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.     

Study on reproductive endocrinology of human placenta (III)--Hormonal regulation of progesterone production by trophoblast tissue of first trimester.

The effect of hormones on progesterone secretion by 6-8 week human trophoblast tissue cultured in serum-free medium has been investigated. GnRH at low concentration (10(-10)-10(-8) mol/L) stimulated progesterone secretion, while high dose (10(-6)-10(-5) mol/L) produced inhibitory effect. The progesterone secretion could be significantly decreased by addition of anti-hCG antiserum or monoclonal anti-hCG IgG in a dose- and time-dependent manner. Various concentrations of TRH, PGE2, PGF2 alpha, testosterone and estradiol were found to be ineffective. These data indicate clearly that progesterone production by human trophoblast tissue at early gestation stage is under the modulation of GnRH and hCG.     

Radical copolymerization of 2‐trifluoromethylacrylic monomers. II. Kinetics,monomer reactivities,and penultimate effect in their copolymerization with norbornenes and vinyl ethers

Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with ¹H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007     

Synthesis and thermal crosslinking of oxazolidine‐functionalized polyurethanes

A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (M_w ～ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007     

Interface analysis of the system Si/YBa2Cu3O7?x

Summary The influence of different preparation conditions and substrate surface orientations on the superconducting properties of thin YBa₂Cu₃O_7–x (YBCO) films on silicon was studied. Comparative electrical and surface spectroscopic measurements were performed. SAM and SIMS depth profile analysis show an enrichment of barium at the interface between the superconductor and silicon for samples with T_c<76 K. Comparison with XPS data obtained for thin silicon films on YBCO indicates the formation of barium and yttrium silicates at the interface under these conditions.     

Synthesis and thermal behaviour of salicylaldimine-based liquid crystalline symmetrical dimers

A series of symmetrical dimers consisting of salicylaldimine moieties connected by flexible alkylene central spacer via ether linkages has been synthesized. In order to validate the empirical rule suggested by Date et al. to account for the smectic behaviour of such dimers, the chain length of the terminal alkoxy chain has been kept constant (C₈) while the number of methylene units in the central spacer was varied from C₃ to C₁₁. Another aim of the present investigation was to understand structure-property relationship in these dimers in which the salicylaldimine mesogenic segment has been used for the first time in dimers. The mesomorphic behaviour of these dimers was evaluated using optical microscopy and differential scanning calorimetry and the structure of some of the mesophases has been further investigated with the help of X-ray diffraction. Our studies reveal that the dimers consisting of 3 to 8 methylene units in the flexible spacer show only smectic (smectic C and smectic A) phases. For the dimers containing 4, 6 and 8 methylene units in the central spacer, a unique filament growth pattern has been observed in the smectic A phase while cooling from the isotropic phase. The dimers containing of C₉ to C₁₁ methylene groups exhibit the nematic phase in addition to smectic modifications. This observation indicates that when the terminal chains are shorter than the spacer, the tendency to form smectic phases is not fully extinguished but is perhaps reduced.     

Impact of two mass scale oscillations on the analysis of atmospheric and reactor neutrino data

We study the stability of the results of the three-neutrino oscillation analysis of atmospheric and reactor neutrino data under departures of the one dominant mass scale approximation. In order to do so we perform the analysis of atmospheric and reactor neutrino data in terms of three-neutrino oscillations where the effect of both mass differences is explicitly considered. We study the allowed parameter space resulting from this analysis as a function of the mass splitting hierarchy parameter which parameterizes the departure from the one dominant mass scale approximation. We consider schemes with both direct and inverted mass ordering. Our results show that in the analysis of the atmospheric data the derived range of the largest mass splitting, , is stable, while the allowed ranges of mixing angles and are wider than those obtained in the one dominant mass scale approximation. Inclusion of the CHOOZ reactor data in the analysis results in the reduction of the parameter space in particular for the mixing angles. As a consequence the final allowed ranges of the parameters from the combined analysis are only slightly broader than when obtained in the one dominant mass scale approximation. Received: 31 May 2002 / Revised version: 10 July 2002 / Published online: 31 October 2002