Electrophilic aromatic nitration: understanding its mechanism and substituent effects

Theoretical calculations and gas-phase mass spectrometric studies were performed for the reaction of the naked (NO2+) and monosolvated (CH3NO2.NO2+) nitronium ion with several monosubstituted aromatic compounds. From these studies, we propose a general model for regioselectivity based on the single-electron transfer (SET) mechanism and an alternative mechanistic scheme for electrophilic aromatic nitration. This scheme considers the SET and the polar (Ingold-Hughes) mechanisms as extremes in a continuum pathway, the occurrence and extents of both mechanisms being governed mainly by the ability, or lack of ability, of the aromatic compound to transfer an electron to NO2+.     

A polymer inclusion membrane based on the ionic liquid trihexyl(tetradecyl)phosphonium chloride and PVC for solid–liquid extraction of Zn(II) from hydrochloric acid solution

Abstract  

Extraction of Zn(II) from aqueous solution using polymer inclusion membranes based on poly(vinyl chloride) containing the phosphonium-based ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos^? IL 101) is described. Zn(II) could efficiently be extracted from 5 M hydrochloric acid solution with membranes containing 30 wt% Cyphos IL 101, whereas back-extraction was successfully achieved with 1 M sulfuric acid. Prepared membranes were evaluated in terms of stability in air as well as in terms of leaching of the ionic liquid from the membranes in aqueous solution.     

Antimicrobial graphene polymer (PVK-GO) nanocomposite films

The first report on the fabrication and application of a nanocomposite containing poly-N-vinyl carbazole (PVK) polymer and graphene oxide (GO) as an antimicrobial film was demonstrated. The antimicrobial film was 90% more effective in preventing bacterial colonization relative to the unmodified surface. More importantly, the nanocomposite thin film showed higher bacterial toxicity than pure GO-modified surface.     

Study on the thermal behavior of the complexes of the type [PdX<Subscript>2</Subscript>(tdmPz)] (X = Cl<Superscript>−</Superscript>, Br<Superscript>−</Superscript>, I<Superscript>−</Superscript>, SCN<Superscript>−</Superscript>)

Four new mononuclear Pd(II) complexes of the type [PdX₂(tdmPz)] {X = Cl⁻ (1); Br⁻ (2); I⁻ (3); SCN⁻ (4); tdmPz = 1-thiocarbamoyl-3,5-dimethylpyrazole} have been synthesized and characterized by elemental analysis, IR spectroscopy, ¹H and ¹³C{¹H}-NMR experiments. The thermal behavior of the complexes 1–4 has been investigated by means of thermogravimetry (TG) and differential thermal analysis (DTA). From the initial decomposition temperatures, the thermal stability of the complexes can be ordered in the sequence: 3 < 4 ≡ 2 < 1. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.     

Spectroscopic and electronic structure studies of a dimethyl sulfoxide reductase catalytic intermediate: implications for electron- and atom-transfer reactivity

The electronic structure of a genuine paramagnetic des-oxo Mo(V) catalytic intermediate in the reaction of dimethyl sulfoxide reductase (DMSOR) with (CH(3))(3)NO has been probed by electron paramagnetic resonance (EPR), electronic absorption, and magnetic circular dichroism (MCD) spectroscopies. EPR spectroscopy reveals rhombic g- and A-tensors that indicate a low-symmetry geometry for this intermediate and a singly occupied molecular orbital that is dominantly metal centered. The excited-state spectroscopic data were interpreted in the context of electronic structure calculations, and this has resulted in a full assignment of the observed MCD and electronic absorption bands, a detailed understanding of the metal-ligand bonding scheme, and an evaluation of the Mo(V) coordination geometry and Mo(V)-S(dithiolene) covalency as it pertains to the stability of the intermediate and electron-transfer regeneration. Finally, the relationship between des-oxo Mo(V) and des-oxo Mo(IV) geometric and electronic structures is discussed relative to the reaction coordinate in members of the DMSOR enzyme family.     

Raman spectroelectrochemical study of Meldola blue, adsorbed and electropolymerized at a gold electrode

Surface-enhanced Raman spectroscopy (SERS) was used to probe the structure of adsorbed and electropolymerized Meldola blue (MB) films on roughened gold surfaces in solutions with pH 1.0 and 7.0 by using 785 nm excitation wavelength. Spectral bands were assigned based on density functional theory (DFT) calculations at B3LYP/6-311+G(2d, p) level. The most characteristic band of the oxidized MB form was found to be the breathing vibration of the central ring containing heteroatoms at 596 cm(-1). Based on a red shift of bands assigned to vibrations of double C=N(C(2)H(6)) bonds and adjacent ring C=C bonds in surface spectra as compared with solution 1 it was suggested that polymerization and interaction with an electrode surface proceed through these moieties. The presence of out-of-plane bands in SERS spectra was attributed to "flat" or slightly "tilted" orientation of aromatic rings at the interface. Potential-dependent spectral changes were followed by SERS spectroscopy. Raman spectra of the reduced MB form were obtained in both pH 1.0 and pH 7.0 solutions by analysis of the potential-difference SERS spectra. Reduced MB form can be recognized by characteristic bands near 1620, 1574, 1374, and 1234 cm(-1). By comparing the intensities of 1637 cm(-1) (oxidized MB form) and 1374 cm(-1) (reduced MB form) bands in experimental spectra of polymerized MB in pH 1.0 solution, a reduction-induced decrease by factor of 7 was estimated. A similar tendency in intensity changes showed calculations indicating that this effect is associated with reduction-induced changes in the molecular structure of the dye.     

In situ microbial fuel cell-based biosensor for organic carbon

The biological oxygen demand (BOD) may be the most used test to assess the amount of pollutant organic matter in water; however, it is time and labor consuming, and is done ex-situ. A BOD biosensor based on the microbial fuel cell principle was tested for online and in situ monitoring of biodegradable organic content of domestic wastewater. A stable current density of 282±23mA/m(2) was obtained with domestic wastewater containing a BOD(5) of 317±15mg O(2)/L at 22±2°C, 1.53±0.04mS/cm and pH 6.9±0.1. The current density showed a linear relationship with BOD(5) concentration ranging from 17±0.5mg O(2)/L to 78±7.6mg O(2)/L. The current generation from the BOD biosensor was dependent on the measurement conditions such as temperature, conductivity, and pH. Thus, a correction factor should be applied to measurements done under different environmental conditions from the ones used in the calibration. These results provide useful information for the development of a biosensor for real-time in situ monitoring of wastewater quality.     

Mapping the orientation of helices in micelle-bound peptides by paramagnetic relaxation waves

Many antimicrobial peptides form alpha-helices when bound to a membrane. In addition, around 80% of residues in membrane-bound proteins are found in alpha-helical regions. The orientation and location of such helical peptides and proteins in the membrane are key factors determining their function and activity. Here we present a new solution state NMR method for obtaining the orientation of helical peptides in a membrane-mimetic environment (micelle-bound) without any chemical perturbation of the peptide-micelle system. By monitoring proton longitudinal relaxation rates upon addition of the freely water-soluble and inert paramagnetic probe Gd(DTPA-BMA) to an alpha-helical peptide, a wavelike pattern with a periodicity of 3.6 residues per turn is observed. The tilt and azimuth (rotation) angle of the helix determine the shape of this paramagnetic relaxation wave and can be obtained by least-square fitting of measured relaxation enhancements. Results are presented for the 15-residue antimicrobial peptide CM15 which forms an amphipathic helix almost parallel to the surface of the micelle. Thus, a few fast experiments enable the identification of helical regions and determination of the helix orientation within the micelle without the need for covalent modification, isotopic labeling, or sophisticated equipment. This approach opens a path toward the topology determination of alpha-helical membrane-proteins without the need for a complete NOE-based structure determination.     

Iodine-poly(2-vinylpyridine-co-styrene-co-divinylbenzene) charge transfer complexes with antibacterial activity

In this work, we have developed three different copolymers based on 2-vinylpyridine, styrene and crosslinked with divinylbenzene (10-30 mol%). The copolymers were morphologically and chemically characterized by apparent density, swelling degree, elemental analysis, Fourier transform infrared spectrophotometry and optical microscopy. The formation of iodine complexes with these copolymers was carried out by two different procedures: with solvent, or not. The influence of the copolymers structure on the capacity of anchoring iodine has been investigated. The antibacterial properties of polymeric charge transfer complexes were determined towards 10³-10⁷ cells/mL dilutions from the auxotrophic AB1157 Escherichia coli strain.