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.     

Can control banding be useful for the safe handling of nanomaterials? A systematic review

Control banding (CB) is a risk management strategy that has been used to identify and recommend exposure control measures to potentially hazardous substances for which toxicological information is limited. The application of CB and level of expertise required for implementation and management can differ depending on knowledge of the hazard potential, the likelihood of exposure, and the ability to verify the effectiveness of exposure control measures. A number of different strategies have been proposed for using CB in workplaces where exposure to engineered nanomaterials (ENMs) can occur. However, it is unclear if the use of CB can effectively reduce worker exposure to nanomaterials. A systematic review of studies was conducted to answer the question “can control banding be useful to ensure adequate controls for the safe handling of nanomaterials.” A variety of databases were searched to identify relevant studies pertaining to CB. Database search terms included ‘control,’ ‘hazard,’ ‘exposure,’ and ‘risk’ banding as well as the use of these terms in the context of nanotechnology or nanomaterials. Other potentially relevant studies were identified during the review of articles obtained in the systematic review process. Identification of studies and the extraction of data were independently conducted by the reviewers. Quality of the studies was assessed using the methodological index for nonrandomized studies. The quality of the evidence was evaluated using grading of recommendations assessment, development and evaluation (GRADE). A total of 235 records were identified in the database search in which 70 records were determined to be eligible for full-text review. Only two studies were identified that met the inclusion criteria. These studies evaluated the application of the CB Nanotool in workplaces where ENMs were being handled. A total of 32 different nanomaterial handling activities were evaluated in these studies by comparing the recommended exposure controls using CB to existing exposure controls previously recommended by an industrial hygienist. It was determined that the selection of exposure controls using CB were consistent with those recommended by an industrial hygienist for 19 out of 32 (59.4 %) job activities. A higher level of exposure control was recommended for nine out of 32 (28.1 %) job activities using CB, while four out of 32 (12.5 %) job activities had in-place exposure controls that were more stringent than those recommended using CB. After evaluation using GRADE, evidence indicated that the use of CB Nanotool can recommend exposure controls for many ENM job activities that would be consistent with those recommended by an experienced industrial hygienist. The use of CB for reducing exposures to ENMs has the potential to be an effective risk management strategy when information is limited on the health risk to the nanomaterial and/or there is an absence of an occupational exposure limit. However, there remains a lack of evidence to conclude that the use of CB can provide adequate exposure control in all work environments. Additional validation work is needed to provide more data to support the use of CB for the safe handling of ENMs.     

A sinapic acid–calix[4]arene hybrid selectively binds Pb over Hg and Cd

The binding affinity for Pb²⁺, Cd²⁺ and Hg²⁺ of the sinapic acid–calix[4]arene hybrid 2, having four sinapyl pendants at the upper rim, has been investigated via an UV–Vis study. Compound 2 has better complexing ability than the monomeric p-phenetidine derivative 1. This highlights that the clustering of sinapyl units in a basket-like structure, dictated by the calixarene scaffold, greatly enhances the complexing properties. Ligand 2 forms complexes even with Hg²⁺, which is not complexed by 1 at all; the complexes formed by 2 with Pb²⁺ and Cd²⁺ are much stronger than the analogous complexes formed by 1. The UV–Vis investigation shows that the hybrid 2 markedly favors Pb²⁺ over Cd²⁺ and Hg²⁺. Information on the structural properties of the complex species was obtained by ¹H NMR spectroscopy. NMR data show that all three metal ions are placed into the cavity consisting of the calixarene scaffold and the sinapyl pendants, though their binding affects the coordinating regions to a different extent.     

Determination of HCHs,PCBs, and DDTs in brain tissues of marine mammals off different age

The concentrations of a number of polychlorinated biphenyls and chlorinated pesticides in brain tissues of marine mammals of different age and regional origin were determined by using high-resolution capillary gas chromatography and electron capture detection. Brain tissues of two neonatal and three stillborn northern fur seals (Callorhinus ursinus) collected in the Bering Sea, Pacific Ocean, were examined. In addition, cerebrum, cerebellum, and hypothalamus of one adult female common dolphin (Delphinus delphis) stranded on the coast of Massachusetts, Atlantic Ocean, were examined. It showed clearly that α-HCH was dominant in all brain tissues (90–203 ng/g extractable lipids) compared with other tissues like liver or blubber (45–61 ng/g extractable lipids). This excess of α-HCH in brain tissue was due to only one enantiomer, (+)-α-HCH, whereas in other tissues both enantiomers contributed to the α-HCH concentration. Comparing the overall general xenobiotic burden, the HCH isomers (99–216 ng/g extractable lipids) resemble the PCB (17–105 ng/g extractable lipids) and DDT (111–171 ng/g extractable lipids) levels in brain tissues. The latter two groups exceed the HCHs in liver tissue and in blubber. On a single compound basis, the highest levels are found in brain for α-HCH (fur seal pups: 90–203 ng/g extractable lipids, adult dolphin: 221–305 ng/g extractable lipids), 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB153) (fur seal pups: 4–25 ng/g extractable lipids, adult dolphin: 260–377 ng/g extractable lipids) and 4,4′-DDE (fur seal pups: 104–164 ng/g extractable lipids, adult dolphin: 364–625 ng/g extractable lipids). The levels of α-HCH and 4,4′-DDE are comparable. No significant difference concerning the xenobiotic burden between neonatal and stillborn northern fur seals could be seen in contrast to the higher concentrations of the adult common dolphin. The patterns of some xenobiotics in the samples were compared with each other by using statistical methods like the similarity index and the principal component analysis (PCA).