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Characterization and redox properties of cytochrome c552 from Thermus thermophilus adsorbed on different self-assembled thiol monolayers, used to model the chemical environment of the redox partner.

The structure of cytochrome c552 (Cyt-c552) from Thermus thermophilus shows many differences to other c-type cytochromes. The rich lysine domain close to the heme does not exist in this cytochrome, allowing us to postulate that the interaction with its redox partner must be different to the cytochrome c/cytochrome c oxidase interaction. We report a study of Cyt-c552 adsorbed on self-assembled monolayers (SAMs) of functionalized alkanethiols used to mimic the chemical properties of its redox partner (ba3-oxydase). Hydrophilic (-COOH), polar (-OH), hydrophobic (-CH3), and mixed (-OH/-CH3) SAMs grafted on roughened silver electrodes were characterized by X-ray photoelectron spectroscopy. Surface enhanced resonance Raman spectroscopy (SERRS) was employed to determine the structure and the redox properties (E degrees and number of transferred electron) of the heme of Cyt-c552 adsorbed on roughened silver electrodes coated by the different SAMs. The surface that most closely models the environment of the ba3-oxidase is a mixed SAM formed by 50% polar [Ag-(CH2)5-CH2OH] and 50% hydrophobic [Ag-(CH2)5-CH3] alkanethiols. Only the native form B1(6cLS) of Cyt-c552 is detected by SERRS when the protein is adsorbed on such a surface that promotes a protein orientation favorable for the electron transfer (number of transferred electron = 1). We shall discuss the differences and similarities of the electron-transfer mechanism of Cyt-c552 compared to cyt-c.

Adsorption↗

Highly accurate nephelometric titrimetry.

A method that accurately indicates the end-point of precipitation reactions by the measurement of the relative intensity of the scattered light in the titrate is presented. A new nephelometric titrator with an internal nephelometric sensor has been devised. The work of the titrator including the sensor and change in the turbidity of the titrate and intensity of the scattered light are described. The accuracy of the nephelometric titrimetry is discussed theoretically. The titration of NaCl with AgNO(3) serves as a model. A relative error as well as deviation is within 0.2% under the experimental conditions. The applicability of the titrimetry in pharmaceutical analyses, for example, phenytoin sodium and procaine hydrochloride, is generally illustrated.

Chemistry, Pharmaceutical↗

A simple spectroscopic method for studying erythrocyte ghost resealing.

A novel spectroscopic method is described for following the kinetics of resealing of hemolysed erythrocyte ghosts. The procedure is based on the broadening of the EPR spectrum of nitroxyl radicals by paramagnetic ions. The method is used to study the effect of Ca2+, Mg2+ and dimethonium ion on the kinetics of resealing.

Bis-Trimethylammonium Compounds↗

Silver accumulation in Daphnia magna in the presence of reactive sulfide.

Previously, we demonstrated a higher silver body burden when Daphnia magna were exposed to silver in the presence of environmentally relevant concentrations (25 nM) of reactive sulfide, but the explanation was unclear. In the present study, D. magna were exposed to AgNO3 (0.93 microg Ag/L=8.6 nM as a mixture of cold Ag and (110m)Ag) in synthetic water in either the presence or absence of 25 nM sulfide as zinc sulfide clusters. After 1-h exposure, daphnids were transferred to clean water for up to 5-h depuration. At different times of Ag exposure and depuration, daphnids were randomly sampled for whole body silver burden. Also, after 1 h, daphnids were sampled for silver accumulation in "gills" (small organs on the thoracic appendages), digestive tract, and carcass. Other groups were exposed to the same silver and sulfide concentrations for 1 h and then sampled for whole-body autoradiography. Silver body burden was about two-fold higher in the presence of sulfide. A two-fold increase in silver burden in "gills" and digestive tract, but not in carcass, was also observed in the presence of sulfide. Absolute differences due to sulfide were greatest in digestive tract and explained most of the difference in whole body burden. Transfer to clean water caused a significant drop in silver concentration in whole body and all compartments to similar levels in the two groups after 5-h depuration. These results indicate that the higher silver body burden observed in the presence of sulfide is mainly due to sulfide-bound silver in the digestive tract of the daphnids. This conclusion is supported by autoradiography, which showed a high concentration of silver in the digestive tract of daphnids exposed to Ag/sulfide.

Animals↗

IR, Raman and SERS studies of methyl salicylate.

The IR and Raman spectra of methyl salicylate (MS) were recorded and analysed. Surface enhanced Raman scattering (SERS) spectrum was recorded in silver colloid. The vibrational wave numbers of the compound have been computed using the Hartree-Fock/6-31G* basis and compared with the experimental values. SERS studies suggest a flat orientation of the molecule at the metal surface.

Salicylates↗

Histochemically-reactive zinc in amyloid plaques, angiopathy, and degenerating neurons of Alzheimer's diseased brains.

Excess brain zinc has been implicated in Alzheimer's neuropathology. Here we evaluated that hypothesis by searching the brains of Alzheimer's patients for abnormal zinc deposits. Using histochemical methods, we found vivid Zn2+ staining in the amyloid deposits of dense-core (senile) plaques, in the amyloid angiopathy surrounding diseased blood vessels, and in the somata and dendrites of neurons showing the characteristic neurofibrillary tangles (NFT) of Alzheimer's. In contrast, brains from age-matched, non-demented subjects showed only occasional staining for Zn2+ in scattered neurons and possible plaques. A role of abnormal zinc metabolism in Alzheimer's neuropathology is suggested.

Aged↗

Covalent coupling of immunoglobulin G to a poly(vinyl)alcohol-poly(acrylic acid) graft polymer as a method for fabricating the interfacial-recognition layer of a surface plasmon resonance immunosensor.

The synthesis of a terminally thiolated poly(vinyl)alcohol (PVA) grafted with Poly (acrylic acid) (PAA) side chains is described. The PVA-PAA graft polymer (PVAg) was end-tethered to silver surfaces via the terminal thiol functionality and the resultant mobile, hydrophilic polymer matrix exploited for the covalent immobilization of large quantities of polyclonal goat (anti-hIgG) antibody (IgG) with low levels of non-specific adsorption. An SPR immunosensor, fabricated with an IgG-PVA-silver interfacial layer proved capable of performing a sensitive label-free assay of human IgG antigen (hIgG) with minimal non-specific binding interference. A detection limit (DL) for hIgG from serum of 0.8 microgram/ml (5 nM) and an assay sensitivity of 0.66 ng hIgG/mm2/nM are reported.

Acrylic Resins↗

Continuous flow analytical microsystems based on low-temperature co-fired ceramic technology. Integrated potentiometric detection based on solvent polymeric ion-selective electrodes.

In this paper, the low-temperature co-fired ceramics (LTCC) technology, which has been commonly used for electronic applications, is presented as a useful alternative to construct continuous flow analytical microsystems. This technology enables not only the fabrication of complex three-dimensional structures rapidly and at a realistic cost but also the integration of the elements needed to carry out a whole analytical process, such as pretreatment steps, mixers, and detection systems. In this work, a simple and general procedure for the integration of ion-selective electrodes based on liquid ion exchanger is proposed and illustrated by using ammonium- and nitrate-selective membranes. Additionally, a screen-printed reference electrode was easily incorporated into the microfluidic LTCC structure allowing a complete on-chip integration of the potentiometric detection. Analytical features of the proposed systems are presented.

Ceramics↗

New Ag(I)-containing coordination polymers generated from multidentate Schiff-base ligands.

The coordination chemistry of the multidentate Schiff-base ligands 2,5-bis(3-methylpyrazinyl)-3,4-diaza-2,4-hexadiene (L5) and 2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene (L6) with inorganic Ag(I) salts has been investigated. Six new Ag(I)-coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. [Ag(L5)]ClO(4).0.5CH(3)OH (1, orthorhombic, Fdd2; a = 20.0896(11) A, b = 48.224(3) A, c = 7.8432(4) A, Z = 16), [Ag(L5)]PF(6).0.5CH(3)OH (2, orthorhombic, Fdd2; a = 20.7255(11) A, b = 46.166(2) A, c = 8.4332(4) A, Z = 16), [Ag(L5)]SbF(6).0.5CH(3)OH (3, orthorhombic, Fdd2; a = 21.5481(11) A, b = 45.196(2) A, c = 8.7331(4) A, Z = 16), and [Ag(L5)](BF(4)).0.5CH(3)OH (4, orthorhombic, Fdd2; a = 19.8897(11) A, b = 48.358(3) A, c = 7.7491(5) A, Z = 16) were obtained by combination of L5 with AgClO(4).xH(2)O, AgPF(6), AgSbF(6), and AgBF(4), respectively, in a methylene chloride/methanol mixed solvent system. Compounds 1-4 are isostructural and feature noninterpenetrating three-dimensional zeolite-like networks. [Ag(4)(L6)(4)](PF(6))(4).CHCl(3) (5, tetragonal, Pc2; a = 16.1067(3) A, b = 16.1067(3) A, c = 14.4935(5) A, Z = 2) was generated from the reaction of L6 with AgPF(6) in a chloroform/ethanol mixed solvent system. It forms with a unique one-dimensional nanometer-tube that can be considered a new polymeric motif based on the [AgN5] coordination sphere. The tubes are square with crystallographic dimensions of 10.3 x 10.0 A. The tubes are further linked together through weak interpolymer C-H...F hydrogen bonding interactions into a novel H-bonded three-dimensional network containing square tubes, in which uncoordinated PF(6)(-) counterions and chloroform guest molecules are located. Compound 6 ([Ag(mu-C(6)H(6)N(2)O)](SO(3)CF(3)), monoclinic, P2(1)/c; a = 12.3435(6) A, b = 20.3548(10) A, c = 9.0861(5) A, Z = 8) was obtained by combination of AgSO(3)CF(3) and L6 in a methylene chloride/benzene mixed solvent system. In 6, 2-acetylpyrazine, which was generated from the hydrolysis reaction of L6 in the presence of CF(3)SO(3)(-) and a small quantity of water in solvent, chelates the Ag(I) centers through the carbonyl O-donor, and the vicinal pyrazine N-donor, furthermore, uses the para-N atoms to link other Ag(I) centers into one-dimensional zigzag chains. The triflate anions link the chains into a three-dimensional network by somewhat long Ag.O contacts.

Ligands↗