C60F14OFPh3, a fluoroxy derivative of C60F15Ph3; evidence for the presence of ‘missing’ fluorine through restricted rotation of a phenyl group

From the reaction of C₆₀F₁₈ with benzene in the presence of SbCl₅ we have isolated a compound of 1252 amu indicated to be C₆₀F₁₄OFPh₃, a fluoroxyfullerene. Temperature-variable ¹H NMR shows that one phenyl group suffers restricted rotation on cooling to 218 K, attributed to the presence of the OF group which, as in the case of the recently characterised C₆₀F₁₇OF, fails to give a signal for this group in the ¹⁹F NMR. We have isolated also, C₆₀F₁₄O₂FPh₃ (1268 amu) a mixture of oxahomo derivatives of C₆₀F₁₄OFPh₃ arising from oxygen insertion into FCCF bonds. Theoretical calculations for C₆₀F₁₄OFPh₃ indicate that the phenyl group nearest to the OF group is twisted out of the plane containing the other two.     

Photo-degradation and photo-stabilisation of the two-phase system poly(vinyl chloride)-polybutadiene

The photo-oxidative degradation of poly(vinyl chloride) (PVC)/polybutadiene (PB) blends has been studied. After uv irradiation, photo-grafting of the PVC and PB phases was observed. Photolysis of PVC accelerates cis-trans isomerisation of PB. Both phases, PVC and PB, are photo-degraded according to free radical oxidation mechanisms. The rates of these processes can be decreased by the addition of metal chelates, such as commercially produced Cyasorb uv light absorber 1084 (2,2′-thiobis(4-t-octylphenolato)-n-butylamine nickel(II)) and Cyasorb uv light absorber 2548 (cobalt dicyclohexyldithiophosphinate).     

Hybrid organic/inorganic films of conducting polymers modified with phthalocyanines. I—Film preparation and voltammetric studies

Conducting polymers were deposited on the surface of platinum and glassy carbon electrodes. The monomers used were N-methyl pyrrole and 3-methyl thiophene. The electrochemical synthesis of the polymer was achieved using constant applied potential or cyclic polarization techniques in acetonitrile as a solvent and tetra-alkyl ammonium salts as supporting electrolyte. The resulting conducting polymeric film was modified with an inorganic metal complex, namely, Cu–phthalocyanine or Co–phthalocyanine. Two different approaches were adopted for the modification: (1) the first was to directly apply the metal–phthalocyanine layer on the surface of the polymer, and (2) the second was by the inclusion of the metal–phthalocyanine in a sol–gel matrix that was in turn applied to the conducting polymer film. In the first part of this work, we studied the effect of changing the type of polymer matrix and the central metal of the inorganic complex on the electrochemical behavior of the resulting film. We also found that changing the method of metal–phthalocyanine application to the polymer film affected the electrochemical response and kinetics at the electrode surface. The new electrode was tested for the reduction of hydrogen peroxide and showed better conversion efficiency compared to conventional surfaces, which suggests its use in fuel cell applications.     

Note on stability theorems for nonlinear mixed integral equations

In this paper we study the stability theorems for nonlinear Fredholm-Volterra integral equations system.     

On a quadratic integral equation with supremum involving Erdélyi‐Kober fractional order

We introduce Erdélyi‐Kober fractional quadratic integral equation with supremum, namely . This equation contains as special cases numerous integral equations studied by other authors. We show that there exists at least one monotonic solution belonging to C[0, 1] of our equation. The main tools in our analysis are Darbo fixed point theorem and the measure of noncompactness related to monotonicity which was introduced by Bana? and Olszowy. Finally, we present an example for illustrating the natural realizations of our abstract results.     

Spectrophotometric analysis of selective serotonin reuptake inhibitors based on formation of charge-transfer complexes with tetracyanoquinodimethane and chloranilic acid

A simple, accurate, and sensitive spectrophotometric method for analysis of selective serotonin reuptake inhibitors (SSRIs) has been developed and validated. The analysis was based on the formation of colored charge-transfer complexes between the intact molecule of SSRI drug as an n-electron donor and each of tetracyanoquinodimethane (TCNQ) or p-chloranilic acid (pCA) as electron acceptors. The formed complexes were measured spectrophotometrically at 842 and 520 nm for TCNQ and pCA, respectively. Different variables and parameters affecting the reactions were studied and optimized. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9975-0.9996) were found between the absorbances and the concentrations of the investigated drugs in the concentration ranges of 4-50 and 20-400 microg/mL with TCNQ and pCA, respectively. With all the investigated drugs, TCNQ gave more sensitive assays than pCA; the limits of assay detection were 2.5-4.8 and 20-40 microg/mL with TCNQ and pCA, respectively. The intra- and interassay precisions were satisfactory; the relative standard deviations did not exceed 2%. The proposed procedures were successfully applied to the analysis of the studied drugs in pure form and pharmaceutical formulations with good accuracy; the recovery values were 98.4-102.8 +/- 1.24-1.81%. The results obtained from the proposed method were statistically comparable with those obtained from the previously reported methods.     

Application of inorganic oxidants to the spectrophotometric determination of ribavirin in bulk and capsules

Eight spectrophotometric methods for determination of ribavirin have been developed and validated. These methods were based on the oxidation of the drug by different inorganic oxidants: ceric ammonium sulfate, potassium permanganate, ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate. The oxidation reactions were performed in perchloric acid medium for ceric ammonium sulfate and in sulfuric acid medium for the other reagents. With ceric ammonium sulfate and potassium permanganate, the concentration of ribavirin in its samples was determined by measuring the decrease in the absorption intensity of the colored reagents at 315 and 525 nm, respectively. With the other reagents, the concentration of ribavirin was determined by measuring the intensity of the developed colored reaction products at the wavelengths of maximum absorbance: 675, 780, 595, 595, 475, and 475 nm for reactions with ammonium molybdate, ammonium metavanidate, chromium trioxide, potassium dichromate, potassium iodate, and potassium periodate, respectively. Different variables affecting the reaction conditions were carefully studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9984-0.9998) were found between the absorbance readings and the concentrations of ribavirin in the range of 4-1400 microg/mL. The molar absorptivities were correlated with the oxidation potential of the oxidants used. The precision of the methods were satisfactory; the values of relative standard deviation did not exceed 1.64%. The proposed methods were successfully applied to the analysis of ribavirin in pure drug material and capsules with good accuracy and precision; the recovery values were 99.2-101.2 +/- 0.48-1.30%. The results obtained using the proposed spectrophotometric methods were comparable with those obtained with the official method stated in the United States Pharmacopeia.     

On Erdélyi–Kober Quadratic Functional-Integral Equation in Banach Algebra

Using the technique of a suitable measure of noncompactness in Banach algebra, we prove an existence theorem for some functional-integral equations in Banach algebra, namely Erdélyi–Kober quadratic functional-integral equation. This equation contains as particular cases a lot of integral equations that appear in many branches of nonlinear analysis and its applications. The obtained result is illustrated by an example.     

On a system of nonlinear integral equations with hysteresis

In this paper we give some sufficient conditions for the existence and uniqueness of a continuous solution of the system of Urysohn-Volterra equation with hysteresis.     

Bestimmung von freiem und komplex gebundenem Cyanid, Cyanat und Ammoniak nebeneinander

Zusammenfassung Es wird eine Analysenmethode für Cyanid, komplexe Cyanide, Ammoniak und Cyanat in oxydierende Chlorverbindungen enthaltenden Lösungen beschrieben. Nach unseren Ergebnissen kann auch in solchen Lösungen freies Cyanid enthalten sein. Die Bestimmungen sind nebeneinander nicht durchzuführen, daher werden nach Reduktion mit Arsenitlösung folgende Trennungen durch Wasserdampfdestillation (Wd.) durchgeführt: 1. Wd. bei pH 12; erfaßt wird NH₃ bzw. NH₄ ⁺ und ein kleiner Teil des Cyanates (Hydrolyse zu NH₃). Dieser Teil ist bei kontrollierten Bedingungen proportional der Cyanatkonzentration. 2. Wd. bei pH 7 (Phosphatpuffer). Erfaßt wird freies Cyanid. 3. Wd. bei pH 0 zur Abtrennung des Gesamtcyanids. 4. Verseifung des Cyanats (pH 1, Cyanatkonzentration unter 1,2 g/l) und Wd. bei pH 12. Erfaßt wird die Summe an Ammoniak und Cyanat.

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Determination of free and complex cyanide, cyanate and ammonia in presence of each other

A procedure is described for the analysis of solutions containing cyanide, complex cyanides, ammonia and oxidizing chlorine compounds. Our results show the possible existence of free cyanide ions in such solutions. Simultaneous determination is impossible; therefore, after reduction with arsenite solution, the following separations are made by steam distillation (s. d.): (1) S.d. at pH 12 gives the sample ammonia and some ammonia produced by hydrolysis of cyanate (this is under controlled conditions proportional to the cyanate concentration). (2) S.d. at pH 7 (phosphate buffer) gives the free cyanide. (3) S.d. at pH 0 separates complex and free cyanide. (4) Hydrolysation of cyanate at pH 1 (cyanate conc. below 1.2 g/l) and following s.d. at pH 12 gives the sum of sample ammonia and the ammonia equivalent to the cyanate content.