Molecular orientation in drawn smectic and crystalline isotactic polypropylene

The drawing behavior of two polypropylene films of different structures was analyzed. The two films differ as a consequence of different quenching conditions. At low temperature, a biphasic smectic-amorphous system was obtained, while quenching at 100°C produced a biphasic crystalline-amorphous system. The drawing of samples was carried out at 110°C at which temperature the smectic phase is not stable and is transformed into the crystalline α-form. The initial structure affects the drawing behavior and the properties of the drawn samples. The mechanical, optical, and X-ray analyses clearly show that high molecular orientation is achieved at lower deformations in the initially smectic sample. In particular, the amorphous phase is highly oriented, inducing higher axial elastic modulus.     

Buccal tablets containing cysteine and chlorhexidine for the reduction of acetaldehyde levels in the oral cavity

There is growing evidence that a large proportion of upper digestive tract tumors are ascribable to heavy alcohol drinking and tobacco consumption. The cancer-promoting action of ethanol is mediated by acetaldehyde, its first metabolite, also derived from the bacterial oxidation of alcohol by the oral microflora, classified by the International Agency for the Research on Cancer as a carcinogen. Acetaldehyde is also one of the major components of tobacco smoke. These findings suggest two different strategies to decrease the risk of alcohol-related oral cancers: the reduction of the levels of alcohol-derived acetaldehyde in saliva and the reduction of oral bacterial flora. Therefore, the aim of our study was to develop and characterize some buccal tablet formulations containing both 20 mg L-cysteine hydrochloride (able to chemically neutralize acetaldehyde) and 10 mg chlorhexidine diacetate (well-known antiseptic compound active against a large spectrum of oral microbes). One of these formulations, chosen on the basis of its favourable delivery kinetics of the active principles, was demonstrated to be able to reduce acetaldehyde concentration in an in vitro system and to lower its salivary levels in volunteers after ethanol contact. Our findings support the hypothesis that the application of buccal devices containing cysteine and chlorhexidine could reduce salivary acetaldehyde levels and thus the incidence of upper gastrointestinal cancer in drinkers and smokers.     

A Brazilian government external individual monitoring service: experience since 1972

Instituto de Radioprote??o e Dosimetria, a Brazilian government research institute, provides individual monitoring services since 1972. Its dosemeters are: film-based thorax for whole body photons, thermoluminescence dosimetry (TLD) albedo for whole body neutrons and TLD ring for extremity photons. About 6000 radiation workers are currently being monitored with film dosemeters in 256 different facilities in Brazil, most of them working in health-related activities. Around 400 Brazilian radiation workers are monitored with TLD albedo neutron monitor and about 500 workers use TLD rings. This paper describes the monitoring systems used, presents the results obtained in internal quality programs and in intercomparison exercises and analyses the measured dose values from 1985 to 2009.     

The potential of perylene bisimide derivatives for the solubilization of carbon nanotubes and graphene

Carbon nanotubes and graphene are outstanding materials of the 21st century with a broad spectrum of applications. However, major challenges are faced such as the intrinsically low solubility of both sp2 carbon allotropes. To overcome this hurdle the potential of noncovalent functionalization is summarized with a special focus on the establishment of the perylene bisimide unit as aromatic anchor to the graphitic surface. Rational surfactant design is unmasked as the key to solubilization of the carbon allotropes, while at the same time tailoring their surface properties, or even electronic properties in a fully reversible fashion.     

Performance and applications of the UVscope instrument

UVscope is a portable multi-pixels photon detector developed at IASF-Pa to support experimental activities in the high-energy astrophysics and cosmic rays field. The instrument, working in single photon counting mode, is designed to directly measure light flux in the wavelengths range 300-650 nm. Thanks to its features and operational flexibility, the instrument can be used in a wide field of applications where the knowledge of the environmental luminosity is required, as in the characterization of sites for ground-based Cherenkov and fluorescence telescopes, and for cross-calibration of their cameras.The present version of UVscope is based on a Multi Anode Photo Multiplier Tube and it is completed by a motorized mount and a filter wheel which allow to make low-light measurements, at programmed pointing directions and at different filter wavelengths. In this paper, the instrument is firstly presented in all its components; then the procedures adopted for its absolute and relative calibration are detailed. The performance of UVscope is evaluated and, finally, current and planned scientific applications are described.     

Oxygen in coal ash: a simplified approach to the analysis of ash and mineral matter in coal

Oxygen was determined accurately in eight U.S. Bureau of Mines coal ash samples A, B, D, F, G, I, and J, NBS coal fly ash 1633 reference material, and two low-temperature ashes (LTA) from lllinois State Geological Survey. The method uses fast-neutron activation (FNA) analysis employing a dual counting and irradiation system which is essentially free from interferences. The stoichiometric balance based on analyses of the ashes performed by the USBM is calculated and summations given in oxide and element percent. Excellent agreement is found with the chemical data obtained by classical silicate analysis methods. Accurate oxygen determination for coal ash and LT-ash (or mineral matter) is important for calculation of data in the ultimate analysis of coal as such. Knowledge is required for recalculation of the data on a dry and dry-ash-free basis. The routinely used ‘oxygen by difference’ values are inadequate for accurate work. In order to determine the organic oxygen in coal one also has to correct for oxygen in mineral matter and oxygen in the water removed as moisture. The Parr formula and other methods of empirical estimation are inadequate and may be replaced in some cases by the oxygen determination. The complete data provide a quantitative basis for stoichiometric interpretation of coal analyses. It was found that the eight coal-ash samples analysed contained 45.5 ± 3% oxygen. Since these ashes represent a large variety of U.S. coals, this figure can be used as an estimate for recalculation and evaluation of the proximate and ultimate coal analyses. It is better, however, to use values actually determined in ash by the rapid fast-neutron activation method. This permits a better estimation of the sum of cations plus sulphates in the ash.     

Enzymatic esterification of glycerol III. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols and 1 (3)-rac-monoacylglycerols derived from unsaturated fatty acids

Lipases that display high regioselectivities and broad substrate tolerance were used as catalysts for the efficient esterification of glycerol under the conditions of irreversible acyl transfer. A variety of unsaturated fatty acids, such as oleic, linoleic, erucic, ricinolic, hydroxystearic and coriolic acid, were used for this purpose in the form of their vinyl esters. Suitable biocatalysts were chosen on the basis of systematic screening experiments regarding their regioselectivities (RE) and substrate tolerances. Distinct differences were found and expressed in numerical RE values as a measure for differences of these biocatalysts as being specific, selective, and nonspecific. Based on these experiments, a variety of molecules were synthesized on a preparative scale (>150 mmol) in good yield (ca.85%) and with high regioisomerical purities (>95% RE).     

Liquid-crystallization induced reactions. Microstructure and morphology of copolyesters synthesized by transesterification of PET with some LCP monomers

The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of PET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion.     

Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2] n

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G^* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP₂NCl₅ and OP₃N₂Cl₅) were compared with those derived fromab initio quantum mechanics using the 6–31G^* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; β=111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.