Determination of tributyltin oxide in coastal marine sediments and mussels by electrothermal atomic absorption spectrometry

We have devised a new method for bis(tributyltin)oxide (TBTO) determination in marine sediments and mussels. This technique involves an n-hexane/methylene chloride mixture extraction and extract purification with a sodium hydroxide wash in order to eliminate interfering compounds. TBTO is then extracted again by nitric acid and converted into an inorganic tin species; the analysis has been effected using Zeeman graphite furnace-atomic absorption spectrophotometry. The method detection limit for the matrices examined is 0.004 μg TBTO g^?1 (wet weight) and is sufficient for the analysis in real samples. The percentage recovery of TBTO from sediments and mussels samples is higher than 85% and 95% respectively. This method has been applied to TBTO level determination in sediments and mussels (Mytilus galloprovincialis) sampled in the harbour area in Taranto, where mussel culture activities are much developed; the TBTO levels obtained in sediments and mussels were in the range 15-47 ng g^?1 (wet weight) and 11-30 ng g^?1 (wet weight) respectively. Such values are comparable with those found in other harbour areas in the Mediterranean Sea.     

Electron-transfer reaction of cinnamic acids and their methyl esters with the DPPH(*) radical in alcoholic solutions

The kinetic behavior of cinnamic acids, their methyl esters, and two catechols 1-10 (ArOH) in the reaction with DPPH(*) in methanol and ethanol is not compatible with a reaction mechanism that involves hydrogen atom abstraction from the hydroxyl group of 1-10 by DPPH(*). The rate of this reaction at 25 degrees C is, in fact, comparatively fast despite that the phenolic OH group of ArOH is hydrogen bonded to solvent molecules. The observed rate constants (k(1)) relative to DPPH(*) + ArOH are 3-5 times larger for the methyl esters than for the corresponding free acids and, for the latter, decrease as their concentration is increased according to the relation k(1) = B/[ArOH](0)(m), where k(1) is given in units of M(-1) s(-1), m is ca. 0.5, and B ranges from 0.02 (p-coumaric acid) to ca. 3.48 (caffeic acid) in methanol and from 0.04 (p-coumaric acid) to ca. 13 (sinapic acid) in ethanol. Apparently, the reaction mechanism of DPPH(*) + ArOH involves a fast electron-transfer process from the phenoxide anion of 1-10 to DPPH(*). Kinetic analysis of the reaction sequence for the free acids leads to an expression for the observed rate constant, k(1), proportional to [ArOH](0)(-1/2) in excellent agreement with the experimental behavior of these phenols. The experimental results are also interpreted in terms of the influence that adventitious acids or bases present in the solvent may have. These impurities dramatically influence the ionization equilibrium of phenols and cause a reduction or an enhancement, respectively, of the measured rate constants.     

Atropisomerism in 1,5-bridged calix[8]arenes

[structure: see text] The first example of two discrete calix[8]arene conformational isomers, 2 and 2a, has been obtained by exhaustive benzylation of 1,5-tetramethylene-bridged calix[8]arene 1. It is demonstrated, with the aid of X-ray crystallography, that these atropisomers have two 3/4-cone halves oriented syn or anti with respect to the bridge/bridgeheads moiety. VT NMR studies indicate that the tert-butyl-through-the-annulus inversion is inhibited in 1, while groups larger than n-hexyl or benzyl are required for curtailing the O-through-the-annulus route.     

Kaolin as support for porous layer open tubular columns

Summary PLOT columns have been prepared with kaolin as the liquid phase support. These columns show good efficiency with different stationary phases and good thermal stability with polar phases. The performance of columns is shown by the separation of various mixtures such as fatty acids, phenols and anilines which are of analytical importance.     

Fast-electron ejection from C,Ni, Ag and Au foils by <Superscript>36</Superscript><Emphasis Type="Italic">Ar</Emphasis><Superscript>18 + </Superscript> (95 MeV/u): Measurements of absolute cross-sections

Doubly differential electron velocity spectra induced by ³⁶Ar^{18 +} (95 MeV/u) from thin target foils (C, Ni, Ag, Au) were measured at GANIL (Caen, France) by means of the ARGOS multidetector and the time-of-flight technique. The main features observed in the forward spectra are convoy electrons, binary-encounter electrons, and (for the Au target only) a high-velocity tail which we attribute to a Fermi shuttle acceleration mechanism. Backward spectra do not show distinct structures. The spectra allow us to determine absolute singly differential cross-sections as a function of the target material and the emission angle. The convoy electron yield increases with the target atomic number, but for C their yield is so small that our experiment is not able to detect them. Absolute doubly differential cross-sections for binary-encounter electron ejection from C targets are well described by a transport theory which is based on the relativistic electron impact approximation (EIA) for electron production and which accounts for angular deflection, energy loss and energy straggling of the transmitted electrons.Received: 1 July 2003, Revised: 15 December 2003, Published online: 13 July 2004PACS: 34.50.Fa Electronic excitation and ionization of atoms (including beam-foil excitation and ionization) - 79.20.Rf Atomic, molecular, and ion beam impact and interactions with surfaces - 25.70.-z Low and intermediate energy heavy-ion reactions     

New experimental constraints on non-Newtonian forces below 100 microm

We have searched for large deviations from Newtonian gravity by means of a finite-frequency microcantilever-based experiment. Our data eliminate from consideration mechanisms of deviation that posit strengths approximately 10(4) times Newtonian gravity at length scales of 20 microm. This measurement is 3 orders of magnitude more sensitive than others that provide constraints at similar length scales.     

Aspect-ratio dependent oscillatory thermocapillary convection in the floating half zone

The dependency of the critical Marangoni number on the geometrical aspect ratio of the floating half zone is essential to predict the onset of oscillatory thermocapillary convection.The experimental studies in the microgravity conditions on floating half zones of several centimeters in diameter have predicted that the critical Marangoni number increases with the increasing aspect ratio,and the terrestrial experimental studies have predicted the contradictory conclusion for floating half zones of several mil...     

Non-Gravitational Effects with Density-Matching in Evaluating the Influence of Sedimentation on Colloidal Coagulation

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions in studies on dynamic behaviour of a colloidal system. However, the associated changes in the solvent composition may bring side effects to the properties investigated and therefore might lead to a faulty conclusion if the relevant correction is not made. To illustrate the importance of this side effect, we present an example of the sedimentation influence on the coagulation rate of suspensions of 2μm （diameter） polystyrene. The liquid mixtures, in the proper proportions of water （H2O）, deuterium oxide （D2O） and methanol （MeOH） as the liquid phase, density-matched and unmatched experiments are performed. Besides the influence of viscosity, the presence of methanol in solvent media, used to enhance the sedimentation effect, causes significant changes （reduction） in rapid coagulation rates compared to that in pure water. Without the relevant corrections for those non-gravitational factors it seems that gravitational sedimentation would retard the coagulation. The magnitude of the contribution from the non-gravitational factor is quantitatively determined, making the relevant correction possible. After necessary the influence of the sedimentation on coagulation rates at corrections for all factors, our experiments show that the initial stage of the coagulation is not observable.