Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction.

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO2 reduction performance after incorporating a Re(bpy)(CO)3Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF). These interactions ultimately lead the Re-f-COF isomer to function as an efficient CO2 reduction photocatalyst, while the Re-r-COF isomer shows minimal photocatalytic activity. These findings not only reveal the essential role linker chemistry plays in COF photophysical and photocatalytic properties but also offer a unique opportunity to design photosensitizers that can selectively direct charges.

Electrochemical Gelation of Metal Chalcogenide Quantum Dots: Applications in Gas Sensing and Photocatalysis.

ConspectusMetal chalcogenide quantum dots (QDs) are prized for their unique and functional properties, associated with both intrinsic (quantum confinement) and extrinsic (high surface area) effects, as dictated by their size, shape, and surface characteristics. Thus, they have considerable promise for diverse applications, including energy conversion (thermoelectrics and photovoltaics), photocatalysis, and sensing. QD gels are macroscopic porous structures consisting of interconnected QDs and pore networks in which the pores may be filled with solvent (i.e., wet gels) or air (i.e., aerogels). QD gels are unique because they can be prepared as macroscale objects while fully retaining the size-specific quantum-confined properties of the initial QD building blocks. The extensive porosity of the gels also ensures that each QD in the gel network is accessible to the ambient, leading to high performance in applications that require high surface areas, such as (photo)catalysis and sensing.Metal chalcogenide QD gels are conventionally prepared by chemical approaches. We recently expanded the toolbox for QD gel synthesis by developing electrochemical gelation methods. Relative to conventional chemical oxidation approaches, electrochemical assembly of QDs (1) enables the use of two additional levers for tuning the QD assembly process and gel structure: electrode material and potential, and (2) allows direct gel formation on device substrates to simplify device fabrication and improve reproducibility. We have discovered two distinct electrochemical gelation methods, each of which enables the direct writing of gels on an active electrode surface or the formation of free-standing monoliths. Oxidative electrogelation of QDs leads to assemblies bridged by dichalcogenide (covalent) linkers, whereas metal-mediated electrogelation proceeds via electrodissolution of active metal electrodes to produce free ions that link QDs by binding to pendant carboxylate functionalities on surface ligands (non-covalent linkers). We further demonstrated that the electrogel composition produced from the covalent assembly could be modified by controlled ion exchange to form single-ion decorated bimetallic QD gels, a new category of materials. The QD gels exhibit unprecedented performance for NO2 gas sensing and unique photocatalytic reactivities (e.g., the "cyano dance" isomerization and the reductive ring-opening arylation). The chemistry unveiled during the development of electrochemical gelation pathways for QDs and their post-modification has broad implications for guiding the design of new nanoparticle assembly strategies and QD gel-based gas sensors and catalysts.

CdS Quantum Dot Gels as a Direct Hydrogen Atom Transfer Photocatalyst for C-H Activation.

Here, we report CdS quantum dot (QD) gels, a three-dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d-HAT) photocatalyst for C-H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α-amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C-H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C-H bonds are activated by the photoexcited CdS QD gel via a d-HAT mechanism. This d-HAT mechanism is supported by the linear correlation between the logarithm of the C-H bond activation rate constant and the C-H bond dissociation energy (BDE) with a Brønsted slope α=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C-H activation.

Quantum dot gels as efficient and unique photocatalysts for organic synthesis.

Here we report CdS quantum dot (QD) gels as highly efficient and unique photocatalysts for organic synthesis. We found that the photocatalytic activity of CdS QD gel was superior to phosphine oxide- and thiolate-capped CdS QDs for dehalogenation and α-amine arylation reactions because of the high accessibility of its surface sites to the substrates. In addition, we discovered the unique reactivity of CdS QD gel for ring-opening during α-amine arylation of tetrahydroisoquinoline via the reductive cleavage of C-N bonds. QD gels provide new opportunities in photocatalysis due to their unique surface interactions with the substrates or intermediates.

Elimination and ecotoxicity evaluation of phthalic acid esters from textile-dyeing wastewater.

Phthalic acid esters (PAEs), presented in fabrics, surfactants and detergents, were discharged into the ecosystem during textile-dyeing wastewater treatment and might have adverse effects on water ecosystems. In this study, comprehensive investigations of the content and component distributions of 12 PAEs across different units of four textile-dyeing wastewater plants were carried out in Guangdong Province, China. Ecotoxicity assessments were also conducted based on risk quotients (RQs). On average, 93.54% TOC and 80.14% CODCr were removed following treatment at the four plants. The average concentration of Σ12PAEs in effluent was 11.78 µg/L. PAEs with highest concentrations were dimethylphthalate (6.58 µg/L), bis(2-ethylhexyl)phthalate (2.23 µg/L), and dibutylphthalate (1.98 µg/L). The concentrations of the main toxic PAEs were 2.23 µg/L (bis(2-ethylhexyl)phthalate), 0.19 µg/L (diisononylphthalate) and 0.67 µg/L (dinoctylphthalate); corresponding RQs were 1.4, 0.55, and 0.54 for green algae, respectively. The RQs of Σ12PAEs in effluent of the four plants were >0.1, indicating that Σ12PAEs posed medium or higher ecological risk to fish, Daphnia and green algae. Physicochemical-biochemical system was found to be more effective than biochemical-physicochemical system for TOC and CODCr removal, because pre-physicochemical treatment helped to remove macromolecular organic substances, and reduced the competition with other pollutants during biochemical treatment. However, biochemical-physicochemical system was more effective than physicochemical-biochemical system for elimination of PAEs and for detoxification, since the biochemical treatment might produce the toxic PAEs that could helpfully be settled by post-physicochemical treatment. Moreover, ecotoxicity evaluation was recommended for current textile-dyeing wastewater treatment plants.

[Investigation on human Cryptosporidium infection in local area of Anhui Province].

OBJECTIVE: To investigate the status of Cryptosporidium infection in the population in the local area of Anhui Province, and discuss the risk factors of the infection, so as to provide the evidence for the prevention and treatment of cryptosporidiosis. METHODS: Qianshan County and Lingbi County of Anhui Province were selected as investigation spots, and the oocysts of Cryptosporidium in the feces of the investigation objects and the specific IgG antibody against Cryptosporidium in the serum were checked by using the pathogenic modified acid fast staining method and ELISA, respectively, so as to determine the status of Cryptosporidium infection in these investigation objects. At the same time, the questionnaire surveys were conducted in the investigation objects so as to know about the risk factors of Cryptosporidium infection. RESULTS: A total of 668 people were investigated in the two counties, 635 people received etiological examinations, and 15 people were positive with the positive rate of 2.36%; 642 people received serological examinations, and 140 people were positive with the positive rate of 21.81%; 628 people received pathogenic and serological examinations at the same time, and the examination results of the both methods showed that 12 people were positive (there were 4 people in Qianshan County and 8 people in Lingbi County) , and the positive rate was 1.94%. The rates of Cryptosporidium infection in the population of Qianshan County and Lingbi County were 1.24% (4/322) and 2.71% (8/295) respectively, and the difference had no statistical significance (P > 0.05). The single factor analysis found that the rate of Cryptosporidium infection was higher in the children and diarrhea patients; the multivariate logistics regression analysis indicated that the rate of Cryptosporidium infection was higher in the people who bred poultry and the diarrhea patients. CONCLUSIONS: The positive rate of serum antibody of Cryptosporidium in the population of the local area of Anhui Province is higher, which indicates that the previous infection is serious, and the rate of Cryptosporidium infection in human is relative to the age, diarrhea and whether there are poultries to be bred in the family, which is worthy of attention in the future prevention and treatment.

Genotypes and mouse virulence of Toxoplasma gondii isolates from animals and humans in China.

BACKGROUND: Recent population structure studies of T. gondii revealed that a few major clonal lineages predominated in different geographical regions. T. gondii in South America is genetically and biologically divergent, whereas this parasite is remarkably clonal in North America and Europe with a few major lineages including Types I, II and III. Information on genotypes and mouse virulence of T. gondii isolates from China is scarce and insufficient to investigate its population structure, evolution, and transmission. METHODOLOGY/PRINCIPAL FINDINGS: Genotyping of 23 T. gondii isolates from different hosts using 10 markers for PCR-restriction fragment length polymorphism analyses (SAG1, SAG2, SAG3, BTUB, GRA6, c22-8, c29-2, L358, PK1 and Apico) revealed five genotypes; among them three genotypes were atypical and two were archetypal. Fifteen strains belong to the Chinese 1 lineage, which has been previously reported as a widespread lineage from swine, cats, and humans in China. Two human isolates fall into the type I and II lineages and the remaining isolates belong to two new atypical genotypes (ToxoDB#204 and #205) which has never been reported in China. Our results show that these genotypes of T. gondii isolates are intermediately or highly virulent in mice except for the strain TgCtwh6, which maintained parasitemia in mice for 35 days post infection although it possesses the uniform genotype of Chinese 1. Additionally, phylogenetic network analyses of all isolates of genotype Chinese 1 are identical, and there is no variation based on the sequence data generated for four introns (EF1, HP2, UPRT1 and UPRT7) and two dense granule proteins (GRA6 and GRA7). CONCLUSION/SIGNIFICANCE: A limited genetic diversity was found and genotype Chinese 1 (ToxoDB#9) is dominantly circulating in mainland China. The results will provide a useful profile for deep insight to the population structure, epidemiology and biological characteristics of T. gondii in China.