O2 ⋅- ) generated by the energy transfer and electron transfer from the photoexcited Zr-MOF to oxidants were the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI-based MOFs for further study on photocatalytic reactions.

Electricity production and key exoelectrogens in a mixed-culture psychrophilic microbial fuel cell at 4 °C.

The electricity production via psychrophilic microbial fuel cell (PMFC) for wastewater treatment in cold regions offers an alternative to avoid the unwanted methane dissolution of traditional anaerobic fermentation. But, it is seldom reported by mixed-culture, especially closed to 0 °C. Thus, a two-chamber mixed-culture PMFC at 4 °C was successfully operated in this study using acetate as an electron donor. The main results demonstrated a good performance of PMFC, including the maximum voltage of 513 mV at 1000 Ω, coulombic efficiency of 53%, and power density of 689 mW/m2. The cyclic voltammetry curves of enriched biofilm showed a direct electron transfer pathway. These good performances of mixed-culture PMFC were due to the high psychrophilic activity of enriched biofilm, including exoelectrogens genera of Geobacter (6.1%), Enterococcus (17.5%), and Clostridium_sensu_stricto_12 (3.8%). Consequently, a mixed-culture PMFC provides a reasonable strategy to enrich exoelectrogens with high activity. For low-temperature regions, the mixed-culture PMFC involved biotechnologies shall benefit energy generation and valuable chemical production in the future. KEY POINTS: • PMFC showed a maximum voltage of around 513 mV under a resistance of 1000 Ω. • The coulombic efficiency was 53% and the max power density was 689 mW/m2. • Geobacter, Enterococcus, and Clostridium_sensu_stricto_12 were key exoelectrogens.

Pillar-Layered Metal-Organic Frameworks for Sensing Specific Amino Acid and Photocatalyzing Rhodamine B Degradation.

Metal-organic frameworks (MOFs) have presented potential for detection of specific species and catalytic application due to their diverse framework structures and functionalities. In this work, two novel pillar-layered MOFs [Cd6(DPA)2(NTB)4(H2O)4]n·n(DPA·5DMA·H2O) (1) and [Cu2(DPA)(OBA)2]n·n(2.5DMF·H2O) (2) [DPA = 2,5-di(pyridin-4-yl)aniline, H3NTB = 4,4',4''-nitrilotribenzoic acid, H2OBA = 4,4'-oxydibenzoic acid, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide] were successfully synthesized and structurally characterized. Both 1 and 2 have three-dimensional framework structures. The fluorescent property of 1 makes it possible for sensing specific amino acid such as L-glutamic acid (Glu) and L-aspartic acid (Asp). While MOF 2 was found to be suitable for photocatalytic degradation of Rhodamine B (RhB) in the presence of H2O2. The results imply that MOFs are versatile and metal centers are important in determining their properties.

Effect of polystyrene microplastics on the degradation of sulfamethazine: The role of persistent free radicals.

Microplastic (MPs) pollution is increasingly becoming a global environmental problem. MPs entering the environment are subjected to various aging processes, among which photoaging is the most important process leading to MPs oxidation. Persistent free radicals (EPFRs) are formed on the surface of MPs during photoaging, but it is not clear whether EPFRs on the surface of MPs can produce reactive oxygen species (ROS) and thus degrade organic pollutants. In this study, with polystyrene (PS) as the representative plastic and sulfamethazine (SMT) degradation as the target pollutant, the effect and mechanism of light-induced PS on SMT degradation were investigated by experiment and theoretical calculation. It was found that PS can stimulate the production of ROS under sunlight, which can significantly improve the degradation rate of SMT. Through quenching experiment and free radical trapping experiment, it was found that the mechanism of PS promoting the degradation of SMT was mainly due to the production of hydroxyl radical (·OH) in the system, and ·OH was the main ROS species affecting the oxidative degradation of SMT. The characterization results show that the high reactive oxygen generation ability of PS under solar irradiation was due to the abundant photoactive oxidation functional groups on its surface. In addition, the key reaction sites of SMT were predicted by density functional theory (DFT) calculation. The results of different calculations consistently showed that the sulfonamide group of SMT, the pyrimidine heterocycle and the amino group of aniline are the reaction sites of ·OH priority attack. The main intermediates were determined by UHPLC-HRMS/MS. Combined with theoretical calculation, it was proposed that the oxidative degradation pathway of SMT mainly includes SN bond cleavage, SMILES rearrangement and SO2 group removal. This study clarified the effect of PS on the degradation of organic pollutants under light, and provided theoretical guidance for the degradation mechanism.

Fluorescent Zn(II) frameworks with multicarboxylate and pyridyl N-donor ligands for sensing specific anions and organic molecules.

Three novel fluorescent Zn(II) frameworks, namely [Zn(DPA)(NDA)]2·2DMF (1), [Zn2(DPA)(OBA)2]·2DMF·4H2O (2) and [Zn(DPA)(HNTB)]·H2O (3) (DPA = 2,5-di(pyridin-4-yl)aniline, H2NDA = 1,4-naphthalenedicarboxylic acid, H2OBA = 4,4'-oxydibenzoic acid, H3NTB = 4,4',4''-nitrilotribenzoic acid, DMF = N,N-dimethylformamide), were successfully fabricated and structurally characterized. Due to the variety of organic linkers, 1-3 exhibit varied topologies: 1 is a 4-c three-dimensional (3D) framework with {65·8} topology, 2 is a 6-c 3D net with point symbol of {44·610·8}, and 3 is a 4-c two-dimensional network that further stacks into a 3D structure by hydrogen bonding interactions with {44·62} topology. Experiments related to fluorescence show that 1-3 can be utilized to quickly identify specific anions of CrO42-/Cr2O72-, and organic molecules such as 2,4,6-trinitrophenol and benzaldehyde.

Metal-organic frameworks incorporating azobenzene-based ligands as a heterogeneous Lewis-acid catalyst for cyanosilylation of imines.

In this work, two novel metal-organic frameworks (MOFs) were synthesized by the reaction of azobenzene-based ligands and Zn(NO3)2/CdCO3 under solvothermal conditions with the formula of {[Zn2(abtc)(azpy)(H2O)2]·4H2O} n (1) and {[Cd(abtc)0.5(azpy)0.5(H2O)]·3H2O} n (2) (H4abtc = 3,3',5,5'-azobenzene tetracarboxylic acid, azpy = 4,4'-azobipyridine). According to the single-crystal X-ray diffraction (SC-XRD) analysis, complexes 1 and 2 possessed quite similar structures except for the coordination modes of the central metal nodes attributed to the difference between the cationic radius of Zn(ii) and Cd(ii). The Zn(ii) cations in 1 adopted a distorted seesaw coordination geometry and the coordination between Zn(ii) and organic linkers gave two-dimensional (2D) coordination networks, while the Cd(ii) cations in 2 could also bind with the carboxylate groups from neighboring coordination networks to form a three-dimensional (3D) coordination framework. Furthermore, complexes 1 and 2 showed high catalytic activity as heterogeneous Lewis-acid catalysts towards the cyanosilylation of imines with satisfactory reusability under mild conditions and the similar catalytic performance of 1 and 2 could be attributed to the similarity in their structures. A prudent mechanism has been proposed as well to elucidate the role of complexes 1 and 2 in the catalytic process.

Luminescent silver(i) complexes with pyrazole-tetraphenylethene ligands: turn-on fluorescence due to the coordination-driven rigidification and solvent-oriented structural transformation.

A new tetrapyrazole-modified tetraphenylethene (TPE) ligand L was designed and found to display "turn-on" fluorescence when it combines with Ag+ ions in dilute solution by restricting intramolecular rotation of TPE. A series of Ag complexes 1-7 were obtained, and they exhibit excellent fluorescence properties in the solid state. Compared with PF6-, the silver complex with the CF3SO3- anion can further enhance its fluorescence due to the transformation of its structure from Ag2L (2) to Ag4L2 (3). As zero-dimensional complexes, 1 and 3 have excellent piezochromic properties with a color change from blue to green. Furthermore, structural changes of 1 and 3 to the corresponding three-dimensional frameworks 4 and 5 occur upon immersing in ethanol. In addition, 1 can act as a potential fluorescent probe for sensing nitrile compounds.

Performance of a novel IAHD-DSR process with methane and sulfide as co-electron donors.

A novel integrated autotrophic and heterotrophic denitrification- denitrifying sulfide removal (IAHD-DSR) process was established in this study for biogas desulfurization to simultaneously remove nitrogen in wastewater. The study demonstrated that the system could utilize methane and sulfide as co-electron donors to replace organic carbon source in IAHD process. Three batch tests (B1, B2 and B3) were set up with IAHD sludge to explore how the novel process works. According to mass balance in B2, methane oxidation and sulfide oxidation contributed 18.75 % and 71.25 % to nitrate removal, respectively; however, the contribution of methane oxidation to total nitrogen (TN) removal reached 84.36 %. Sulfide was mainly responsible for the reduction of nitrate to nitrite, while the methane was for nitrite to nitrogen gas in the presence of insufficient sulfide as electron donors. The TN removal in B2 was almost the same as in normal IAHD-DSR process B3-C. The functional genes mcrA and pmoA responsible for methane oxidation were detected in all three batches, with the abundance of 2.23 ×106 copies/(g dry soil) for mcrA in B1 being the highest in three batches. The sulfide addition in B2 increased the abundance of gene pmoA, indicating the enhancement of nitrite reduction coupled with methane oxidation.

Lack of associations between the FTO polymorphisms and gestational diabetes: A meta-analysis and trial sequential analysis.

BACKGROUND: Molecular epidemiological studies have sought associations between Fat mass and obesity associated (FTO) gene polymorphisms and gestational diabetes mellitus (GDM) risk, but findings are inconsistent. Hence, we performed a meta-analysis to clarify this problem. METHODS: Case-control studies reporting the relationship of three FTO polymorphisms (rs9939609, rs8050136, and rs1421085) and GDM published before June 2018 were searched in 6 electronic databases such as PubMed and Embase. Pooled odds ratios (ORs) with 95% confidence intervals (CIs) were used to assess the strength of associations. Trial sequential analysis (TSA) was performed to evaluate the type 1 and type 2 errors. RESULTS: A total of 5 studies involving 703 GDM cases and 2700 controls for rs9939609, 3 studies involving 1144 GDM cases and 909 controls for rs8050136, and 2 studies involving 207 GDM cases and 205 controls for rs1421085, were included in the meta-analysis. No association was observed between the three polymorphisms with the GDM risk under all genetic models. For example, the ORs and its 95% CIs under dominant genetic model were 0.88 (0.59, 1.33) for rs9939609, 1.11 (0.91, 1.35) for rs8050136, and 0.91 (0.58, 1.41) for rs1421085, respectively. Under TSA, there are insufficient levels of evidence for all of these three polymorphisms. CONCLUSION: The present meta-analysis provides statistical evidence indicating a lack of association between FTO polymorphismsand GDM risk. More studies with larger sample size are needed to confirm these null associations.