Rationally Designed Fluorescence .OH Probe with High Sensitivity and Selectivity for Monitoring the Generation of .OH in Iron Autoxidation without Addition of H2O2

The first sensitive fluorescence ^.OH probe ( 1 ) that is capable of monitoring the generation of trace ^.OH in iron autoxidation is presented. The probe 1 was designed by utilizing both the unique aromatic hydroxylation and the electrophilicity of ^.OH, and prepared by incorporating a strong electron‐donating methoxy group into a cyanine fluorochrome to enhance the trapping ability for ^.OH. Reaction of 1 with ^.OH leads to a larger π‐conjugation formation and near‐infrared fluorescence off–on response. The capability of probe 1 has been demonstrated by imaging ^.OH generated in living cells under iron autoxidation as well as various stimuli, which reveals that the basal level of ^.OH in RAW 264.7 cells is lower than that in HeLa cells. The superior analytical performance of probe 1 makes it useful for detecting trace ^.OH in some critical physiological and pathological processes associated with iron autoxidation.     

Visible‐Light‐Driven Chemoselective Hydrogenation of Nitroarenes to Anilines in Water through Graphitic Carbon Nitride Metal‐Free Photocatalysis

Green and efficient procedures are essential for the chemoselective hydrogenation of functionalized nitroarenes to form industrially important anilines. Herein, it is shown that visible‐light‐driven, chemoselective hydrogenation of functionalized nitroarenes with groups sensitive to forming anilines can be achieved in good to excellent yields (82–100 %) in water under relatively mild conditions and catalyzed by low‐cost and recyclable graphitic carbon nitride. The process is also applicable to gram‐scale reaction, with a yield of aniline of 86 %. A study of the mechanism reveals that visible‐light‐induced electrons are responsible for the hydrogenation reactions, and thermal energy can also promote the photocatalytic activity. A study of the kinetics shows that this reaction possibly occurs through one‐step hydrogenation or stepwise condensation routes. A wide range of applications can be expected for this green, efficient, and highly selective photocatalysis system in reduction reactions for the synthesis of fine chemicals.     

A Porous Organic Poly(triphenylimidazole) Decorated with Palladium Nanoparticles for the Cyanation of Aryl Iodides

A new porous organic poly(triphenylimidazole), PTPI‐Me, was prepared through a Yamamoto self‐coupling reaction of 2,4,5‐tris‐(4‐bromophenyl)‐1‐methyl‐1H‐imidazole (TPI‐Me) in the presence of bis(1,5‐cyclooctadiene)nickel(0). The polymer was subsequently decorated with Pd nanoparticles (NPs) to afford a heterogeneous cyanation catalyst, Pd@PTPI‐Me. Pd NPs with an average diameter of 2.7 nm were grown within the PTPI‐Me framework, owing to the coordination of the imidazole rings to the Pd species. The resultant Pd@PTPI‐Me catalyst, with a Pd loading of 0.13 mmol g^?1, exhibited superior catalytic activity for the cyanation of aryl iodides. More importantly, the heterogeneous catalyst was also readily recycled and displayed negligible deactivation after five cycles.     

Synthesis of tetrahydroindolones and tetrahydrocarbazolones via palladium catalyzed C–H activation

The treatment of bromo homoallyl pyrrolyl/indolyl ketone derivatives with Pd(OAc)₂ in the presence of PPh₃ and Cs₂CO₃ in DMF resulted in the formation of tetrahydroindolones and tetrahydrocarbazolones in moderate to good isolated yields.     

Novel graphene oxide/bentonite composite for uranium(VI) adsorption from aqueous solution

A novel graphene oxide/bentonite composite (GO/bentonite) was synthesized and then characterized through powder X-ray diffraction, fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and energy dispersive spectroscopy. Adsorption achieved equilibrium within 10 min. Moreover, U(VI) adsorption on GO/bentonite was highly dependent on solution pH and independent of ionic strength. These characteristics suggested that inner-sphere surface complexes of U(VI) formed on GO/bentonite. The adsorption of U(VI) from aqueous solution on GO/bentonite was fitted to the pseudo-second-order and Freundlich isotherm models. The maximum sorption capacity of GO/bentonite was 234.19 mg g^?1 under neutral pH at 303 K. GO/bentonite is a potentially powerful adsorbent for the efficient removal of U(VI) from aqueous solutions.     

Effect of pretreatment on microstructure and photocatalytic activity of kaolinite/TiO<Subscript>2</Subscript> composite

Kaolinite/TiO₂ composites were prepared by using sol-gel method and raw kaolin, pretreated kaolinite and tetrabutyl titanate as the main raw materials. X-ray diffractometer, field-emission scanning electron microscope and infrared spectrometer analysis were carried out to characterize the phase composition and microstructure of the samples. The photocatalytic performance of the kaolinite/TiO₂ composites were evaluated by degrading the methylene blue (MB) and phenol aqueous solution, respectively. The results show that intercalation and exfoliation reduced the size and thickness of kaolinite particles. Acid treatment improved the distribution and the loading quantity of TiO₂ grains. When the kaolinite/TiO₂ composites were calcined at 500?°C, the tetragonal structure of anatase particles of 30–100?nm in size were obtained, but the exfoliated kaolinite crystals were damaged. The degradation rate of MB increased gradually with the extension of photocatalytic reaction time and the enhancement of photocatalyst dosage. The adsorption performance of acid-treated kaolinite/TiO₂ composite (AKT) was nearly the same as that of raw kaolin/TiO₂ composite (RKT), but that of the exfoliated kaolinite/TiO₂ composite (EKT) was the most excellent. The photocatalytic performance of AKT and EKT were better than that of RKT, and AKT exhibited the optimum property. Under a certain photocatalyst dosage and photocatalysis time, the absorption rate and the degradation rate decreased gradually with the enhancement of initial concentration of MB. Similar result was also acquired for the degradation of phenol. Both the acid treating and the exfoliating to kaolinite enhanced the photocatalytic performance of the kaolinite/TiO₂ composite photocatalysts, but acid treatment may be more helpful to the preparation of high performance kaolinite/TiO₂ composite photocatalyst.

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Cold atmospheric Plasma Jet-Generated Oxidized Derivatives of Tryptophan and Their Selective Effects on Murine Melanoma and Fibroblast Cells

Cold atmospheric pressure plasma is widely used in research for biomedical applications and is a promising therapy to selectively eradicate cancer cells. However, fundamental information related to the plasma modification of biomolecules in aqueous solution remains elusive. In this work, we studied the chemical basis of tryptophan (Trp) oxidation using an Ar plasma jet and investigated the effects of plasma-treated tryptophan (PTT) on cell viability. The results show that the main product of the Trp of plasma induced oxidation is a mixture of hydroxyl derivatives and hydroperoxides in aqueous form. The products result primarily from the hydroxyl radical (·OH) attacking the Trp, which can be explained by the interaction with both the aromatic and the pyrrole rings. We observed that the PTT has a different proliferation effect between the growth of the B16 melanoma cells and the L929 fibroblast cells. The experimental results indicated that the effect of the PTT is dose-dependent in the B16 cells, ranging from cell proliferation to cytotoxic damage with apoptosis. Furthermore, we examined the intracellular changes in hydrogen peroxide (H₂O₂) and superoxide radicals (\({\text{O}}_{2}^{{\bar{ \cdot }}}\)) following the Trp-derived treatment using the fluorescence probe method. Rigorous identification of the reactive oxygen species (ROS) produced by PTT in cells as \({\text{O}}_{2}^{{\bar{ \cdot }}}\) and H₂O₂ helped establish the cellular source of ROS. It is shown that the intracellular H₂O₂ might originate from the activation of NADPH. These results suggested that the amino acid and protein hydroperoxides may play a crucial role in the action of plasma on the biologic target.     

Liquid-phase oxidation of toluene to benzaldehyde with molecular oxygen catalyzed by copper nanoparticles supported on graphene

Highly-dispersed copper nanoparticles (Cu NPs) were fabricated on the surface of reduced graphene oxide via direct hydrazine hydrate reduction of Cu²⁺ in aqueous solution. Scanning electron microscope and transmission electron microscope images show that the Cu NPs are distributed on the surface of graphene nanosheets, and the average particle size was about 40 nm. The Cu NPs supported on graphene have high reaction activity for the oxidation of toluene to corresponding benzaldehyde. It was found that the selectivity reached 66.5% and the conversion of toluene reached 11.5%.     

Ion-pair recognition based on halogen bonding: a case of the crown-ether receptor with iodo-trizole moiety

The development of halogen-bond-based ditopic receptors capable of binding simultaneously both a cation and an anion has attracted recent research interest. In this work, the crown-ether receptor 1, which consists of an iodo-trizole moiety for anion recognition through halogen bonding and a Lewis-basic center for cation binding, was investigated using density functional theory calculations. The structural and energetic features for the complexes of 1 with single cations, single halide anions, and ion pairs were explored. Intermolecular interactions in these complexes were systematically analyzed by the atoms in molecules and noncovalent interaction index methods. The presence of the coordinated cation significantly increases the anion-binding affinity, while the binding of halide anions has a slight influence on the cation-binding affinity. Anti-cooperative effects were found in the ion-pair recognition of 1, due to the strong attraction between the two counterions in the complexes. The solvent weakens the interaction strength considerably, and anti-cooperativity becomes very small in solvent. The results reported in this work are of fundamental importance in the design of ion-pair receptors based on halogen bonding.     

Modeling liquid-liquid interface level in a horizontal three-phase separator with a bucket and weir

The flow behavior in a three-phase separator with a bucket and weir was analyzed, and a theoretical equation for calculating the liquid-liquid interface level (H_H) in gravity separation zone was derived. The analysis indicates that the H_H increases as the flow rate and the density ratio of heavy to light liquid increase, and decreases linearly with increasing height difference between heavy and light liquid overflow weirs. The calculated H_H under different operating conditions is in good agreement with the experimental. With the proposed equation, the thicknesses of heavy and light liquid layers can be calculated, and then the minimum lengths of two phase layers required for separation can be determined separately. From the minimum lengths it can be clearly indicated that the governing step of liquid-liquid separation is in heavy or light liquid layers, hence the sizing of the separator can be optimized.