Micellar properties of tetradecyltrimethylammonium nitrate in aqueous solutions at various temperatures and in water-benzyl alcohol mixtures at 25 °C

The micellar properties of tetradecyltrimethylammonium nitrate (C14TANO₃) in aqueous solutions in the temperature range of 10 to 35 °C and in aqueous solutions of benzyl alcohol (BzOH) at 25 °C were studied conductometrically. The specific conductivity data served for the evaluation of critical micelle concentration, cmc, and the degree of ionization of the micelles, , of the surfactant. From the temperature dependence of the cmc the thermodynamic parameters for micellization of C14TANO₃ were calculated by applying Mullers modified equation. BzOH was found to affect strongly the cmc and values of the surfactant. The plot of the cmc/cmc_o ratio (where cmc_o is for pure water) as a function of BzOH molality, exhibits a characteristic break, which was attributed to the commencement of self-association of BzOH in aqueous solution at a molality of ca. 0.05. By applying the theoretical treatment suggested by Motomura for binary surfactant systems, the molar fraction of BzOH in the micelles at cmc, was estimated as a function of molality of the alcohol. C14TANO₃ appears to be slightly more hydrophobic compared to the corresponding bromide.     

Comparison of protective effects against reactive oxygen species of mononuclear and dinuclear Cu(II) complexes with N-substituted benzothiazolesulfonamides

Copper(II) complexes of N-benzothiazolesulfonamides (HL1=N-2-(4-methylphenylsulfamoyl)-6-nitro-benzothiazole, HL2=N-2-(phenylsulfamoyl)-6-chloro-benzothiazole, and HL3=N-2-(4-methylphenylsulfamoyl)-6-chloro-benzothiazole) with ammonia have been synthesized and characterized. The crystal structures of the [Cu(L1)2(NH3)2].2MeOH, [Cu(L2)2(NH3)2], and [Cu(L3)2(NH3)2] compounds have been determined. Compounds and present a distorted square planar geometry. In both compounds the metal ion is coordinated by two benzothiazole N atoms from two sulfonamidate anions and two NH3 molecules. Complex is distorted square-pyramidal. The Cu(II) ion is linked to the benzothiazole N and sulfonamidate O atoms of one of the ligands, the benzothiazole N of another sulfonamidate anion, and two ammonia N atoms. We have tested the superoxide dismutase (SOD)-like activity of the compounds and compared it with that of two dinuclear compounds [Cu2(L4)2(OCH3)2(NH3)2] and [Cu2(L4)2(OCH3)2(dmso)2] (HL4=N-2-(phenylsulfamoyl)-4-methyl-benzothiazole). In vitro indirect assays show that the dimeric complexes are better SOD mimics than the monomeric ones. We have also assayed the protective action provided by the compounds against reactive oxygen species over Deltasod1 mutant of Saccharomyces cerevisiae. In contrast to the in vitro results, the mononuclear compounds were more protective to SOD-deficient S. cerevisiae strains than the dinuclear complexes.     

Antimony(V) volatilization with bromide and determination by inductively coupled plasma atomic emission spectrometry

Antimony(V) is volatilized by reaction with potassium bromide in concentrated sulfuric acid media. After volatilization, the gases can be transported to an inductively coupled plasma spectrometer for atomic emission of antimony and its analytical determination. The influent factors, concentrated sulfuric acid volume, concentration and volume of the potassium bromide aqueous solution and carrier gas flow were investigated and optimized using different alternatives. A detection limit of 48 ng ml⁻¹ of Sb was achieved under the optimized conditions with a precision of 7.6% and the calibration graph was linear from 0.10 to 10.0 μg ml⁻¹ for a sample injection of 130 μl.The study of interferences from common cations and anions revealed a good tolerance for most ions, although there was a significant improvement in Sb(V) volatility when As(III) was present. Furthermore, the As(III) sensitization was only produced with Sb(V) species, while the volatility of the Sb(III) bromide species was unaltered.The method was applied to the determination of Sb in real river waters. The results were checked using alternative atomic spectroscopy methods.     

Kinetics and mechanisms of homogeneous catalytic reactions. Part 5. Regioselective reduction of heteroaromatic nitrogen compounds catalysed by [OsH(CO)(NCMe)2(PPh3)2]BF4

The [OsH(CO)(NCMe)₂(PPh₃)₂]BF₄ complex (1) is an efficient and regioselective precatalyst for the hydrogenation of the nitrogen-containing ring of quinoline (Q), isoquinoline (iQ), 5,6- and 7,8-benzoquinoline (BQ), and acridine (A) under mild reaction conditions (125 °C and 4 atm H₂). Kinetic studies of the hydrogenation of Q and iQ to give tetrahydroquinoline (THQ) and tetrahydroisoquinoline (THiQ), respectively, lead to the rate law r = K ₁ k ₂/(1 + K ₁[H₂])[Os][H₂]², which becomes r = K ₁ k ₂[Os][H₂]², at low hydrogen concentrations (below 1 atm H₂); the catalytically active species is of the type [OsH(CO)(L)( ¹-N)(PPh₃)₂]BF₄ [(2a): L = NCMe, N = Q; (2b): L = N = iQ]. The generic mechanisms involve a rapid and partial hydrogenation of the coordinated substrate (N) of complex (2) to yield the corresponding dihydroderivative (DHN) species [OsH(CO)(L)( ¹-DHN)(PPh₃)₂]BF₄ [(3a): L = NCMe, DHN = DHQ; (3b): L = iQ or THiQ, DHN = DHiQ], followed by the rate-determining second hydrogenation of the DHN ligand, which yield [OsH(CO)(L)( ¹-THN)(PPh₃)₂]BF₄ [(4a): L = NCMe, THN = THQ; (4b): L = iQ or THiQ, THN = THiQ]; substitution of the THN ligand by a new molecule of the respective substrate regenerates the active species and restarts the catalytic cycle. For the hydrogenation of acridine to give 9,10-dihidroacridine (acridane), the rate law was r = k ₁[Os][H₂]; the mechanism involves the hydrogenation of the active species [OsH(CO)(NCMe)( ¹-A)(PPh₃)₂]BF₄ (2c) to yield acridane and the unsaturated species [OsH(CO)(NCMe)(PPh₃)₂]BF₄ as the rate-determining step.     

One-dimensional oxalato-bridged Cu(II), Co(II), and Zn(II) complexes with purine and adenine as terminal ligands

The reaction of nucleobases (adenine or purine) with a metallic salt in the presence of potassium oxalate in an aqueous solution yields one-dimensional complexes of formulas [M(mu-ox)(H(2)O)(pur)](n) (pur = purine, ox = oxalato ligand (2-); M = Cu(II) [1], Co(II) [2], and Zn(II) [3]), [Co(mu-ox)(H(2)O)(pur)(0.76)(ade)(0.24)](n)(4) and ([M(mu-ox)(H(2)O)(ade)].2(ade).(H(2)O))(n) (ade = adenine; M = Co(II) [5] and Zn(II) [6]). Their X-ray single-crystal structures, variable-temperature magnetic measurements, thermal behavior, and FT-IR spectroscopy are reported. The complexes 1-4 crystallize in the monoclinic space group P2(1)/a (No. 14) with similar crystallographic parameters. The compounds 5 and 6 are also isomorphous but crystallize in the triclinic space group P (No. 2). All compounds contain one-dimensional chains in which cis-[M(H(2)O)(L)](2+) units are bridged by bis-bidentate oxalato ligands with M(.)M intrachain distances in the range 5.23-5.57 A. In all cases, the metal atoms are six-coordinated by four oxalato oxygen atoms, one water molecule, and one nitrogen atom from a terminal nucleobase, building distorted octahedral MO(4)O(w)N surroundings. The purine ligand is bound to the metal atom through the most basic imidazole N9 atom in 1-4, whereas in 5 and 6 the minor groove site N3 of the adenine nucleobase is the donor atom. The crystal packing of compounds 5 and 6 shows the presence of uncoordinated adenine and water crystallization molecules. The cohesiveness of the supramolecular 3D structure of the compounds is achieved by means of an extensive network of noncovalent interactions (hydrogen bonds and pi-pi stacking interactions). Variable-temperature magnetic susceptibility measurements of the Cu(II) and Co(II) complexes in the range 2-300 K show the occurrence of antiferromagnetic intrachain interactions.     

Influence of hydrolysis, purification, and calibration method on furosine determination using Ion-pair reversed-phase high-performance liquid chromatography

The influence of HCI concentration (6M, 8M, and 10M) and the ratio of sample protein to acid (1 or 5 mg of protein per mL of acid) on furosine formation during sample hydrolysis is studied. The conditions that maximize furosine formation are 10M HCI in the ratio of 1 mg of protein to 1 mL of acid. Purification of the hydrolysate by solid-phase extraction is also considered by examining the effect of hydrolysate volume and volume of 3M HCI used to elute the furosine. Furosine quantitation is carried out using the standard additions and external standard methods. The results indicate that there is no interference by the sample matrix and that external calibration is adequate.     

On the decomposition theorem for meromorphic Fredholm resolvents

In this note results of B. Gramsch and W. Kaballo [8] on the decomposition of meromorphic (semi-) Fredholm resolvents are sharpened. A condition on an Orlicz function is given, under which the singular part in this decomposition can be chosen meromorphic inN , the ideal of -nuclear operators. Then the necessity of this condition is studied. Moreover, it is shown that for the rather steep Orlicz functions relevant to this question,N equalsS , the ideal of -approximable operators.Dedicated to Professor Albert Schneider on the occasion of his 60 ^th birthdayresearch supported by a grant from DAAD     

Smallness and the Covering of a Banach Space

We consider the notion of smallness and its applications to the characterization of isomorphically polyhedral Banach spaces and the existence of different coverings of either the unit sphere or the unit ball of a Banach space.     

Influence of the Phenological Stage and Harvest Date on the Bioactive Compounds Content of Green Pepper Fruit

Green pepper fruit is often consumed before it is completely ripe. However, the influence of the phenological stage in which the green pepper is consumed as a potential influencing factor in its bioactive compounds content and antioxidant capacity remains unknown. In addition, no literature is available concerning the bioactive compounds changes in ‘Lamuyo’ green peppers along its developmental and growth cycle. For this, two different approaches have been carried out, one using twelve different phenological stages (S1 to S12), and in the other, seven different harvest dates (from 27 February to 20 April). Moreover, bioactive compounds changes during 21 days of postharvest storage at 8 °C were investigated. In this study, bioactive compounds (ascorbic acid, dehydroascorbic acid, and total phenolic content) and the total hydrophilic and lipophilic (TAA-H and TAA-L) antioxidant activity were analysed. In addition, total soluble solids, total acidity, individual sugars, and organic acids were determined. Vitamin C levels increased along the phenological stages and harvest dates due to significant increases in ascorbic and dehydroascorbic acid levels. Our results show that the total phenol content decreases as vegetables develop and subsequently increases both as ripening begins and by the last harvest date. Furthermore, TAA-H was also greater by the phenological stage S12 and the 20 April harvest date. In conclusion, the phenological stage and harvest date are key factors that significantly influence the bioactive compounds of green peppers, and those that appear by S12 and 20 April could be more beneficial to health.     

Templated synthesis and catalytic properties of an Rh/ceria-zirconia catalyst

Ceria-zirconia nanophase with structural defects and high thermal stability was synthesized by a surfactant-templated method. The 0.5 wt.% Rh/ceria-zirconia catalyst shows high activity for NO reduction by CO under an oxygen-rich condition, and the selectivity to 100% N₂ below 200°C was achieved.