The water oxidation reaction (WOR), which is pivotal to storing energy in chemical bonds, requires a catalyst to overcome its inherent kinetic barrier. In bulk solutions, sacrificial oxidants (SOs) can regenerate the catalysts to ensure that the homogeneous WOR can be operated with long-term consistent performance. To implement this strategy for organic WOR systems, we modified four common SOs with tetra--butylammonium ([NBu])─[NBu][Ce(NO)], [NBu][IO], [NBu][HSO], and [NBu][SO]─and examined their chemical stability and electrochemical behaviors in various organic solvents.
View Article and Find Full Text PDFInterferenceless-coded aperture correlation holography (I-COACH) is a promising single-shot 3D imaging method in which a coded phase mask (CPM) is used to encode 3D information about an object into an intensity distribution. However, conventional CPM encoding methods usually lead to intensity dilution, especially in the recording of point spread holograms (PSHs), resulting in low-resolution reconstruction of I-COACH. Here, we propose accelerating quad Airy beams with four mainlobes as a point response to enable weak diffraction propagation and a sharp maximum intensity in the transverse direction.
View Article and Find Full Text PDFElectrochemical water oxidation is known as the anodic reaction of water splitting. Efficient design and earth-abundant electrocatalysts are crucial to this process. Herein, we report a family of catalysts (-) bearing bis(benzimidazole)pyrazolide ligands ( - ).
View Article and Find Full Text PDFElectrical stimulation (ES) is proposed as a therapeutic solution for managing chronic wounds. However, its widespread clinical adoption is limited by the requirement of additional extracorporeal devices to power ES-based wound dressings. In this study, a novel sandwich-structured photovoltaic microcurrent hydrogel dressing (PMH dressing) is designed for treating diabetic wounds.
View Article and Find Full Text PDFIn this study, dinuclear cobalt complexes (1 and 2) featuring bis(benzimidazole)pyrazolide-type ligands (H L and Me L) were prepared and evaluated as molecular electrocatalysts for water oxidation. Notably, 1 bearing a non-innocent ligand (H L) displayed faster catalytic turnover than 2 under alkaline conditions, and the base dependence of water oxidation and kinetic isotope effect analysis indicated that the reaction mediated by 1 proceeded by a different mechanism relative to 2. Spectroelectrochemical, cold-spray ionization mass spectrometric and computational studies found that double deprotonation of 1 under alkaline conditions cathodically shifted the catalysis-initiating potential and further altered the turnover-limiting step from nucleophilic water attack on (H L)Co (superoxo) to deprotonation of (L)Co (OH) .
View Article and Find Full Text PDFThe utilization of earth-abundant low-toxicity metal ions in the construction of highly active and efficient molecular catalysts promoting the water oxidation reaction is important for developing a sustainable artificial energy cycle. However, the kinetic and thermodynamic properties of the currently available molecular water oxidation catalysts (MWOCs) have not been comprehensively investigated. This Review summarizes the current status of MWOCs based on first-row transition metals in terms of their turnover frequency (TOF, a kinetic property) and overpotential (η, a thermodynamic property) and uses the relationship between log(TOF) and η to assess catalytic performance.
View Article and Find Full Text PDFThe functionalization of methane, ethane, and other alkanes derived from fossil fuels is a central goal in the chemical enterprise. Recently, a photocatalytic system comprising [CeCl(OR)] [Ce, cerium(IV); OR, -OCH or -OCClCH] was disclosed. The system was reportedly capable of alkane activation by alkoxy radicals (RO•) formed by Ce-OR bond photolysis.
View Article and Find Full Text PDFThe selective reduction of O, typically with the goal of forming HO, represents a long-standing challenge in the field of catalysis. Macrocyclic transition-metal complexes, and cobalt porphyrins in particular, have been the focus of extensive study as catalysts for this reaction. Here, we show that the mononuclear Co-tetraarylporphyrin complex, Co(por) (por = meso-tetra(4-methoxyphenyl)porphyrin), catalyzes either 2e/2H or 4e/4H reduction of O with high selectivity simply by changing the identity of the Brønsted acid in dimethylformamide (DMF).
View Article and Find Full Text PDFA soluble, bis-ketiminate-ligated Co complex [Co(NO)] was recently shown to catalyze selective reduction of O to HO with an overpotential as low as 90 mV. Here we report experimental and computational mechanistic studies of the Co(NO)-catalyzed O reduction reaction (ORR) with decamethylferrocene (Fc*) as the reductant in the presence of AcOH in MeOH. Analysis of the Co/O binding stoichiometry and kinetic studies support an O reduction pathway involving a mononuclear cobalt species.
View Article and Find Full Text PDFA series of mononuclear pseudomacrocyclic cobalt complexes have been investigated as catalysts for O reduction. Each of these complexes, with Co reduction potentials that span nearly 400 mV, mediate highly selective two-electron reduction of O to HO (93-99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first-order dependence on [Co] and [AcOH], but no dependence on [O] or [Fc*].
View Article and Find Full Text PDFGuang Pu Xue Yu Guang Pu Fen Xi
November 2016
The conventional qualitative analysis of near infrared spectroscopy (NIR) commonly uses one single classification model. This paper focused on the fusion of multiple classifiers based on different single classifiers by using the fused classifier to determine different varieties of red-wines. NIR spectra of 170 red-wine samples were collected by using Fourier transform near-infrared spectrometer.
View Article and Find Full Text PDFT-helper 17 (Th17) cells, a recently identified CD4+ T subset with a unique characteristic to produce Interleukin-17 (IL-17), are critical for the development of autoimmune diseases such as multiple sclerosis, in which IL-23 plays an important role in the differentiation of Th17 cells through IL-23/IL-23-receptor/STAT3 pathway. Previously, soluble recombinant human IL-23 receptor cytokine-binding homology region (hIL23R-CHR) was constructed in our laboratory to neutralize IL-23 and inhibit murine Th17 development in vitro. Herein we present that hIL23R-CHR could inhibit both differentiation and function of human/murine Th17 cells.
View Article and Find Full Text PDFMetastable TiO(2) polymorphs are more promising materials than rutile for specific applications such as photocatalysis or catalysis support. This was clearly demonstrated for the anatase phase but still under consideration for brookite, which is difficult to obtain as pure phase. Moreover, the surface doping of anatase with lanthanum ions is known to both increase the thermal stability of the metastable phase and improve its photocatalytic activity.
View Article and Find Full Text PDFA series of hemilabile ligands of alpha-aminoaldimines and their methylpalladium complexes have been prepared and characterized. Neutral square-planar methylpalladium complexes in the form of [R(1)R(2)NCMe(2)CH horizontal lineNR]Pd(Me)Cl (R = Me, R(1) = R(2) = Me (3a); R = Me, R(1) = R(2) = Et (3b); R = Et, R(1) = R(2) = Me (4a); R = (n)Pr, R(1) = R(2) = Me (5a); R = (i)Pr, R(1) = R(2) = Me (6a); R = (i)Pr, R(1) = R(2) = Et (6b); R = (i)Pr, (R(1), R(2)) = c-C(4)H(8) (6c); R = (i)Pr, R(1) = (i)Pr, R(2) = H (6d); R = (i)Pr, R(1) = (t)Bu, R(2) = H (6e); R = (t)Bu, R(1) = R(2) = Me (7a); R = (t)Bu, R(1) = R(2) = Et (7b); R = (t)Bu, (R(1), R(2)) = c-C(4)H(8) (7c); R = (t)Bu, R(1) = (i)Pr, R(2) = H (7d); R = (t)Bu, R(1) = (t)Bu, R(2) = H (7e); R = Ph, R(1) = R(2) = Me (8a); R = Ph, R(1) = R(2) = Et (8b)) show geometrical isomerism. The relative ratios of trans/cis isomers appear to be predominated by the steric hindrance between the Pd-bound methyl group and imino or amino substituents (R and R(1) and R(2)).
View Article and Find Full Text PDFHuan Jing Ke Xue
November 2008
High algae-laden water was treated respectively by single-recycle and step-recycle counter current flotation. The results indicate that step-recycle mode of dissolved air water can strengthen capturing of bubbles and flocs association suspension bed, and extend the collision time of smaller flee and bubble because of reducing the thickness of suspension bed and increasing that of transition bed. Given the condition that other parameters were same, the biggest hydraulic loading of single-recycle could reach 11 m/h, and that of step-recycle could reach 17 m/h which is increased by 50%.
View Article and Find Full Text PDFMicrocysits aeruginosa (MA) was removed by polyaluminium chloride (PAC) in the coagulation-flotation process. The test studied removing effect and morphological characteristics of PAC-MA flocs in the different coagulation conditions and discussed the correlation of them. Fractal dimension was measured by image analysis.
View Article and Find Full Text PDFObjective: To observe the effect and mechanism of Chinese herbs in the treatment of taeniasis.
Methods: Five hundred and forty-eight cases of taeniasis were treated with Binlang Chengqi Decoction (BLCQD). The tapeworm scolices of ten cases were observed by electron microscope (EM).