Spectrophotometric determination of sulfate by solvent extraction with the non-ionic surfactant span 20 and crystal violet

The sulfate ion is extracted into toluene with Span 20 (sorbitan monolaurate) and crystal violet. The calibration graph is linear over the range 2.5 × 10^-5–2.5 × 1O^-4 mol l^-1 sulfate (2.4–24 mg l^-1) in the aqueous phase when the extracted crystal violet is measured at 600 nm. The method is applied to natural waters.     

2-(8-quinolylazo)-4,5-diphenylimidazole — a sensitive extraction spectrophotometric reagent for mercury

Mercury(II) reacts with 2-(8-quinolylazo)-4,5-diphenylimidazole in aqueous solution; the complex can be extracted with chloroform or 1,2-dichloroethane at pH 4.5–9.5 to give a stable reddish-purple solution. The system conforms to Beer's law; the optimal range in chloroform is 0.05–2 ppm mercury (1-cm cells). Of 25 metal ions investigated, only copper and vanadium interfere seriously. The proposed method is exceptionally sensitive; the molar absorptivity in the chloroform extract is 7.3 × 10⁴ l mol^?1 cm^?1 at 580 nm; the Sandell sensitivity is 0.0027μg Hg cm^?2.     

Spectrophotometric study of the molybdenum(VI) chelate of flavon-3-ol-2'-sulfonic acid in strong acid solutions

Molybdenum(VI) reacts with flavon-3-ol-2'-sulfonic acid (HL) in strong acid solutions to form a 1:1 chelate which has a stability constant (log K) of 3.04 at 25°C and ionic strength (l) of 1.0. Beer's law is obeyed in the range 0.69–8.20μg Mo ml^-1 in 0.3 M perchloric acid; the molar absorptivity at 370 nm is 1.4 × 10⁴ l mol^-1 cm^-1.     

MULTIPLE CHROMOPHORE SPECIES IN PHYTOCHROME*,†,‡

Abstract— Buffered aqueous solutions of pure phytochrome, when irradiated at 730 nm, had a main absorption band at about 660 nm and a shoulder or secondary band at 580–600 nm. When irradiated at 660 nm, these absorption bands bleached and a pair of bands at 670 and 725–730 nm appeared. When 660 nm irradiated samples were placed in the dark the 730 nm absorption slowly bleached and the 670 nm absorption band shifted to 660 nm. The kinetics of the bleaching indicated that two populations of P_FR existed initially. These two populations decayed by first order kinetics with k's of 4.8 × 10^-4 sec^-1 and 3.1 × 10^--⁵ sec^-1at 25°. While the bleaching of P_FR was occumng, the appearance of the 660 nm and 580–600 nm absorption bands characteristic of P_R took place. The kinetics of the increase in the 580 and 660 nm absorption bands indicated that it was arising from two populations of reactants by two first order reactions with k's of 6.4 × 10^-4 sec^-1 and 3.1 × 10^-5sec^-1 at 25°. When the sodium chloride concentration of the solvent was changed the proportions of the kinetically different populations were altered. In some conditions, especially in the presence of air. reversible but non-reciprocal changes in the four absorption bands were observed. These effects were evident after the lapse of many hours in the dark. When native phytochrome was treated with sodium dodecyl sulfate all absorption bands but the 580–600 nm absorption band were bleached and photoreversibility was lost. When native phytochrome was treated with glutaraldehyde, the 730 nm absorption band was bleached but photoreversibility was retained. It was concluded that at least four species of chromophore exist in phytochrome with absorption maxima at 580, 660 , 670 and 730 nm. Each chromophore is capable of being bleached by appropriate irradiation or in the dark by chemical reactions rather than photochemical reactions. The reactions are probably coupled redox reactions between the 580–660 nm pair and the 670–730 pair of chromophores. Discrepancies observed in the reciprocity of the absorption changes in these paired bands are probably due to various degrees of uncoupling and secondarily to the redox potential of the solvent when such uncoupling occurs.     

Extraction—spectrophotometric and fluorimetric determination of thallium with 2-(4-methoxyphenyl)-5,7-diphenyl-4h-l,3,4-thiadiazolo[3,2-α] pyridinium chloride

The synthesis, characteristics and applications of 2-(4-methoxyphenyl)-5,7-diphenyl-4H⁺-1, 3,4-thiadiazolo[3,2-α]pyridinium chloride (TDZP) as a reagent for the formation of ion-pair complexes is described. Tetrachlorothatllate(III) can be extracted into isoamyl acetate as an ion-pair with TDZP. Thallium can be determined spectrophotometrically and fluorimetrically in the range 1–25 and 0.1–2 μg of thallium per 5 ml of organic layer, respectively. The molar absorptivity is 3.9 × 10⁴ l mol^-1 cm^-1. The quantum efficiency of the reagent is 0.42. The method is applicable to the determination of thallium in sphalerites and zinc or cadmium concentrates.     

Chlorophosphonazo-m-NO2, a new reagent for the spectrophotometric determination of cerium sub-group rare earth elements in the presence of yttrium sub-group elements

The synthesis of chlorophosphonazo-m-NO₂ is described. Cerium sub-group rare earth elements can be determined in the presence of 10–40 fold amounts of yttrium sub-group elements when the latter are masked by oxalic acid at pH 1.6. Under the experimental conditions employed, the apparent molar absorptivities of lanthanum and cerium at 666 nm are 9.5 × 10⁴ and 9.3 × 10⁴ l mol^-1 cm^-1, respectively. Beer's law is obeyed for 0–12 μg of lanthanum or cerium in 25 ml of solution. The coefficients of variation for La and Ce are 0.37% and 0.92%, respectively.     

High-efficiency process for production of sulfur from metallurgical sulfur dioxide gases

Process in which sulfur is produced from a gas containing 25–55% SO₂ was studied in order to evaluate the real efficiency of the catalytic post-reduction of sulfur dioxide in a pilot unit with gas flow rate of up to 1.2 nm³ h^–1 at the following temperatures (°C): thermal stage 850–1100, catalytic conversion 350–570, and Claus reactor 219–279. It was found that the conversion at 400–550°C and space velocity of 1600 h^–1 on AOK-78-57 promoted aluminum oxide catalyst provides full processing of organosulfur compounds (CS₂ and COS). The temperature dependence of the conversion/generation of hydrogen sulfide on AOK-78-57 catalyst corresponds to the equilibrium model. It was experimentally confirmed that the homogeneous reduction of sulfur dioxide gas with methane at T ≈ 1100°C, with catalytic post-reduction at 400–550°C and subsequent Claus-conversion of the reduced gas at 230–260°C, provide a sufficiently deep (by 92–95%) general processing of sulfur dioxide gas to sulfur.     

Kinetics of oxidation of methanol and mono-deutero-methanol by chromium(VI) in perchloric acid medium

Kinetics of the oxidation of methanol and mono-deutero-methanol by Cr(VI) over a wide range of temperature (25–40°) have been studied in perchloric acid medium at constant ionic strength (μ = 1.0 M) adjusted with sodium perchlorate. Each reaction is first order with respect to the substrate and dichromate concentrations but the order with respect to [H⁺] is nearly 3 in each case. Both these reactions take place at almost the same rate under identical experimental conditions. The activation parameters of the reactions are not widely different and the values of ΔH3 and ΔS3 for the oxidation of methanol are 79.5 kJ mole ^-1 and - 38.1 J deg^-1 mole^-1 respectively, whereas the corresponding values for the deuterated compound are 83.8 kJ mole^-1 and -23.9 J deg^-1 mole^-1. The probable mechanism of the reactions is discussed.     

Photometric determination of calcium with antipyrylazo III

Antipyrylazo III or diantipyrylazo (3,6-bis(4-antipyrylazo)-4,5-dihydroxy-2, 7-napthalenedisulfonic acid) forms at PH 12.7 a complex Ca₂HL with calcium. The logarithmic overall stability constant, 10g β₂₁₁, is 23.99 ±0.03 (0.1 MNaClO₄,25°C).The effective molar absorptivity is 21,500 ±100 l mole^-1 cm^-1 at 605 nm. The complex can be used for a selective photometric determination of calcium(0.25–3.50μmole) if tri-and tetravalent ions are removed by extraction with cupferron (into chloroform) and transition divalent ions are masked with sodium cyanide. Only strontium (0.5 μmole) and EDTA (0.1 μmole) interfere seriously.     

Glucose Oxidase Electrode Based on Graphite and Methylthio Tetrathiafulvalene as Mediator

Abstract

A glucose sensor based on glucose oxidase and a new mediator - 4,5-dimethyl-4′-methylthio-Δ 2,2′-bi-1,3-dithiole (MTTTF) is described. The background for sensor action is the effective MTTTF cation interaction (apparent bimolecular constant (2.0+/-0.5)?10⁶ M^?1 s^?1 at 25°C and pH 7.0) with reduced glucose oxidase and the high electrochemical rate of mediator transformation.

A glucose sensor was prepared by adsorbing mediator (MTTTF) and glucose oxidase on graphite rods. The sensor responds to glucose at electrode potentials higher than 50 mV vs SCE, but the maximal activity is obtained at a potential of 250 mV. In air saturated solution the electrode shows a non-linear calibration curve with a half-saturation concentration 10.4 mM and Hill coefficient 2.08 at 250 mV. Sensor response changes little at pH 6.5–8.0. The energy of activation of the sensor response calculated from the Arrhenius equation was 64.5 kJ/mol, and the temperature coefficient at 25°C was 9.2%.     

“Stat” methods in continuous flow analysis : Determination of Copper,Iron, Iodide and Hydrochloric Acid

A continuous flow “stat” method is described in which a certain arbitrarily imposed state in the flowing stream is automatically maintained by regulating the rate of flow of one of the components. The electronic system is regulated by measuring a physical phenomenon in the flowing solution. The method is illustrated by the examples of a continuous flow absorptiostat [Fe(III)/S₂O₃^2-/Cu(II)]for determinations of copper(II) (1–10 μg ml^-1), iron(III) (25–250 or 12.5–125 μg ml^-1), as well as for determination of iodide (12.8–128 μg ml^-1). A continuous flow conductostat [HCl/NaOH] for determination of 1–2.5 × 10^-4 M HCl is also described. This analytical technique is intended for automatic continuous monitoring of sample streams.     

Kinetics of the reaction of OH radicals with acetylene in 25–8000 torr of air at 296 K

Relative rate techniques were used to study the kinetics of the reaction of OH radicals with acetylene at 296 K in 25–8000 Torr of air, N₂/O₂, or O₂ diluent. Results obtained at total pressures of 25–750 Torr were in good agreement with the literature data. At pressures >3000 Torr, our results were substantially (～35%) lower than that reported previously. The kinetic data obtained over the pressure range 25–8000 Torr are well described (within 15%) by the Troe expression using k_o = (2.92 ± 0.55) × 10^?30 cm⁶ molecule^?2 s^?1, k_∞ = (9.69 ± 0.30) × 10^?13 cm³ molecule^?1 s^?1, and F_c = 0.60. At 760 Torr total pressure, this expression gives k = 8.49 × 10^?13 cm molecule^?1 s^?1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 191–197, 2003     

Adsorptive behavior and electrochemical determination of the anti-fungal agent ketoconazole

The adsorptive properties and electrochemical behavior of ketoconazole, an oral anti-fungal agent, are demonstrated at a glassy carbon electrode. The adsorption of the compound obeys the Frumkin isotherm with an interaction factor (α) of 0.985 and adsorptive coefficient (β) of 1.98 × 10⁶ L mol^–1. The Gibbs energy of adsorption (ΔG) is –3.59 × 10⁴ J mol^–1 at 25?°C. A very sensitive electroanalytical method has been developed for determination of the drug with a detection limit of 4.0 × 10^–11 mol L^–1. Relationships between stripping current and concentration of ketoconazole were linear in the range 10^–6–10^–10 mol L^–1 with different preconcentration periods. The method has been used to measure the ketoconazole content of tablets.     

Spectrophotometric and fluorimetric determinations of trichothecene mycotoxins with reagents for formaldehyde

Several trichothecene mycotoxins, such as fusarenone-X (F-X) and T-2 toxin (T-2), readily liberate formaldehyde on heating with sulfuric acid. Spectrophotometric and fluorimetric methods for the determination of trichothecenes with reagents for formaldehyde are therefore possible. F-X (or T-2) can be determined in the 50–1000 mg l^-1 (or 50–1500 mg l^-1) range by the chromotropic acid method, in the 30–1200 mg l^-1 (or 50–2000 mg l^-1) range by the phenyl J acid method, and in the 1.25–25 mg l^-1 (or 2–40 mg l^-1) range by the J acid method. Other trichothecenes, neosolaniol, nivalenol, tetraacetylnivalenol, diacetoxyscirpenol and HT-2 toxin, etc. also give positive reactions but trichothecin and dihydronivalenol do not.     

Redetermination of the standard ph values for potassium hydrogenphthalate reference buffer solution from 0 to 85°c

Values of pH(S) for 0.05 mol kg^-1 solutions of potassium hydrogenphthalate in the temperature range 0–85 °C have been obtained from cells without transport. The results are compared with re-analysed results from previous investigations by a new method of multilinear regression of pH as a function of both temperature and added chloride concentration. The results fit the equation pH(S) = 4.005 + 1.0068 × 10^-3 (T — 298.15) + 3.275 × 10^-5 (T — 298.15)² where T is the temperature expressed in Kelvin; pH(S) = 4.005 at 25°C.     

Spectroscopic analysis of pindolol irradiated in the solid state

Pindolol ((2RS)-(1-(1H-indol-4-iloxy)-3- [(1-metyloetylo)amino]-2-propanol) in substantia was exposed to ionising radiation emitted by high energy electrons from an accelerator, in the standard sterilisation dose of 25 kGy and in higher doses from the range 50–400 kGy. The effects of irradiation were checked by spectrometric methods (UV, MS, FT-IR, EPR) and hyphenated methods (HPLC-MS) and the results were referred to those obtained for non-irradiated sample. EPR results indicated the presence of free radicals in irradiated samples, in the amount of 1.36 × 10¹⁶ spin g^?1 for 25 kGy and 3.70×10¹⁶ spin g^?1 for 400 kGy. The loss of pindolol content determined by HPLC was 1.34% after irradiation with 400 kGy, while the radiolytic yield of the total radiolysis for this dose of irradiation was 2.69×10⁷ mol J^?1. By means of HPLC-MS it was possible to separate and identify one product of radiolytic decomposition, which probably is 2-((R)-3-(1H-indol-4-yloxy)-2-hydroxypropylamino)propan-1-ol formed upon oxidation. In the range of sterilisation doses (25–50 kGy), pindolol was found to show high radiochemical stability and would probably be safely sterilised by the standard dose of 25 kGy.      

Controlled Preparation and Reactive Silver‐Ion Sorption of Electrically Conductive Poly(N‐butylaniline)–Lignosulfonate Composite Nanospheres

Electroconductive poly(N‐butylaniline)–lignosulfonate (PBA–LS) composite nanospheres were prepared in a facile way by in situ, unstirred polymerization of N‐butylaniline with lignosulfonate (LS) as a dispersant and dopant. The LS content was used to optimize the size, structure, electroconductivity, solubility, and silver ion adsorptive capacity of the PBA–LS nanospheres. Uniform PBA–LS10 nanospheres with a minimal mean diameter of 375 nm and high stability were obtained when the LS content was 10 wt %. The PBA–LS10 nanospheres possess an increased electroconductivity of 0.109 S cm^?1 compared with that of poly(N‐butylaniline) (0.0751 S cm^?1). Furthermore, the PBA–LS10 nanospheres have a maximal silver‐ion sorption capacity of 815.0 mg g^?1 at an initial silver ion concentration of 50 mmol L ^?1 (25 °C for 48 h), an enhancement of 70.4 % compared with PBA. Moreover, a sorption mechanism of silver ions on the PBA–LS10 nanospheres is proposed. TEM and wide‐angle X‐ray diffraction results showed that silver nanoparticles with a diameter size range of 6.8–55 nm was achieved after sorption, indicating that the PBA–LS10 nanospheres had high reductibility for silver ions.     

Influence of the Conditions for Preparing LaPO<Subscript>4</Subscript>-Based Materials with Inclusions of the LaP<Subscript>3</Subscript>O<Subscript>9</Subscript> Phase on Their Thermal and Mechanical Properties

A material based on lanthanum orthophosphate LaPO₄ with inclusion of particles of lanthanum metaphosphate LaP³O₉ was synthesized. The influence of the process parameters of the synthesis on the structure and properties of the material was determined. Heat treatment of the coprecipitated lanthanum phosphates at 700°C leads to the formation of a nanopowder with the LaPO₄crystallite size of approximately 17 nm. Heat treatment of the nanopowder at temperatures from 1100 to 1500°C yields compact materials based on the LaPO₄–LaP₃O₉ system. The heat treatment of the nanopowder at 1100°C leads to a sharp decrease in the porosity of the material (to ~5%) at insignificant grain growth (200–400 nm); under these conditions, the thermal conductivity [λ(25°C) = 3.2 W m–1 K^–1], microhardness [Hv(25°C) = 4.6 ± 0.4 GPa], Young’s modulus [E(25°C) = 132 ± 9 GPa], and cracking resistance [K_1c(25°C) = 1.6 ± 0.1 MPa m^1/2] pass through maxima. The thermal expansion coefficient of the material depends on the heat treatment conditions only slightly and amounts to (8.2 ± 0.2) × 10^–6 K^–1.     

Phospho‐l‐tyrosine‐agarose chromatography: Adsorption of human IgG and its proteolytic fragments

The behavior of human immunoglobulin G (IgG) and antigen‐binding fragment (Fab fragment) adsorption onto phospho‐l ‐tyrosine immobilized on agarose (P‐Tyr‐agarose) was evaluated by pseudoaffinity chromatography. The effects of buffer systems MES, MOPS, Bis–Tris, Tris–HCl and sodium phosphate (NaP) and pH on IgG adsorption were studied and high purity values were obtained (96%, based on ELISA analysis of albumin, transferrin and immunoglobulins A, G and M) when IgG was purified from human plasma diluted in 10 mmol L^?1 NaP buffer at pH 6.0. The capture of IgG by the P‐Tyr‐agarose was also promising, since 91% of the IgG was adsorbed when plasma was diluted in 25 mmol L^?1 MES buffer at pH 5.5, recommending its use for IgG depletion from human plasma under this condition. The experimental data on IgG adsorption kinetics were in agreement with the pseudo‐second‐order model. The adsorption isotherm data were well described by the Langmuir–Freundlich model with the value of parameter n being <1 (0.72), indicating negative cooperativity. Selectivity was achieved on P‐Tyr‐agarose from digested human IgG in HEPES 25 mmol L^?1 buffer at pH 7.0 where Fab fragments were obtained in eluted fractions without Fc fragments (but with uncleaved IgG) with 86.2% recovery.     

Reaction of trans-[Co(en)2(SO3)(H2O)]+ with imidazole and containing ligands

trans-[Co(en)₂(SO₃)(H₂O)]⁺ reacts with imidazole (ImH) and imidazole containing ligands (L) to form trans-[Co(en)₂(SO₃)L]⁺ in the pH range 6.0–9.0. The complex seems to react both in the hydroxy and in the aquo form. The rate constant for the reaction of imidazole with the aquo form is 6.0±0.7 and 4±1M^?1s^?1 for the reaction with the hydroxy form at 25°C. The apparent equilibrium constant for formation of the imidazole complex at pH 7 is consistent with the value of 3 x 10² measured previously. Appreciable amounts of complex form only in the pH 6–9 range. Above pH 9 NMR spectra show that even the immediate products are different. In aged solutions at all pHs other products form.