Core-shell structure of sulphur vacancies-CdS@CuS: Enhanced photocatalytic hydrogen generation activity based on photoinduced interfacial charge transfer.

To regulate the charge flow of the photocatalyst in photocatalytic hydrogen reactions is highly desirable. In this study, a highly efficient sulphur vacancies-CdS@CuS core-shell heterostructure photocatalyst (denoted CdS-SV@CuS) was developed through the surface modification of CdS-sulphur vacancies (SV) nanoparticles by CuS based on photoinduced interfacial charge transfer (IFCT). This novel photocatalyst with modulated charge transfer was prepared by hydrothermal treatment and subsequent cation-exchange reactions. The SV confined in CdS and the IFCT facilitate the charge carrier's efficient spatial separation. The optimized CdS-SV@CuS(5%) catalyst exhibited a remarkably higher H2 production rate of 1654.53 µmol/g/h, approximately 6.7 and 4.0 times higher than those of pure CdS and CdS-SV, respectively. The high photocatalytic performance is attributed to the rapid charge separation, caused by the intimate interactions between CdS-SV and CuS in the core-shell heterostructure. This is the first time that a straightforward method is adopted to construct a metal sulphide core-shell structure for superior H2-production activity by IFCT.

Surface oxygen vacancies enriched FeOOH/Bi2MoO6 photocatalysis- fenton synergy degradation of organic pollutants.

To achieve rapid separation of photogenerated charges, increase photocatalytic degradation activity, a visible light-driven FeOOH/Bi2MoO6-OVs photocatalyst was designed and successfully fabricated via solvothermal synthesis and calcination. H2O2 was added under visible light irradiation to form a heterogeneous photocatalysis-Fenton synergy system. Using visible light irradiation, 10% FeOOH/Bi2MoO6-OVs had the best degradation activity. The removal efficiency of phenol was 100% within 3 h, which was 1.54 times and 1.33 times of the degradation efficiency of photocatalysis and Fenton alone, respectively. The catalyst has high removal activity for various pollutants and good cycle stability. Hydroxyl radicals and superoxide radicals have proven to be the main active substances and a reasonable catalytic mechanism was proposed. Surface oxygen vacancy can not only reduce the width of band gap, promote the separation and migration of photogenerated electron-hole pairs, but also make the OO bond of H2O2 elongate and weaken, making it easier to react with FeOOH and realize the synergistic effect of photocatalysis-Fenton. Simultaneously, the oxygen vacancies located near the valence band can capture holes, and the holes are rapidly transferred to the surface of the catalyst and participated in the degradation of pollutants.

Facile Fabrication of 3D Graphene⁻Silica Hydrogel Composite for Enhanced Removal of Mercury Ions.

Adsorption is a highly promising and widely used approach to remove Hg(II) ions from contaminated water. The key to this technology is exploring the effective adsorbent. The three-dimensional (3D) graphene as reduced graphene oxide hydrogel (rGH)-encapsulated silica gel (SG-PEI/rGH) was prepared by a moderate chemical reduction strategy using ascorbic acid. This composite structure was characterized by FTIR, XRD, and SEM analysis and used as adsorbents for Hg(II) ions. Its adsorption capacity toward Hg(II) ions was 266 mg/g and increased about 32% compared with the silica gel because of reduced graphene oxide hydrogel (rGH). Mechanism study showed that the high adsorption ability was due to the formation of an N⁻Hg complex with multi-amino groups on the surface of polyethyleneimine-modified silica gel (SG-PEI) and the rapid diffusion of adsorbed ions attributed to the rGH network structure. This composite SG-PEI/rGH would be a promising material for the removal of Hg(II) ions.

The Supramolecular Organogel Formed by Self-Assembly of Ursolic Acid Appended with Aromatic Rings.

Ursolic acid (UA) as a natural ursane-triterpenoid has rich pharmacological activities. We have found that it possesses aggregation properties and could self-assemble into organogels. Based on the aggregation property of ursolic acid in suitable solvents, its derivative appended with aromatic rings by amide groups was synthesized. The property of self-assembly into organogel was studied in this paper. The results revealed that this derivative could form supramolecular gel in halogenated benzene and also gelate chloroform in the presence of toluene or p-xylene. By Fourier-transform infrared spectra (FT-IR) and variable temperature proton nuclear magnetic resonance (¹H NMR), it was proved that intermolecular hydrogen bonding and π⁻π stacking interaction were the primary driving forces for the aggregation to form organogel.

Ag3PO4@UMOFNs Core-Shell Structure: Two-Dimensional MOFs Promoted Photoinduced Charge Separation and Photocatalysis.

Metal-organic frameworks (MOFs) are a new type of functional material that is self-assembled by metal ions and organic ligands. In this paper, a bimetal-organic framework was synthesized and stripped into two-dimensional nanosheets structure via an ultrasonic method. We coated the UMOFNs (ultrathinning MOFs into two-dimensional nanosheets) on Ag3PO4 nanoparticles to obtain Ag3PO4@UMOFNs core-shell photocatalysts. Under visible-light irradiation, the degradation of phenol was 100% within 16 min, and the degradation of biphenyl A was 98.9% within 20 min via Ag3PO4@UMOFNs (5 wt %). These values were 1.6- and 1.8-times higher than Ag3PO4, respectively. The activity of the Ag3PO4@UMOFNs increased due to the synergistic effects. The π-π bonds of the organic ligands and weak interactions between UMOFNs and Ag3PO4 collectively promote charge transfer. In addition, matching energy-level structures and a sufficiently large contact area accelerate the separation of the photogenerated charges and improve the activity. This remarkably improves the photocatalytic activity.

Highly ordered TiO2 nanotube arrays wrapped with g-C3N4 nanoparticles for efficient charge separation and increased photoelectrocatalytic degradation of phenol.

Novel graphitic carbon nitride nanoparticles (NPs)-wrapped TiO2 nanotube arrays (NTAs) (g-C3N4/TiO2) were fabricated by a two-step method including an electrochemical anodization technique followed by impregnation under vacuum using urea as precursor. The as-prepared photoelectrode exhibited outstanding photoelectric properties and excellent photelectrocatalytic (PEC) performance for the degradation of phenol under stimulated solar light, which was due to the enhanced light absorption property and improved charge separation efficiency. The introduction of g-C3N4 NPs strongly decreased the charge transfer resistance and boosted the charge separation efficiency of TiO2. The optimum ratio of the g-C3N4/TiO2 yielded a pronounced 4.18-fold higher photocurrent density than TiO2. Besides, the combination of g-C3N4 NPs could negatively shift for the flat band potential of TiO2, resulting in an enhanced reduction property for the photoelectrocatalytic degradation of organic pollutants. The PEC process for the degradation of phenol over g-C3N4/TiO2 was much higher than the sum of photocatalytic (PC) and electrocatalytic (EC) processes indicating that a photoelectric synergy was achieved on the as-prepared photoelectrode and resulting in an improved PEC performance for the composite photoelectrode.

Oil-in-Water Self-Assembled Synthesis of Ag@AgCl Nano-Particles on Flower-like Bi2O2CO3 with Enhanced Visible-Light-Driven Photocatalytic Activity.

In this work, a series of novel flower-like Ag@AgCl/Bi2O2CO3 were prepared by simple and feasible oil-in-water self-assembly processes. The phase structures of as-prepared samples were examined by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS), X-ray fluorescence spectrometer (XRF), etc. The characterization results indicated that the presence of Ag@AgCl did not affect the crystal structure, but exerted a great influence on the photocatalytic activity of Bi2O2CO3 and enhanced the absorption band of pure Bi2O2CO3. The photocatalytic activities of the Ag@AgCl/Bi2O2CO3 samples were determined by photocatalytic degradation of methylene blue (MB) under visible light irradiation. The Ag@AgCl (10 wt %)/Bi2O2CO3 composite showed the highest photocatalytic activity, degrading 97.9% MB after irradiation for 20 min, which is over 1.64 and 3.66 times faster than that of pure Ag@AgCl (calculated based on the equivalent Ag@AgCl content in Ag@AgCl (10 wt %)/Bi2O2CO3) and pure Bi2O2CO3, respectively. Bisphenol A (BPA) was also degraded to further prove the degradation ability of Ag@AgCl/Bi2O2CO3. Photocurrent studies indicated that the recombination of photo-generated electron-hole pairs was decreased effectively due to the formation of heterojunctions between flower-like Bi2O2CO3 and Ag@AgCl nanoparticles. Trapping experiments indicated that O2-, h⁺ and Cl° acted as the main reactive species for MB degradation in the present photocatalytic system. Furthermore, the cycling experiments revealed the good stability of Ag@AgCl/Bi2O2CO3 composites. Based on the above, a photocatalytic mechanism for the degradation of organic compounds over Ag@AgCl/Bi2O2CO3 was proposed.

Enhanced Visible Light Photocatalytic Degradation of Organic Pollutants over Flower-Like Bi2O2CO3 Dotted with Ag@AgBr.

A facile and feasible oil-in-water self-assembly approach was developed to synthesize flower-like Ag@AgBr/Bi2O2CO3 micro-composites. The photocatalytic activities of the samples were evaluated through methylene blue degradation under visible light irradiation. Compared to Bi2O2CO3, flower-like Ag@AgBr/Bi2O2CO3 micro-composites show enhanced photocatalytic activities. In addition, results indicate that both the physicochemical properties and associated photocatalytic activities of Ag@AgBr/Bi2O2CO3 composites are shown to be dependent on the loading quantity of Ag@AgBr. The highest photocatalytic performance was achieved at 7 wt % Ag@AgBr, degrading 95.18% methylene blue (MB) after 20 min of irradiation, which is over 1.52 and 3.56 times more efficient than that of pure Ag@AgBr and pure Bi2O2CO3, respectively. Bisphenol A (BPA) was also degraded to further demonstrate the degradation ability of Ag@AgBr/Bi2O2CO3. A photocatalytic mechanism for the degradation of organic compounds over Ag@AgBr/Bi2O2CO3 was proposed. Results from this study illustrate an entirely new approach to fabricate semiconductor composites containing Ag@AgX/bismuth (X = a halogen).

TDDFT study on the sensing mechanism of a fluorescent sensor for fluoride anion: Inhibition of the ESPT process.

The fluoride-sensing mechanism of a reported salicylaldehyde-based sensor (J. Photochem. Photobiol. B 2014, 138, 75) has been investigated by the TDDFT method. The present theoretical study indicates that there is an excited-state proton transfer (ESPT) process from the phenolic O-H moiety to the neighbor N atom in the sensor. The added fluoride anion could capture the proton in the O-H moiety and the corresponding phenolic anion is formed, which could inhibit the ESPT process. The experimental UV/Vis and fluorescence spectra are well reproduced by the calculated vertical excitation energies. Frontier molecular orbital analysis indicates that the local excited state of phenolic anion is responsible for its enhanced fluorescence. Due to this reason, the sensor can be used to sense fluoride anion by monitoring the fluorescent change.

Novel Cu2O quantum dots coupled flower-like BiOBr for enhanced photocatalytic degradation of organic contaminant.

Here we report a highly efficient novel photocatalyst consisting of Cu2O quantum dots (QDs) incorporated into three-dimensional (3D) flower-like hierarchical BiOBr (hereafter designated QDs-Cu2O/BiOBr), which were synthesized via a simple reductive solution chemistry route and applied to decontaminate the hazardous wastewater containing phenol and organic dyes. The deposition of Cu2O QDs onto the surface of the BiOBr was confirmed by structure and composition characterizations. The QDs-Cu2O/BiOBr composites exhibited superior activity for organic contaminant degradation under visible light and 3 wt% QDs-Cu2O/BiOBr composite showed the highest degrade rate for phenol and methylene blue (MB), which was 11.8 times and 1.4 times than that of pure BiOBr, indicated the QDs-Cu2O/BiOBr composite has the great potential application in purifying hazardous organic contaminant. The incorporated Cu2O QDs played an important role in improving the photocatalytic performance, due to the enhancement of visible light absorption efficiency as well as the efficient separation of the photogenerated charge carriers originating from the intimately contacted interface and the well-aligned band-structures, which was confirmed by the results of PL, photocurrent and EIS measurements. The possible photocatalytic mechanism was proposed based on the experiments and theoretical results.

Failure of FIV-infected cats to control Toxoplasma gondii correlates with reduced IL2, IL6, and IL12 and elevated IL10 expression by lymph node T cells.

Increased susceptibility to intracellular pathogens in HIV-infected individuals and FIV-infected cats is attributed to a defective T-helper 1 (Th1) immune response. However, little is known about specific cytokine responses to secondary pathogens. To address this question, control and FIV-infected cats were challenged with Toxoplasma gondii, and lymph node cells analyzed for cytokine mRNA expression. Twenty-four weeks post-FIV infection, prior to T. gondii challenge, IL2 and IL12 mRNAs were depressed, whereas IL10 and IFNgamma mRNAs were increased in CD4+ and CD8+ subsets. Following T. gondii challenge, control cats showed increased expression of IL2, IFNgamma, IL10, IL12, and IL6 mRNAs. In contrast, IL2, IL6, IFNgamma, and IL12 mRNAs were suppressed in FIV-T. gondii co-infected cats, whereas IL10 remained at the high prechallenge levels. IFNgamma and IL10 mRNAs were produced by both CD4+ and CD8+ cells in FIV-T. gondii cats. Elevated IL10 may suppress a Th1 cytokine response to T. gondii challenge.

Mouse CD20 expression and function.

CD20 plays a role in human B cell proliferation and is an effective target for immunotherapy. In this study, mouse CD20 expression and biochemistry were assessed for the first time using a new panel of CD20-specific mAb, with CD20 function assessed using CD20-deficient (CD20(-/-)) mice. CD20 expression was B cell restricted and was initiated during late pre-B cell development. The frequency and density of CD20 expression increased during B cell maturation in the bone marrow, with a subpopulation of transitional IgM(hi) B cells expressing higher CD20 levels than the majority of mature recirculating B cells. Transitional T1 B cells in the spleen also expressed high CD20 levels, providing a useful new marker for this B cell subset. In CD20(-/-) mice, immature and mature B cell IgM expression was approximately 20-30% lower relative to B cells from wild-type littermates. In addition, CD19-induced intracellular calcium responses were significantly reduced in CD20(-/-) B cells, with a less dramatic effect on IgM-induced responses. These results reveal a role for CD20 in transmembrane Ca(2+) movement in mouse primary B cells that complements previous results obtained using human CD20 cDNA-transfected cell lines. Otherwise, B cell development, tissue localization, signal transduction, proliferation, T cell-dependent antibody responses and affinity maturation were normal in CD20(-/-) mice. Thus, mouse and human CD20 share similar patterns of expression and function. These studies thereby provide an animal model for studying CD20 function in vivo and the molecular mechanisms that influence anti-CD20 immunotherapy.