Application of solid-phase microextraction combined with gas chromatography-mass spectrometry to the determination of butylated hydroxytoluene in bottled drinking water

Butylated hydroxytoluene (BHT) is an antioxidant utilized as additive in foods and packaging plastic. Its presence in drinking water is possible if it is used as an antioxidant in the packaging plastic because it may migrate into the package's contents. A method for the determination of BHT in water by means of solid-phase microextraction and gas chromatography-mass spectrometry has been developed and evaluated with respect to the time of fiber exposure, limits of detection and quantitation, linearity and precision. Finally, the method was applied to evaluate the presence of this substance in samples of mineral and mineralized bottled drinking water, and it appeared to be present in seven out of a total of fifteen commercial brands.     

Nitrogen inversion in cyclic amines and the bicyclic effect

The hitherto unsolved problem of the origin of the unusually high nitrogen inversion-rotation (NIR) barriers in 7-azabicyclo[2.2.1]heptanes (the bicyclic effect) was examined using the natural bond orbital (NBO) approach. Reinvestigating the NIR barrier for tropane by DNMR, we found that NIR barriers increase smoothly on going from nitrogen-bridged bicyclic systems of a larger ring size to the smaller ring homologous systems. The experimental NIR barriers are reproduced with good accuracy using the MP2/6-31G level of theory. The NBO analysis for these and other azabicycles led to the conclusion that the height of these barriers is mostly determined by the energy of the sigma-orbitals of the C(alpha)(-)C(beta) bonds as well as the nitrogen lone pair. Thus, the bicyclic effect is actually an extreme case of a common C(alpha-)N-C(alpha) tripyramid geometry-NIR barrier dependence for N-bridged bicyclic amines. By establishing the rate-determining role of the C(alpha-)N-C(alpha) tripyramid fragment for NIR, we have derived the first sufficiently accurate quantitative correlations amine geometry-NIR barrier for monocyclic as well as bicyclic N-H and N-Me amines (i.e., for an amine set which also includes the bicyclic effect systems).     

Photodynamics of the bacteriochlorophyll-carotenoid system. 2. Influence of central metal,solvent and beta-carotene on photobleaching of bacteriochlorophyll derivatives

Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both).     

Stereochemical study of phosphonothioate cleavage by a metallomicelle

[reaction: see text] The copper metallomicellar hydrolysis of O-methyl O-4-nitrophenyl phenylphosphonothioate to O-methyl phenylphosphonothioic acid takes place with effectively complete inversion at phosphorus.     

Quantum cloning with an optical fiber amplifier

It has been shown theoretically that a light amplifier working on the physical principle of stimulated emission should achieve optimal quantum cloning of the polarization state of light. We demonstrate close-to-optimal universal quantum cloning of polarization in a standard fiber amplifier for telecom wavelengths. For cloning 1-->2 we find a fidelity of 0.82, the optimal value being 5 / 6=0.83.     

Two definitions of exponential dichotomy for skew-product semiflow in Banach spaces

In this paper we introduce a concept of exponential dichotomy for linear skew-product semiflows (LSPS) in infinite dimensional Banach spaces, which is an extension of the classical concept of exponential dichotomy for time dependent linear differential equations in Banach spaces. We prove that the concept of exponential dichotomy used by Sacker-Sell and Magalhães in recent years is stronger than this one, but they are equivalent under suitable conditions. Using this concept we where able to find a formula for all the bounded negative continuations. After that, we characterize the stable and unstable subbundles in terms of the boundedness of the corresponding projector along (forward/backward) the LSPS and in terms of the exponential decay of the semiflow. The linear theory presented here provides a foundation for studying the nonlinear theory. Also, this concept can be used to study the existence of exponential dichotomy and the roughness property for LSPS.

     

Determination of iridium concentration in sedimentary rocks and in the geochemical standard PCC-1 by radiochemical neutron activation analysis

A radiochemical neutron activation analysis procedure is described for the determination of concentration levels of iridium in sedimentary rocks and in the geochemical standard PCC-1. After irradiation, the powdered rock samples and standard are dissolved with a mixture of HF, HNO₃ and HClO₄ in a teflon bomb. The final solution obtained, in dilute HCl, is passed through a column containing the cationic resin Bio Rad AG 50W-X8. The interfening radionuclides are sorbed by the resin. The effluent solution containing iridium is concentrated for counting by evaporation. Experiments with radioactive tracer for checking radiochemical separation yield are carried out. The accuracy of the method is evaluated by means of analysis of the USGS “standard rock” peridotite, PCC-1. The precision is about 25% in the ppb range. The method is used for the determination of iridium in 16 samples of sedimentary rocks collected at different depths in the “Campos” basin-RJ (BRAZIL).     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.