Hollow-Architected Heteroatom-Doped Carbon-Supported Nanoscale Cu/Co as an Enhanced Magnetic Activator for Oxone to Degrade Toxicants in Water.

Even though transition metals can activate Oxone to degrade toxic contaminants, bimetallic materials possess higher catalytic activities because of synergistic effects, making them more attractive for Oxone activation. Herein, nanoscale CuCo-bearing N-doped carbon (CuCoNC) can be designed to afford a hollow structure as well as CuCo species by adopting cobaltic metal organic frameworks as a template. In contrast to Co-bearing N-doped carbon (CoNC), which lacks the Cu dopant, CuCo alloy nanoparticles (NPs) are contained by the Cu dopant within the carbonaceous matrix, giving CuCoNC more prominent electrochemical properties and larger porous structures and highly nitrogen moieties. CuCoNC, as a result, has a significantly higher capability compared to CoNC and Co3O4 NPs, for Oxone activation to degrade a toxic contaminant, Rhodamine B (RDMB). Furthermore, CuCoNC+Oxone has a smaller activation energy for RDMB elimination and maintains its superior effectiveness for removing RDMB in various water conditions. The computational chemistry insights have revealed the RDMB degradation mechanism. This study reveals that CuCoNC is a useful activator for Oxone to eliminate RDMB.

Preparation of Polyacrylonitrile-Based Immobilized Copper-Ion Affinity Membranes for Protein Adsorption.

A polyacrylonitrile (PAN)-based immobilized metal-ion affinity membrane (IMAM) was prepared with a high capacity for protein adsorption. PAN was selected as the substrate due to its excellent thermal and chemical stability. The cyano groups on the PAN membrane were substituted with carboxyl groups, followed by reactions with ethylenediamine (EDA) and ethylene glycol diglycidyl ether (EGDGE) to produce the terminal epoxy groups. The chelating agent iminodiacetic acid (IDA) was then bound to the modified PAN membrane and further chelated with copper ions. The immobilized copper ion amount of membrane was analyzed to obtain the optimal reaction conditions, which were 60 °C/3 h for EDA coupling and 60 °C/4 h for EGDGE grafting. Furthermore, under the use of minor IDA and copper ion concentrations, the immobilized copper ion capacity of the IMAM was 4.8 µmol/cm2 (253.4 µmol/mL, or 1.47 µmol/mg). At a neutral pH, the cationic lysozyme exhibited a large adsorption capacity with the IMAM (1.96 µmol/mL), which was most likely multilayer binding, whereas the adsorption capacity for bovine serum albumin (BSA) and histidine-tagged green fluorescent protein (GFP-His6) was 0.053 µmol/mL and 0.135 µmol/mL, respectively, with a monolayer adsorption arrangement. The protein desorption efficiency was greater than 95%, implying that the prepared IMAM could be reused for protein adsorption.

Boosting elimination of sunscreen, Tetrahydroxybenzophenone (BP-2), from water using monopersulfate activated by thorny NanoBox of Co@C prepared via the engineered etching strategy: A comparative and mechanistic investigation.

As sunscreens, benzophenones (BPs), are regarded as emerging contaminants, most of studies are focused on removal of 2-hydroxy-4-methoxybenzophenone (BP-3), which, however, has been employed for protecting skin. Another major class of BPs, which is used to prevent UV-induce degradation in various products, is completely neglected. Thus, this present study aims to develop a useful advanced oxidation process (AOP) for the first time to eliminate such a class of BP sunscreens from contaminated water. Specifically, 2,2',4,4'-Tetrahydroxybenzophenone (BP-2) would be focused here as BP-2 is intensively used in perfumes, lipsticks, and plastics for preventing the UV-induced degradation. As monopersulfate (MPS)-based AOP is practical for degrading emerging contaminants, a facile nanostructured cobalt-based material is then developed for maximizing catalytic activities of MPS activation by immobilizing Co nanoparticles onto carbon substrates. In particular, ZIF-67 is employed as a template, followed by the etching and carbonization treatments to afford the thorny nanobox of Co@C (TNBCC) with the hollow-nanostructure. In comparison to the solid (non-hollow) nanocube of Co@C (NCCC) from the direct carbonization of ZIF-67, TNBCC possesses not only the excellent textural features, but also superior electrochemical properties and highly reactive surfaces, making TNBCC exhibit the significantly higher catalytic activity than NCCC as well as Co3O4 in activating MPS to degrade BP-2. Mechanisms of BP-2 degradation are also elucidated and ascribed to both radical and non-radical routes. These advantageous features make TNBCC a useful catalyst of activating MPS in BP-2 degradation.

Modulating Direct Growth of Copper Cobaltite Nanostructure on Copper Mesh as a Hierarchical Catalyst of Oxone Activation for Efficient Elimination of Azo Toxicant.

As cobalt (Co) has been the most useful element for activating Oxone to generate SO4•-, this study aims to develop a hierarchical catalyst with nanoscale functionality and macroscale convenience by decorating nanoscale Co-based oxides on macroscale supports. Specifically, a facile protocol is proposed by utilizing Cu mesh itself as a Cu source for fabricating CuCo2O4 on Cu mesh. By changing the dosages of the Co precursor and carbamide, various nanostructures of CuCo2O4 grown on a Cu mesh can be afforded, including nanoscale needles, flowers, and sheets. Even though the Cu mesh itself can be also transformed to a Cu-Oxide mesh, the growth of CuCo2O4 on the Cu mesh significantly improves its physical, chemical, and electrochemical properties, making these CuCo2O4@Cu meshes much more superior catalysts for activating Oxone to degrade the Azo toxicant, Acid Red 27. More interestingly, the flower-like CuCo2O4@Cu mesh exhibits a higher specific surface area and more superior electrochemical performance, enabling the flower-like CuCo2O4@Cu mesh to show the highest catalytic activity for Oxone activation to degrade Acid Red 27. The flower-like CuCo2O4@Cu mesh also exhibits a much lower Ea of Acid Red 27 degradation than the reported catalysts. These results demonstrate that CuCo2O4@Cu meshes are advantageous heterogeneous catalysts for Oxone activation, and especially, the flower-like CuCo2O4@Cu mesh appears as the most effective CuCo2O4@Cu mesh to eliminate the toxic Acid Red 27.

Antioxidants from the leaves of Cinnamomum kotoense.

Two novel antioxidants, obtusilactone A (1) and (-)-sesamin (2) have been identified in Cinnamomum kotoense Kanehira. Both showed effective 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity compared with vitamin C, and reducing power compared with BHA. These results suggest that these constituents of C. kotoense act as natural antioxidants and play a potential role in cancer prevention.

(-)-N-Formylanonaine from Michelia alba as a human tyrosinase inhibitor and antioxidant.

Tyrosinase is the first and rate limiting enzyme in the synthesis of melanin pigments for coloring hair, skin, and eyes. As reported in this study, a natural product, (-)-N-formylanonaine isolated from the leaves of Michelia alba D.C. (Magnolianceae), was found to inhibit mushroom tyrosinase with an IC50 of 74.3 microM and to have tyrosinase and melanin reducing activities in human epidermal melanocytes without apparent cytotoxicity to human cells, superior to the known tyrosinase inhibitors, such as kojic acid and 1-phenyl-2-thiourea (PTU). Based on homology modeling, the compound binds the active site by coordinating with two Cu2+ ions. In addition, the compound had antioxidation activities in tests for scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH), reducing power, and chelating metal ions. To our knowledge, this is the first study to reveal the bioactivities of (-)-N-formylanonaine from this plant species.

The permeability of gap junction channels to probes of different size is dependent on connexin composition and permeant-pore affinities.

Gap junctions have traditionally been characterized as nonspecific pores between cells passing molecules up to 1 kDa in molecular mass. Nonetheless, it has become increasingly evident that different members of the connexin (Cx) family mediate quite distinct physiological processes and are often not interchangeable. Consistent with this observation, differences in permeability to natural metabolites have been reported for different connexins, although the physical basis for selectivity has not been established. Comparative studies of different members of the connexin family have provided evidence for ionic charge selectivity, but surprisingly little is known about how connexin composition affects the size of the pore. We have employed a series of Alexa dyes, which share similar structural characteristics but range in size from molecular weight 350 to 760, to probe the permeabilities and size limits of different connexin channels expressed in Xenopus oocytes. Correlated dye transfer and electrical measurements on each cell pair, in conjunction with a three-dimensional mathematical model of dye diffusion in the oocyte system, allowed us to obtain single channel permeabilities for all three dyes in six homotypic and four heterotypic channels. Cx43 and Cx32 channels passed all three dyes with similar efficiency, whereas Cx26, Cx40, and Cx45 channels showed a significant drop-off in permeability with the largest dye. Cx37 channels only showed significant permeability for the smaller two dyes, but at two- to sixfold lower levels than other connexins tested. In the heterotypic cases studied (Cx26/Cx32 and Cx43/Cx37), permeability characteristics were found to resemble the more restrictive parental homotypic channel. The most surprising finding of the study was that the absolute permeabilities calculated for all gap junctional channels in this study are, with one exception, at least 2 orders of magnitude greater than predicted purely on the basis of hindered pore diffusion. Consequently, affinity between the probes and the pore creating an energetically favorable in-pore environment, which would elevate permeant concentration within the pore and hence the flux, is strongly implicated.

A transient diffusion model yields unitary gap junctional permeabilities from images of cell-to-cell fluorescent dye transfer between Xenopus oocytes.

As ubiquitous conduits for intercellular transport and communication, gap junctional pores have been the subject of numerous investigations aimed at elucidating the molecular mechanisms underlying permeability and selectivity. Dye transfer studies provide a broadly useful means of detecting coupling and assessing these properties. However, given evidence for selective permeability of gap junctions and some anomalous correlations between junctional electrical conductance and dye permeability by passive diffusion, the need exists to give such studies a more quantitative basis. This article develops a detailed diffusion model describing experiments (reported separately) involving transport of fluorescent dye from a "donor" region to an "acceptor" region within a pair of Xenopus oocytes coupled by gap junctions. Analysis of transport within a single oocyte is used to determine the diffusion and binding characteristics of the cellular cytoplasm. Subsequent double-cell calculations then yield the intercellular junction permeability, which is translated into a single-channel permeability using concomitant measurements of intercellular conductance, and known single-channel conductances of gap junctions made up of specific connexins, to count channels. The preceding strategy, combined with use of a graded size series of Alexa dyes, permits a determination of absolute values of gap junctional permeability as a function of dye size and connexin type. Interpretation of the results in terms of pore theory suggests significant levels of dye-pore affinity consistent with the expected order of magnitude of typical (e.g., van der Waals) intermolecular attractions.