A calcium-sensitive microelectrode suitable for intracellular measurement of calcium(II) activity

A calcium-selective microelectrode with a l-μm diameter tip suitable for impaling single neurons has been developed. The electroactive material is di[p-(1,1,3,3-tetramethyl-butyl) phenyl] phosphoric acid (t-HDOPP). The selectivity coefficients are about 5 · 10^-7 for k_Ca,K, 1–4·10^-7 for k_Ca,Na, and 10^-3 for k_Ca,Mg. Values reported previously for other calcium-selective electrodes based on long-chain phenylphosphoric acids are given for comparison. The calcium-selective microelectrodes have a linear response in 0.2 M KCl solutions over the range 10^-2–10^-XXX M CaCl₂; 10^-7 and 10^-8 M CaCl₂ solutions containing 0.2 M KCl can be detected but the response is not linear.     

Trace fluoride determination with specific ion electrode

A method is described for determining 10^-5–10^-4M fluoride in a variety of solutions potentiometrically with a fluoridc-specific electrode, by a standard addition method. Any change of ionic strength or the nature of the solution that might alter activity coefficients or junction potentials is minimized. The relationship between potential and fluoride concentration thus follows the Nernst equation, and the unknown concentration can be calculated. Experimental data are given for solutions of sodium choride, sodium nitrate, acidified sodium silicate and sodium hydroxide, lithium chloride, and phosphoric acid. Metal ions (e.g., Al³⁺, UO₂²⁺, Fe³⁺, Th⁴⁺) that interfere by forming complexes with fluoride can be precomplexed with phosphoric acid. The relative error is estimated at 10%, and the relative standard deviation is less than 5% over the concentration range 10^-5–10^-4M fluoride.     

Interaction of tris(2,2′-bipyrazine)ruthenium(2+) ion with radiolytically-generated radicals in aqueous solution. Reactivity of Ru(bpz)+3 toward electron relays

The one-electron reduction of Ru(bpz)²⁺₃ by (CH₃)₂ḢOH is rapid (k = 3.5 × 10⁹ M^-1 s^-1) and quantitative. The product of the reaction, which possesses a ligand-radical coordinated to a Ru(II) center, can be written generically as Ru(bpz)⁺₃, and represented as Ru(bpz)₂(^.bpz^-)⁺ in alkaline solution and its conjugate acid [Ru(bpz)₂(^.bpzH)²⁺; pK_a = 7.1] in acidic solution. The reaction of Ru(bpz)²⁺₃ with ^.OH (k = 5.5 × 10⁹ M^-1 s^-1) yields the OH-adduct to the ring system of the ligands; Ru(bpz)₂(^.bpzOH)²⁺ is unstable toward bimolecular decay (k ∼4× 10⁸ M^-1 s^-1). Reaction with H^. (k = 3 × 10⁹ M^-1 s^-1) results in hydrogenation at a ring-carbon; this product is unstable in the time frame of seconds. No reaction is observed between Ru(bpz)²⁺₃ and Cl^-.₂. Ru(bpz)₂(^.bpz^-)⁺ reduces Co(sep)³⁺ (k = 3.3 × 10⁵ M^-1 s^-1) at pH 10, but there is no reaction at pH 4. However, Ru(bpz)₂(^.bpzH)²⁺ establishes an electron-transfer equilibrium (K_eq = 7) with Cr(bpy)³⁺₃ at pH 3.     

Radiochromic dye dosimeter solutions as reference measurement systems

Solutions of leucocyanides of triphenylmethane dyes in organic solvents are designed as stable reference dosimeters for large radiation doses, with useful characteristics, both for steady-state and pulsed radiation fields. These radiochromic solutions may be used in conventional glass ampoules to cover the absorbed dose range 10²–10⁴kGy, when analyzed spectrophotometrically at visible wavelengths at the maxima of radiation-induced absorption bands. The radiation chemical yields of dye formation (G-values) and molar linear absorption coefficients (ϵ_m) of the dyes in several formulations, with and without dissolved polymer and weak oxidizing agents, are established. The most stable formulation before and after irradiation consists of new fuchsin cyanide in a mixture of dimethyl sulfoxide and triethyl phosphate containing small amounts of acetic acid, p-nitrobenzoic acid and polyvinyl butyral. The useful range of doses for this solution is 10²-4 x 10³ Gy when measured at 557 nm wavelength. The radiation chemical yield, G-value for dye production, is 3.35 x 10¹⁵ molec J^-1 (0.0055 μmol J^-1) and the value of ϵ_m at this wavelength is 1.32 x 10⁵ M^-1 cm^-1.     

An electrochemical sensor for dipyrone determination based on nickel-salen film modified electrode

An amperometric dipyrone sensor based on a polymeric nickel-salen (salen = N,N´-ethylenebis(salicydeneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at a platinum electrode in acetonitrile/tetrabuthylamonium perchlorate by cyclic voltammetry. After cycling the modified electrode in a 0.50 mol L^-1 KCl solution, the estimated surface concentration was found to be equal to 1.29 x 10^-9 mol cm^-2. This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the nickel(II)/nickel(III) couple. A plot of the anodic current versus the dipyrone concentration for chronoamperometry (potential fixed = +0.50 V) at the sensor was linear in the 4.7 x 10^-6 to 1.1 x 10^-4 mol L^-1 concentration range and the concentration limit was 1.2 x 10^-6 mol L^-1. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.     

Kinetic determination of ascorbic acid by the 2,6-dichlorophenolindophenol reaction with a stopped-flow technique.

The reaction of ascorbic acid with 2.6-dichlorophenolindophenol is applied for the kinetic determination of ascorbic acid in 0.05M oxalic acid. Stopped-flow techniques are used; the concentrations of the reactants of the second-order reaction can be adjusted so that the transmittance signal remains nearly invariant for a wide range of voltage. Theoretical and experimental results are in very good agreement. Analytical working curves are presented for the determination of ascorbic acid in the ranges 5.0·10^-4–1.0·10^-2M and 5.0·10^-5–1.0-·10^-3M with errors of 1.0% and 2.2%. respectively. The method is simple, fast and sensitive.     

Kinetics of one-electron oxidation by the ClO radical

Pulse radiolysis studies were carried out to determine the rate constants for reactions of ClO radicals in aqueous solution. These radicals were produced by the reaction of OH with hypochlorite ions in N₂O saturated solutions. The rate constants for their reactions with several compounds were determined by following the build up of the product radical absorption and in several cases by competition kinetics. ClO was found to be a powerful oxidant which reacts very rapidly with phenoxide ions to form phenoxyl radicals and with dimethoxybenzenes to form the cation radicals (k = 7 × 10⁸ −2 × 10⁹ M^-1 s^-1). ClO also oxidizes ClO^-₂ and N^-₃ ions rapidly (9.4 × 10⁸ and 2.5 × 10⁸ M^-1 s^-1, respectively), but its reactions with formate and benzoate ions were too slow to measure. ClO does not oxidize carbonate but the CO^-₃ radical reacts with ClO^- slowly (k = 5.1 × 10⁵ M^-1 s^-1).     

Application of semidifferential electroanalysis to anodic stripping voltammetry

A new voltammetric technique, Semidifferential electroanalysis, in which the semiderivative, e, of the current, i, is measured as a function of electrode potential, has been applied for detection in anodic stripping voltammetry. The semiderivative of the current is defined by [fx131-1.tif] Cd²⁺, Pb²⁺, and Tl⁺ in 0.1 M KNO₃ at different pH values were tested as samples on a hanging mercury drop working electrode. Symmetrical sharp peaks were observed for the re-dissolution processes of metal amalgams formed during pre-electrolysis at -1.0 V vs. SCE. The peak potentials of e vs. E curves for the above three amalgams agreed well with the literature values for d.c. polarographic half-wave potentials. The peak heights were proportional to the pre-electrolysis time up to about 5 min, to the potential scan rate in the range 60–160 mV s^-1, and to the concentrations of Cd²⁺, Pb²⁺, and Tl⁺ in the original solution in the range 10^-6–10^-9 M. The relative standard deviation for the determination of Cd²⁺ was about ±4% at the 2 × 10^-5 M level.     

Application of iso-temperature method of multiple rate to kinetic analysis

A new method of the multiple rate iso-temperature was used to define the most probable mechanism g(α) of a reaction; the iterative iso-conversional procedure has been employed to estimate apparent activation energy E _a, the pre-exponential factor A was obtained on the basis of E _a and g(α). In this new method, the thermal analysis kinetics triplet of dehydration of calcium oxalate monohydrate is determined, which apparent activation energy E _a is 82.83 kJ mol^-1, pre-exponential factor A is 1.142·10⁵-1.235·10⁵ s^-1, the most probable mechanism belongs to phase boundary reaction R_n with integral form g(α)=1-(1-α)ⁿ and differential form f(α)=n(1-α)^1-(1/n), where accommodation factor n=2.40-1.40.     

Free radical inactivation of trypsin

Reactivities of free radical oxidants, ^.OH, Br^-·₂ and Cl₃COO^. and a reductant, CO^-·₂, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20°C. Highly reactive free radicals, ^.OH, Br^-·₂ and CO^-·₂, react with trypsin at diffusion controlled rates, k(^.OH + trypsin) = 8.2 × 10¹⁰ M^-1 s^-1, k(Br^-·₂ + trypsin) = 2.55 × 10⁹ M^-1 s^-1 and k(CO^-·₂ + trypsin) = 2.6 × 10⁹ M^-1 s^-1. Moderately reactive trichloroperoxy radical, k(Cl₃COO^. + trypsin) = 3 × 10⁸ M^-1 s^-1, preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by ^.OH, Br^-·₂ and CO^-·₂ are low, G(inactivation) = 0.6-0.8, which corresponds to ∾ 10% of the initially produced radicals. In contrast, Cl₃COO^. inactivates trypsin with ∾ 50% efficiency, i.e. G(inactivation) = 3.2.     

Electron-cation recombination in rigid organic glasses: simulation of charge distribution and isothermal luminescence kinetics

Recent results on isothermal luminescence decays, observed from 10^?8 to 10⁴ s after irradiation of a rigid glass at 77 K, are interpreted in terms of tunnelling electron-ion recombination. After 10^?6 s, recombination of isolated pairs is dominant. Electron-ion distance distributions are obtained by computer simulation and used to calculate the corresponding decay kinetics I(t). I(t) ∝ t^?1.0 is found with realistic chosen parameters throughout the whole time range investigated experimentally, so that tunnelling recombination is quantitatively consistent with observation. Experimental study at shorter times (10^?8-10^?6 s) indicates a contribution from recombinations of pairs which are not isolated. A very simple computer simulation of these effects is proposed and shown to agree with experiment.     

Synthesis of (+)-(3S,7S,10S)- and (+)-(3S,7S,10R)-3,7,10-trimethylboratrane. Amplification of enantiomeric purity in the reacti

The synthesis is described of the two enantiomerically pure isomers (+)-(3S,7S,10S)- and (+)-(3S,7S,10R)-3,7,10-trimethylboratr The structures were determined by ¹H- and ¹³C-NMR spectroscopy. A method for increasing the enantiomeric purity by trimerization reactions of partially-resolved (S) propylene oxide is proposed. The reaction was studied from the kinetic viewpoint and interpreted according to a binomial probability scheme. The experimental findings point to a rapid growth in enantiomeric purity for the (SSS) trimer compared with the starting material, whilst no increase was found for the (SSR) trimer.     

Using 4-methyl-4-phenyl-2-pentanone as a singlet probe of benzene,cyclohexane, tributylphosphate and its multiple scavenger effects

A special probe of excited singlet states was established. The Norrish type II elimination reaction of 4-methyl-4-phenyl-2-pentanone (MPP) induced by γ-rays was reinvestigated. By measuring the G value of the sensitization radiolytic product α-methylstyrene (α-MS), we obtained the G value of excited singlet states. It was found that the G value of benzene excited singlets is 1.4±0.2, the rate constant of excitation energy transfer from benzene excited singlets to MPP is (5.2±0.5)×10⁹dm³mol^-1s^-1; the G value of excited tributylphosphate singlets is 1.4±0.3, the lifetime of its excited singlets is (1.3±0.1)×10^-7s; the G value of excited cyclohexane singlets is 1.5±0.2, the rate constant of excitation energy transfer from cyclohexane excited singlets to MPP is (4.1±0.4)×10¹⁰dm³mol^-1s^-1. It was found that MPP has multiple effects in quenching the active species formed in the radiolysis of benzene and tributylphosphate, both excitation energy transfer and reaction with subexcitation electrons have occured. A yield of subexcitation electrons of benzene 4.0, that of tributylphosphate 5.0, was obtained. The kinetics of both processes were also discussed.     

Calcium ion selective membrane electrode

The calcium salts of the mono- and diesters of [4-(1,1,3,3-tetramethylbutyl)phenyl phosphoric acid] have been prepared, and the individual esters as well as mixtures of the esters have been used with several varieties of polyvinyl chloride to construct macro membrane electrodes selective to calcium ions. These electrodes have been calibrated by using solutions of CaCl₂ and Ca ion buffers. The mixed ester electrodes showed Nernstian response in the concentration range 10^-1 to 10^-7M; the diester electrodes showed Nernstian response down to 7.9 x 10^-8M. The detection limit of the mixed ester electrode was 10^-8M, whereas that of the diester electrode was 7.9 x 10^-9M. Contrary to these results, the monoester electrodes showed unsatisfactory behavior. The responses of both the mixed ester and diester electrodes to calcium ions were not affected by the presence of sodium, potassium, or other divalent ions. Only ferric and lanthanum ions showed interferences with the electrode response to calcium ions. p]The electrode response was independent of pH in the approximate range 5–8 at a CaCl₂ concentration of 10^-4M. As the Ca ion concentration was increased, the range of pH independence widened to approximately 4–8. The dynamic response time constant of the mixed ester electrode was in the range 0.7–1.5 sec, whereas that of the diester electrode was in the range 0.5–0.75 sec.     

Mechanisms and kinetics of the ozonolysis reaction of cis-3-hexenyl acetate and trans-2-hexenyl acetate in atmosphere: a theoretical study

Gas-phase reaction mechanisms of ozone with cis/trans-3-hexenyl acetate and cis/trans-2-hexenyl acetate are performed using density functional theory. The reactions are initiated by the formation of the primary ozonides which are followed by the reactions of biradicals with H₂O or NO. The formation of the secondary ozonide (SOZ) is also studied. On the basis of the above DFT calculations, the modified multichannel RRKM theory is used to evaluate the rate constants. At 298 K and 101 kPa, the calculated total rate constants are 9.84 × 10^?17, 1.39 × 10^?17, 2.50 × 10^?17, and 7.37 × 10^?17 cm³ mol^?1 s^?1 for cis-3-hexenyl acetate, trans-2-hexenyl acetate, cis-2-hexenyl acetate, and trans-3-hexenyl acetate, respectively. Our results are in good agreement with experimental values. The total rate coefficients are almost pressure-independent in the range of 0.01–10,000 Torr, but show temperature dependence over the whole study range (200–2,000 K). In addition, branching ratios of the favorable reaction channels are obtained.     

Rapid determination of nicotinic acid by immobilized lactobacillus arabinosus

A rapid determination of aicotinic acid by using immobilized Lactobacillus arabinosus and a combined glass electrode is reported. L. arabinosus is immobilized in agar gel. The optimum agar concentration is from 2–2.5% ($\text{w}\text{v}$) and the optimum bacterial concentration in the agar gel matrix is 10 mg wet cells ml^-1. The relationship between the potential difference and the logarithm of the nicotinic acid concentration is linear over the range 5 X 10^-8–5 X 10^-6 g ml^-1. The assay requires only 1 h; potentials are reproducible with an average relative error of 5%. The growth of L. arabinosus in agar gel matrix is observed in the medium containing nicotinic acid. Immobilized L. arabinosus is stable for 30 days.     

Extractive spectrophotometric determination of nitrite in polluted waters

Nitrite is diazotised with p-nitroaniline in hydrochloric acid and coupled with 8-quinolinol in alkaline medium to give a purple azo dye (λ_max = 550 nm, ? = 3.88 × 10⁴ l mol^-1 cm^-1). Extraction of the dye into 3-methyl-1-butanol shifts the absorption maximum to 570 nm and improves the apparent molar absorptivity to 5.852 × 10⁴ l mol^-1 cm^-1. Beer's law is obeyed for 0.01–0.06 ppm nitrite. The Sandell sensitivity is 0.00078 μg cm^-2. The method is applicable to polluted waters.     

Flow-injection spectrophotometric determination of palladium in catalysts and dental alloys with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropyl-amino)aniline

2-(5-Bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)aniline rapidly forms a water-soluble complex with palladium in an acetate-buffered medium at pH 3.2.The molar absorptivity of the complex is 9.84×10⁴l mol^?1 at 612 nm. The calibration graph is linear over the range of 10–100 μg l^?1 palladium; the detection limit is 2 μg l^?1 and the relative standard deviation is 0.6% for 100 μg l^?1 palladium. The sample throughput is 50 h^?1. Divalent transition metals (Fe, Ni, Co) do not interfere at levels from 2 to 10 mg l^?1. Interference from copper is prevented by adding 10^?3 M EDTA solution to the carrier stream. Palladium in solutions of catalysts and dental alloys can be determined selectively, sensitively and rapidly.     

Some electrophilic substitution reactions of closo-[1-CB11H12]− and one-boron insertion into nido-7-L-7-CB10H12 (L = H− or Me3N) compounds. Isolation of all three B-substituted closo-Me3N-1-CB11H11 derivatives

Electrophilic deuteration of closo-[1-CB₁₁H₁₂]⁻ in the DCl/D₂O system confirmed the expected order of reactivity on individual skeletal atoms, decreasing in the series B(12) > B(7–11) > B(2–6) > C(1). In contrast, electrophilic B-substitution of closo-[1-CB₁₁H₁₂]⁻ with H₂NOSO₃H is consistent with the preference of the B(7)-substitution to suggest a different mechanism for almost exclusive formation of 7-H₃N-closo-1-CB₁₁H₁₁. 7-Me₃N-closo-1-CB₁₁H₁₁ was isolated along with the remaining 2- and 12-Me₃N-1-CB₁₁H₁₁ isomers as side products of the thermal decomposition of [BH₂(NMe₃)₂]⁺[nido-7-CB₁₀H₁₃]⁻ at 270°C, which is inconsistent with a specific insertion of the BNMe₃ fragment into the open face of nido-[7-CB₁₀H₁₃]⁻. Nevertheless, clean ¹⁰B-insertion was observed in the reactions of Et₃N¹⁰BH₃ with both nido-[7-CB₁₀H₁₃]⁻ and 7-Me₃N-nido-7-CB₁₀H₁₂ to give respectively closo-[1-CB₁₁H₁₂]⁻ and [1-Me₂N-1-CB₁₁H₁₁]⁻ labelled by ¹⁰B exclusively at the B(2) site. Cage rearrangement was observed, however, in the reaction of 7-Me₃N-8-PhCH₂-nido-7-CB₁₀H₁₁ with Et₃NBH₃ under similar conditions to produce only the 1-Me₃N-7-PhCH₂-1-CB₁₁H₁₀ closo-isomer.     

Solution properties of poly[1-(9-carbazyl)-2,3-(diethoxycarbonyl)-butane-1,4-diyl]

Poly[1-(9-carbazyl)-2,3-(diethoxycarbonyl)-butane-1,4-diyl] (I), obtained by radical copolymerization of 9-vinylcarbazole with diethylfumarate, has been characterized by viscometry and light scattering. The Huggins constant in benzene at 25 is k_H = 0.33. The Mark-Houwink relationship suggests that benzene is a good solvent for the alternating copolymer I (a = 0.67; K = 1.46·10^?2 ml/g). The unperturbed dimension of the chain is given by value (R₀²/M)^0.5 = 5.73·10^?9 cm·mol^0.5 g^?0.5. The steric factor σ = 2.51 indicates a higher flexibility for this polymer than for poly[1-(9-carbazyl)ethylene].