Synthesis and the Effect of Anions on the Spectroscopy and Electrochemistry of Mono(dimethyl sulfoxide)-Ligated Cobalt Corroles.

A new series of cobalt A3-triarylcorroles were synthesized and the compounds examined as to their electrochemical and spectroscopic properties in CH2Cl2 or dimethyl sulfoxide (DMSO) containing 10 different anions added to the solution in the form of tetrabutylammonium salts. The investigated anions were PF6-, BF4-, HSO4-, ClO4-, Br-, I-, Cl-, OAc-, F-, OTs-, and CN-, all but three of which were found to facilitate reduction of the cobalt corrole in dilute CH2Cl2 solutions, as determined by a combination of UV-vis spectroscopy and spectroelectrochemistry. The synthesized corroles are represented as (Ar)3CorCo(DMSO), where Ar is a meso-phenyl group containing one of 10 different electron-donating or -withdrawing substituents. The axial DMSO ligand was found to dissociate in dilute (10-5 M) CH2Cl2 solutions, but this was not the case at the higher electrochemical concentration of 10-3 M, where the investigated corroles exhibit a rich redox reactivity, undergoing up to five reversible one-electron-transfer reactions under the different solution conditions. The reversible half-wave potentials for generation of the singly oxidized corroles varied by over 1.0 V with a change in the electron-donating or -withdrawing meso-phenyl substituents and type of anion added to the solution, ranging from E1/2 = 0.83 V in one extreme to -0.42 V in the other. Much smaller shifts in the potentials (on the order of ∼210 mV) were observed for the reversible first reduction as a function of changes of the anion and/or corrole substituents, with the only exception being in the case of CN-, where the E1/2 values in CH2Cl2 ranged from +0.08 V in solutions containing 0.1 M TBAClO4 to >-1.8 V upon the addition of CN-.

Ligand Noninnocence in Cobalt Dipyrrin-Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles.

Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innocence or noninnocence of the macrocyclic ligand as a function of the changes in the solvent properties and degree of axial coordination. Electron paramagnetic resonance spectra of the compounds are obtained to experimentally assess the electron spin state. An X-ray structure of the six-coordinate complex is also presented. The investigated chemical properties of DPPCo compounds under different solution conditions are compared to those of cobalt corroles, where the macrocycle and metal ion also possess formal 3- and 3+ oxidation states in their air-stable forms.

Spectral, Electrochemical, and ESR Characterization of Manganese Tetraarylporphyrins Containing Four ß,ß'-Pyrrole Fused Butano and Benzo Groups in Nonaqueous Media.

Two series of ß,ß'-pyrrole butano- and benzo-substituted mangenese(III) tetraarylporphyrins were synthesized and characterized with regard to their spectral and electrochemical properties. The investigated compounds have the general formula butano(Ar)4PorMnCl and benzo(Ar)4PorMnCl, where Por is the dianion of the porphyrin and Ar is a p-CH3Ph, Ph or p-ClPh group on each of the four meso-positions of the macrocycle. Each manganese(III) butano- or benzoporphyrin was examined in CH2Cl2 and/or pyridine containing 0.1 M tetra- n-butylammonium perchlorate and the data then were compared to that of the parent tetraarylporphyrins having the same meso-substituents. Up to four reductions are observed for each compound, the first being metal-centered to generate a Mn(II) porphyrin, and the second and third being porphyrin ring-centered to give a Mn(II) porphyrin π-anion radical and dianion, respectively. The one-electron reduced manganese porphyrins have an ESR spectrum with signals at g⊥= 5.6-5.8 and g// = 2.0, indicating a mixture of the four- and five-coordinated Mn(II) complexes in a high-spin state (3d5, S = 5/2, I = 5/2). Data from cyclic voltammetry and spectroelectrochemistry both suggest that formation of the porphyrin dianion is followed by a chemical reaction at the electrode surface to give an electroactive phlorin anion. The effects of solvent and porphyrin substituents on ultraviolet-visible light (UV-vis) spectra, redox potentials, and electron transfer mechanisms are discussed.

Synthesis and Electrochemical Characterization of Acetylacetone (acac) and Ethyl Acetate (EA) Appended ß-Trisubstituted Push-Pull Porphyrins: Formation of Electronically Communicating Porphyrin Dimers.

Two new families of "push-pull" tetraphenylporphyrins with one acetylacetone (acac) or ethyl acetate (EA) moiety at a ß-pyrrole position of the macrocycle and two Br or Ph substituents at the antipodal ß-positions were synthesized and structurally, spectroscopically, and electrochemically characterized. The examined porphyrins are represented as MTPP(R)2acac and MTPP(R)2EA (where R = Br or Ph and M = H2, Co, Ni, Cu, or Zn). NiTPP(Br)2acac exhibits an extremely nonplanar conformation (Δ24 = 0.44 Å, ΔCß = 0.82 Å), while H2TPP(Br)2EA and ZnTPP(Ph)2EA exhibit a quasi-planar conformation. All of the synthesized acac-appended porphyrins show a keto-enol tautomerism in solution, which results in formation of hydrogen bonded dimers as evidenced by 1H NMR and mass spectrometry. Dimers were also detected under the electrochemical conditions for the dibromo derivatives but not the diphenyl substituted porphyrins. A facile stepwise and reversible electrogeneration of the electronically communicating porphyrin dimers is observed for MTPP(Br)2acac where M = CuII, NiII, or ZnII.

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media.

A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central cobalt ion, the electroactive conjugated macrocycle, and the electroactive meso-nitrophenyl groups are all discussed in terms of solvent binding and the number of the nitrophenyl groups and other substituents on the meso-nitrophenyl rings of the compounds.

Synthesis, Characterization, and Electrochemistry of Open-Chain Pentapyrroles and Sapphyrins with Highly Electron-Withdrawing meso-Tetraaryl Substituents.

A series of open-chain pentapyrroles and sapphyrins with highly electron-withdrawing substituents (i.e., CN, CF3 , or CO2 Me) on the meso-phenyl rings was synthesized and characterized as to the spectral properties, protonation reactions, and electrochemistry in non-aqueous media. The investigated compounds are represented as (Ar)4 PPyH3 and (Ar)4 SapH3 where PPy and Sap correspond to the tri-anion of the open-chain pentapyrrole and sapphyrin, respectively, and Ar=p-CNPh, p-CF3 Ph, or p-CO2 MePh. UV/Vis and 1 H NMR spectroscopy as well as mass spectrometry data are given for the confirmation of the structures for the newly synthesized compounds. An X-ray structure for one of the pentapyrroles, that is, (p-CF3 Ph)4 PPyH3 (2), is also presented. The protonation processes were examined by UV/Vis absorption spectroscopy during the titration of the compounds with trifluoroacetic acid (TFA) in CH2 Cl2 . Equilibrium constants for the protonation reactions were calculated by using both the Hill equation and the mole ratio method. The protonation-initiated conversion of pentapyrroles to sapphyrins upon oxidation was also investigated. Cyclic voltammetry was used to measure the redox potentials in CH2 Cl2 , PhCN, and/or pyridine (Py). Electrochemical properties, protonation constants, and chemical reactions of the six compounds in the two series were then analyzed as a function of the solvent properties and the type of the electron-withdrawing groups on the meso-phenyl rings.

Porphyrins as Photoredox Catalysts: Experimental and Theoretical Studies.

Metalloporphyrins not only are vital in biological systems but also are valuable catalysts in organic synthesis. On the other hand, catalytic properties of free base porphyrins have been less explored. They are mostly known as efficient photosensitizers for the generation of singlet oxygen via photoinduced energy transfer processes, but under light irradiation, they can also participate in electron transfer processes. Indeed, we have found that free base tetraphenylporphyrin (H2TPP) is an efficient photoredox catalyst for the reaction of aldehydes with diazo compounds leading to α-alkylated derivatives. The performance of a porphyrin catalyst can be optimized by tailoring various substituents at the periphery of the macrocycle at both the ß and meso positions. This allows for the fine tuning of their optical and electrochemical properties and hence their catalytic activity.

Annexin-V modified QCM sensor for the label-free and sensitive detection of early stage apoptosis.

An easily-made Annexin-V modified quartz crystal microbalance (QCM) sensor was constructed for the quantitative detection of early stage apoptosis for the first time, achieving the goals of specific capture and sensitive detection of target cells in one step without the need for cell labelling.

ß-Functionalized trans-A2B2 push-pull tetrabenzoporphyrins.

A series of ß-functionalized trans-A2B2 tetrabenzoporphyrins have been successfully designed and synthesized through newly developed regioselective bromination chemistry of porphyrins and a Pd(0) catalyzed three-step-one pot reaction. These benzoporphyrins exhibit unique patterns of UV-Vis absorptions and emissions.

An aptamer-based quartz crystal microbalance biosensor for sensitive and selective detection of leukemia cells using silver-enhanced gold nanoparticle label.

An aptamer-based quartz crystal microbalance (QCM) biosensor was developed for the selective and sensitive detection of leukemia cells. In this strategy, aminophenylboronic acid-modified gold nanoparticles (APBA-AuNPs) which could bind to cell membrane were used for the labeling of cells followed by silver enhancement, through which significant signal amplification was achieved. Both the QCM and fluorescence microscopy results manifested the selectivity of the sensor designed. A good linear relationship between the frequency response and cell concentration over the range of 2×10(3)-1×10(5)cells/mL was obtained, with a detection limit of 1160cells/mL. This approach provides a simple, rapid, and economical method for leukemia cell analysis which might have great potential for further use.

Sensitive and visible detection of apoptotic cells on Annexin-V modified substrate using aminophenylboronic acid modified gold nanoparticles (APBA-GNPs) labeling.

A new strategy for sensitive detection of early stage apoptosis was proposed based on silver-enhanced gold nanoparticle (GNP) label method. Annexin-V modified substrate was constructed via layer-by-layer (LBL) method for specific capture of early stage apoptotic Jurkat cells. A new kind of aminophenylboronic acid modified gold nanoparticle (APBA-GNP) was synthesized and utilized for labeling cells, followed by silver enhancement. Anodic stripping voltammetry (ASV) was applied to sensitive detection of Ag(+) dissolved from the deposited silver particles, which reflected the number of cells. A good linear range from 1 × 10(2) to 3.5 × 10(3) cells was achieved, with a detection limit of 38 apoptotic cells. Moreover, the gray color of silver enhancement could be observed by the naked eye, which could be used to tell apoptotic cells apart from normal cells. Therefore, using the silver-enhanced GNP label method, apoptotic cells could not only be sensitively detected via electrochemical technique, but also can be discriminated from normal cells by the naked eye.

Polymer nanocomposites with graphene-based hierarchical fillers as materials for multifunctional water treatment membranes.

Phase inversion of polymer casting mixtures filled with hierarchical functional nanostructures is proposed as a synthetic route for the design of multifunctional membranes. The study tested the hypothesis that by regulating the relative content of components representing different levels in the nanofiller hierarchy, the structure and additional functions of such membranes could be controlled separately. Exfoliated graphite nanoplatelets (xGnPs) decorated by Au nanoparticles (Au NPs), used as a model hierarchical nanofiller, were added to the casting mixture of polysulfone, N-Methyl-2-pyrrolidone and polyethylene glycol prior to forming the membrane by phase inversion. The resulting porous asymmetric nanocomposites were shown to be permselective and catalytically active ultrafiltration membranes that were more resistant to compaction, more permeable than xGnP-free membranes and at least as selective. By designing membrane compositions with different relative amounts of Au-decorated xGnPs and Au-free xGnPs, the structure (controlled by the loading of xGnPs) and catalytic activity (controlled by the loading of Au NPs) could be controlled largely independently.

Single-walled carbon nanotubes dispersed in aqueous media via non-covalent functionalization: effect of dispersant on the stability, cytotoxicity, and epigenetic toxicity of nanotube suspensions.

As the range of applications for carbon nanotubes (CNTs) rapidly expands, understanding the effect of CNTs on prokaryotic and eukaryotic cell systems has become an important research priority, especially in light of recent reports of the facile dispersion of CNTs in a variety of aqueous systems including natural water. In this study, single-walled carbon nanotubes (SWCNTs) were dispersed in water using a range of natural (gum arabic, amylose, Suwannee River natural organic matter) and synthetic (polyvinyl pyrrolidone, Triton X-100) dispersing agents (dispersants) that attach to the CNT surface non-covalently via different physiosorption mechanisms. The charge and the average effective hydrodynamic diameter of suspended SWCNTs as well as the concentration of exfoliated SWCNTs in the dispersion were found to remain relatively stable over a period of 4 weeks. The cytotoxicity of suspended SWCNTs was assessed as a function of dispersant type and exposure time (up to 48 h) using general viability bioassay with Escherichia coli and using neutral red dye uptake (NDU) bioassay with WB-F344 rat liver epithelia cells. In the E. coli viability bioassays, three types of growth media with different organic loadings and salt contents were evaluated. When the dispersant itself was non-toxic, no losses of E. coli and WB-F344 viability were observed. The cell viability was affected only by SWCNTs dispersed using Triton X-100, which was cytotoxic in SWCNT-free (control) solution. The epigenetic toxicity of dispersed CNTs was evaluated using gap junction intercellular communication (GJIC) bioassay applied to WB-F344 rat liver epithelial cells. With all SWCNT suspensions except those where SWCNTs were dispersed using Triton X-100 (wherein GJIC could not be measured because the sample was cytotoxic), no inhibition of GJIC in the presence of SWCNTs was observed. These results suggest a strong dependence of the toxicity of SWCNT suspensions on the toxicity of the dispersant and point to the potential of non-covalent functionalization with non-toxic dispersants as a method for the preparation of stable aqueous suspensions of biocompatible CNTs.

Interactions of aqueous NOM with nanoscale TiO2: implications for ceramic membrane filtration-ozonation hybrid process.

The combined effect of pH and calcium on the interactions of nonozonated and ozonated natural organic matter (NOM) with nanoscale TiO2 was investigated. The approach included characterization of TiO2 nanoparticles and NOM, extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) modeling of NOM-TiO2 and NOM-NOM interactions, batch study on the NOM adsorption onto TiO2 surface, and bench-scale study on the treatment of NOM-containing feed waters using a hybrid process that combines ozonation and ultrafiltration with a 5 kDa ceramic (TiO2 surface) membrane. It was demonstrated that depending on pH and TiO2 loading, the adsorption of NOM species is controlled by either the availability of divalent cations or by preozonation of NOM. XDLVO surface energy analysis predicts NOM adsorption onto TiO2 in the ozone-controlled regime but not in the calcium-controlled regime. In both regimes, short-range NOM-NOM and NOM-TiO2 interactions were governed by acid-base and van der Waals forces, whereas the role of electrostatic forces was relatively insignificant. Ozonation increased the surface energy of NOM, contributing to the hydrophilic repulsion component of the NOM-NOM and NOM-TiO2 interactions. In the calcium-controlled regime, neither NOM-TiO2 nor NOM-NOM interaction controlled adsorption. Non-XDLVO interactions such as intermolecular bridging by calcium were hypothesized to be responsible for the observed adsorption behavior. Adsorption data proved to be highly predictive of the permeate flux performance.

Stable colloidal dispersions of C60 fullerenes in water: evidence for genotoxicity.

Stable aqueous suspensions of colloidal C60 fullerenes free of toxic organic solvents were prepared by two methods: ethanol to water solvent exchange (EthOH/nC60 suspensions) and extended mixing in water (aqu/nC60 suspensions). The extended mixing method resulted in the formation of larger (dp approximately 178 nm) and less negatively charged (zeta approximately -13.5 mV) nC60 colloids than nC60 prepared by ethanol to water solvent exchange (dp approximately 122 nm, zeta approximately -31.6 mV). Genotoxicity of these suspensions was evaluated with respect to human lymphocytes using single-cell gel electrophoresis assay (Comet assay). The assay demonstrated genotoxicity for both types of suspensions with a strong correlation between the genotoxic response and nC60 concentration, and with genotoxicity observed at concentrations as low as 2.2 microg/L for aqu/nC60 and 4.2 microg/L for EtOH/nC60. The Olive tail moments (OTM) for these two concentrations were 1.54 +/- 0.24 and 1.34 +/- 0.07, respectively, which in comparison to the negative control OTM of 0.98 +/- 0.17 is statistically different with a p value of at least 0.05. Aqu/nC60 suspensions elicited higher genotoxic response than EthOH/nC60 for the same nC60 concentration. The results represent the first genotoxicity data for colloidal fullerenes produced by simple mixing in water.