MECHANISM OF ACTION OF COBALT IONS ON RAT OSSEOUS PLATE ALKALINE-PHOSPHATASE

Polidocanol-solubilized osseous plate alkaline phosphatase was modulated by cobalt ions in a similar way as by magnesium ions. For concentrations up to 1 mu M, the Chelex-treated enzyme was stimulated by cobalt ions, showing K-d = 6.0 mu M, V = 977.5 U/mg, and site-site interactions (n = 2.5). Cobalt-enzyme was highly unstable at 37 degrees C, following a biphasic inactivation process with inactivation constants of about 0.0625 and 0.0015 min(-1). Cobalt ions stimulated the enzyme synergistically in the presence of magnesium ions (K-d = 5.0 mu M; V = 883.0 U/mg) or in the presence of zinc ions (K-d = 75.0 mu M; V = 1102 U/mg). A steady-state kinetic model for the modulation of enzyme activity by cobalt ions is proposed.

2 END-TO-SIDE NEURORRHAPHIES AND NERVE GRAFT WITH REMOVAL OF THE EPINEURAL SHEATH - EXPERIMENTAL-STUDY IN RATS

We have studied a new type of end-to-side nerve repair in rats. The healthy (donor) nerve was not divided but an epineural window was created. In our experiment, a nerve graft bridged the tibial nerve to the distal end of the divided peroneal nerve. Electrophysiological studies showed electrical impulses conducted through both end-to-side nerve junctions. Histological studies demonstrated axons leaving the lateral surface of the healthy (donor) nerve. Based on these observations, we suggest that end-to-side neurorrhaphy from a healthy nerve may bridge a neural deficit.

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

The effects of copper ions on the synthesis of periplasmic and membrane proteins in Acidithiobaeillus ferrooxidans as analyzed by SDS-PAGE and 2D-PAGE

The effects of 200 mM copper ions on the synthesis of membrane and periplasmic proteins were investigated in iron-grown cells of Acidithiobacillus ferrooxidans (At. ferrooxidans). Total membrane protein profiles of cells grown in the absence of copper ions (unadapted cells) and in the presence of copper ions (copper-adapted cells) were compared by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE). Crude preparations of outer membrane and periplasmic proteins were analyzed by SDS-PAGE. The synthesis of proteins was diminished or increased in the presence of copper ions. Low molecular weight proteins (< 14 kDa) were significantly repressed by copper. These proteins are probably acidic proteins located in the outer membrane. An over-expression of a periplasmic protein of about 17 kDa was detected in the copper-adapted cells and was assumed to be rusticyanin, a 16.5-kDa periplasmic copper protein present in At. ferrooxidans cells and involved in the electron-transport chain of the iron oxidation pathway. To our knowledge, this is the first report of a possible involvement of the rusticyanin and outer membrane proteins in the mechanism of copper resistance in At. ferrooxidans. (C) 2003 Elsevier B.V. All rights reserved.

Use of a carbon paste electrode modified with spinel-type manganese oxide as a potentiometric sensor for lithium ions in flow injection analysis

A potentiometric sensor constructed from a mixture of 25% (m/m) spinel-type manganese oxide (lambda-MnO2), 50% (m/m) graphite powder and 25% (m/m) mineral oil is used for the determination of lithium ions in a flow injection analysis system. Experimental parameters, such as pH of the carrier solution, flow rate, injection sample volume, and selectivity for Li+ against other alkali and alkaline-earth ions and the response time of this sensor were investigated. The sensor response to lithium ions was linear in the concentration range 8.6 x 10(-5) - 1.0 x 10(-2) mol L-1 with a slope 78.9 +/- 0.3 mV dec(-1) over a wide pH range 7 - 10 (Tris buffer), without interference of other alkali and alkaline-earth metals. For a flow rate of 5.0 mL min(-1) and a injection sample volume of 408.6 muL, the relative standard deviation for repeated injections of a 5.0 x 10(-4) mol L-1 lithium ions was 0.3%.

ALLOSTERIC MODULATION BY ATP, CALCIUM AND MAGNESIUM-IONS OF RAT OSSEOUS PLATE ALKALINE-PHOSPHATASE

Alkaline phosphatase from rat osseous plate is allosterically modulated by ATP, calcium and magnesium at pH 7.5. At pH 9.4, the hydrolysis of ATP and PNPP follows Michaelis-Menten kinetics with K0.5 values of 154 muM and 42 muM, respectively. However, at pH 7.5 both substrates exhibit more complex saturation curves, while only ATP exhibited site-site interactions. Ca2+-ATP and Mg2+-ATP were effective substrates for the enzyme, while the specific activity of the enzyme for the hydrolysis of ATP at pH 7.5 was 800-900 U/mg and was independent of the ion species. ATP, but not PNPP, was hydrolyzed slowly in the absence of metal ions with a specific activity of 140 U/mg. These data demonstrate that in vitro and at pH 7.5 rat osseous plate alkaline phosphatase is an active calcium or magnesium-activated ATPase.

Removal of radionuclides from acid mine waters by retention on adsorbing materials

This study proposes a method for decontamination of acid drainage water from a uranium mine, as an alternative process to lime treatment. The research embodied the recovery of uranium with an ion-exchange resin, treatment of effluent resin with lime, or with inorganic adsorbents and biosorbents. The uranium decontamination level using the resin process was 94% and allowed the recovery of this element as a commercial product. Among the inorganic adsorbents studied, phosphogypsum was effective for Ra-226, Ra-228, and Pb-210 removal. Among the biosorbents, Sargassum sp.was superior in relation to its specific capacity to accumulate and remove Ra-226.

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

Variable influence of ferric and cupric ions on Saccharomyces cerevisiae strains used in asymmetric organic synthesis.

Fe (III) and Cu (II) each at 50 mu M in four commercial strains of Saccharomyces cerevisiae induced an increase of NAD(P)(+) reduction in one strain (Turkish), but two others (Chilean and Brazilian), the presence of Fe(III) and/or Cu(II) diminished NAD(P)(+) reduction presumably due to free radicals formation inside these living cells. Suprisingly, in the American strain, Fe(III) induced a decrease and Cu (II) an increase of NAD(P)(+) reduction.

Spectroscopic studies of the Eu3+ and Er3+ ions in the fluorozirconate LaZr2F11 matrix

An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

The acid-base impact of free water removal from, and addition to, plasma

Water, compared with plasma at a pH of 7.4, is a weak acid. The addition of free water to a patient should have an acidifying effect (dilutional acidosis) and the removal of it, an alkalinizing effect (concentrational alkalosis). The specific effects of free water loss or gain in a relatively complex fluid such as plasma has, to the authors' knowledge, not been reported. This information would be useful in the interpretation of the effect of changes in free water in patients. Plasma samples from goats were either evaporated in a tonometer to 80% of baseline volume or hydrated by the addition of distilled water to 120% of baseline volume. The pH and partial pressure of carbon dioxide, sodium, potassium, ionized calcium, chloride, lactate, phosphorous, albumin, and total protein concentrations were measured. Actual base excess (ABE), standard bicarbonate, anion gap, strong ion difference, strong ion gap, unmeasured anions, and the effects of sodium, chloride, phosphate, and albumin changes on ABE were calculated. Most parameters changed 20% in proportion to the magnitude of dehydration or hydration. Bicarbonate concentration, however, increased only 11% in the evaporation trial and decreased only -2% in the dehydration trial. The evaporation trial was associated with a mild, but significant, metabolic alkalotic effect (ABE increased 3.2 mM/L), whereas the hydration trial was associated with a slight, insignificant metabolic acidotic effect (ABE decreased only 0.6 mM/L). The calculated free water ABE effect (change in sodium concentration) was offset by opposite changes in calculated chloride, lactate, phosphate, and albumin ABE effects.