Positronium formation in NaY-zeolites studied by lifetime, positron beam Doppler broadening and 3-gamma detection techniques

Results of positron annihilation measurements on NaY pressed powders and deposited thin films using slow positron beam and conventional fast positron techniques are presented. In lifetime experiments using an external ²²Na source an averaged long lifetime of 1.8 ns with a sum intensity of 27% was observed in pressed powders in the presence of air at room temperature (RT). In literature this lifetime is ascribed to positrons annihilating in water filled or β cages Habrowska, A.M., Popiel, E.S., 1987. Positron annihilation in zeolite 13X. J. Appl. Phys. 62, 2419. By means of isotopic exchange some of the Na was replaced by ²²Na. These powders showed a long lifetime component of 7–8 ns with an intensity increasing from 1 to 12% when heated under normal atmosphere from RT to 200°C. No significant increase of the shorter (1.5 ns) lifetime was observed, while its intensity dropped from 13.4 to 6.6%. Both effects are ascribed to the loss of water from cages only. The beam experiments revealed a high fraction of 3-gamma annihilations in the pressed powder and thin film samples, indicating the annihilation of o-Ps and thereby the existence of large open volumes.     

Positronium trapping in free volume of polymers

Positronium trapping process caused by slow thermalization of Ps inside intermolecular spaces of polymer is considered. The pickoff annihilation rate of Ps decreases from an initial value, characteristic for the delocalized Ps, to a final value, relating to its localized state. The elastic thermalization lifetime analysis of polymers spectra with a new ETLT program is proposed to determine the total Ps intensity (I_Ps), Ps trapping rate (γ), its initial (τ₀) and final (τ_∞) pickoff lifetimes as well as the relative e⁺–e⁻ contact density (η). The model is tested through the analysis of polyurethane spectra measured in a wide range of temperature, containing the glass transition point (T_g). In contrast to the conventional analysis, I_Ps does not display any change at T_g. The results indicated slow trapping rate (about 1 ns⁻¹) of Ps in the cavities.     

The temperature dependence of the two positronium bubble states in liquid SF6

Positron lifetime measurements have been performed on liquid SF₆ in the temperature range from −45°C to 71°C (T_c = 45.65°C). The positron lifetime spectra were resolved into four lifetime components. In the order of increasing lifetimes the four lifetime components are associated with the decay of para-positronium (p-Ps), free positrons, ortho-positronium (o-Ps) from a small bubble state, and o-Ps from a large bubble state. The lifetime of o-Ps annihilating from the large bubble state τ₄ increases from 5.7 ns at −45°C to 19.5 ns at 53°C. The lifetime of o-Ps annihilating from the small bubble state τ₃ was found to be 2–2.5 ns in the main part of the temperature range studied. Apparently, this is the first observation of two different o-Ps states in a liquid. The intensity I₄ (I₃) increases (decreases) from 16.9% (16%) at −45°C to 47.2% (6.4%) at the critical point while above I₃ and I₄ are essentially temperature independent. The large Ps bubble state seems to be similar to the Ps bubble state found in most liquids.     

Analysis of wine phenolics by high-performance liquid chromatography using a monolithic type column

A polyacrylamide gel crosslinked with allyl-β-cyclodextrin can be used repeatedly for several weeks for the separation of DNA fragments, since bubbles are not generated during a run. Allyl-β-cyclodextrin can easily be synthesized in one step from allylglycidylether and β-cyclodextrin. The plate numbers for DNA fragments, up to about 1500 bp, are high: for the separation of pBR322/HaeIII fragments they were in the range 450 000–1 600 000 m⁻¹. The resolution was almost independent of the concentration of the crosslinker (allyl-β-cyclodextrin) — in sharp contrast to gels crosslinked with N,N′-methylenebisacrylamide.     

High pressure studies of the static permittivity tensor components in the nematic phase of 6CB

The dielectric permittivity tensor components, ε_II and ε_⊥, in the nematic phase of 6CB (4-n-hexyl-4'-cyanobiphenyl) were measured in the pressure range 0.1-130 MPa and the temperature range 12-58°C. The dielectric anisotropy, Δε(p, V, T) = ε_II - ε_⊥, was analysed in isothermal, isobaric and isochoric conditions taking into account the pVT data and the well known Maier and Meier equation. On that basis the nematic order parameter S(p, V, T) was determined. This was used to calculate the parameter Γ relating the interaction potential with the volume (density). Its value Γ = 4.1 agrees very well with other estimates.     

Analysis of major ovine milk proteins by reversed-phase high-performance liquid chromatography and flow injection analysis with electrospray ionization mass spectrometry

Ovine milk proteins were analyzed both by coupling HPLC and electrospray ionization mass spectrometry (ESI-MS) and by flow injection analysis and ESI-MS detection after separation and collection of fractions from gel permeation chromatography. These methods resolved the four ovine caseins and whey proteins and made it possible to study the complexity of these proteins associated with genetic polymorphism, post-translational changes (phosphorylation and glycosylation) and the presence of multiple forms of proteins. The experimental molecular masses of ewe milk proteins were: 19 373 for κ-casein 3P; 25 616 for _s2-casein 10P; 23 411 for _s1-casein C-8P; 23 750 for β-casein 5P; 18 170 and 18 148 for β-lactoglobulins A and B; 14 152 for -lactalbumin A and 66 322 for serum albumin.     

Laser-induced breakdown spectroscopy of γ-Fe2O3 nanoparticles in a biocompatible alginate matrix

An intensive multi-disciplinary research effort is underway at Wayne State University to synthesize and characterize magnetic nanoparticles in a biocompatible matrix for biomedical applications. The particular system being studied consists of 3–10 nm γ-Fe₂O₃ nanoparticles in an alginate matrix, which is being studied for applications in targeted drug delivery, as a magnetic-resonance imaging (MRI) contrast agent, and for hyperthermic treatments of malignant tumors. In the present work we report on our efforts to determine if laser-induced breakdown spectroscopy (LIBS) can offer a more accurate and substantially faster determination of iron content in such nanoparticle-containing materials than competing technologies such as inductively-coupled plasma (ICP). Standardized samples of -Fe₂O₃ nanoparticles (5–25 nm diameter) and silver micropowder (2–3.5 μm diameter) were created with thirteen precisely known concentrations and pressed hydraulically to create solid “pellets” for LIBS analysis. The ratio of the intensity of an Fe(I) emission line at 371.994 nm to that of an Ag(I) line at 328.069 nm was used to create a calibration curve exhibiting an exponential dependence on Fe mass fraction. Using this curve, an “unknown” γ-Fe₂O₃/alginate/silver pellet was tested, leading to a measurement of the mass fraction of Fe in the nanoparticle/alginate matrix of 51 ± 3 wt.%, which is in very good agreement with expectations and previous determinations of its iron concentration.     

Electric field effect on positronium formation in gamma-irradiated polypropylene and polyethylene

The effect of an external electric field (up to 48 kV cm⁻¹) on positronium (Ps) formation in γ-irradiated polypropylene and polyethylene has been studied by means of positron lifetime spectroscopy. The application of an electric field to unirradiated polypropylene and polyethylene considerably decreased the Ps formation. For example, the intensity of the longest-lived component (I₃) for one of the polypropylene samples was reduced from 26% to 18% by a field of 48 kV cm⁻¹. It was found that the electric field effect for the irradiated samples becomes weaker when increasing the irradiation dose. This result is discussed on the basis of the spur reaction model of Ps formation.     

As, Cd, Cr, Ni and Pb pressurized liquid extraction with acetic acid from marine sediment and soil samples

Rapid leaching procedures by Pressurized Liquid Extraction (PLE) have been developed for As, Cd, Cr, Ni and Pb leaching from environmental matrices (marine sediment and soil samples). The Pressurized Liquid Extraction is completed after 16 min. The released elements by acetic acid Pressurized Liquid Extraction have been evaluated by inductively coupled plasma-optical emission spectrometry. The optimum multi-element leaching conditions when using 5.0 ml stainless steel extraction cells, were: acetic acid concentration 8.0 M, extraction temperature 100 °C, pressure 1500 psi, static time 5 min, flush solvent 60%, two extraction steps and 0.50 g of diatomaceous earth as dispersing agent (diatomaceous earth mass/sample mass ratio of 2). Results have showed that high acetic acid concentrations and high extraction temperatures increase the metal leaching efficiency. Limits of detection (between 0.12 and 0.5 μg g^− 1) and repeatability of the over-all procedure (around 6.0%) were assessed. Finally, accuracy was studied by analyzing PACS-2 (marine sediment), GBW-07409 (soil), IRANT-12-1-07 (cambisol soil) and IRANT-12-1-08 (luvisol soil) certified reference materials (CRMs). These certified reference materials offer certified concentrations ranges between 2.9 and 26.2 μg g^− 1 for As, from 0.068 to 2.85 μg g^− 1 for Cd, between 26.4 and 90.7 μg g^− 1 for Cr, from 9.3 to 40.0 μg g^− 1 for Ni and between 16.3 and 183.0 μg g^− 1 for Pb. Recoveries after analysis were between 95.7 and 105.1% for As, 96.2% for Cd, 95.2 and 100.6% for Cr, 95.7 and 103% for Ni and 94.2 and 105.5% for Pb.     

Transients and cooperative action of β-carotene, vitamin E and C in biological systems in vitro under irradiation

Using N^•₃ species as specific electron acceptor a defined ascorbate radical: AH^•↔A^•−+H⁺ (λ_max=360 nm, =3400 dm³ mol⁻¹ cm⁻¹) is observed. The attack of DMSO^•+ on vit.E results in a vit.E^• radical (k=1×10⁹ dm³ mol⁻¹ s⁻¹; λ_max=425 nm, =2400 dm³ mol⁻¹ cm⁻¹; 2k=4.7×10⁸ dm³ mol⁻¹ s⁻¹). Vit.E-acetate leads to the formation of a radical cation (vit.E-ac^•+). β-carotene reacts also with DMSO^•+ forming a radical cation, β-car^•+ (k=1.75×10⁸ dm³ mol⁻¹ s⁻¹; λ_max=942 nm, =14 600 dm³ mol⁻¹ cm⁻¹), which probably leads to the formation of a dimer radical cation, (β-car)^•+₂ (k=2.5×10⁷ dm³ mol⁻¹ s⁻¹).

Using E.coli bacteria (AB1157) as a model system in vitro it was found that all three vitamins are rather efficient radiation protecting agents. They can also increase the activity of cytostatica, e.g., mitomycin C (MMC), by electron transfer process. The mixture of vit.E-ac and β-car acts contradictory, but adding vit.C to it a strong cooperative enhancement of the MMC activity is observed once again. A relationship between the pulse radiolysis and the radiation biological data is found and discussed. A possible explanation of the previously reported trials concerning the role of vit.E and β-car on the increased occurence of lung and other types of cancer in smokers and drinkers is presented.     

A new series of nematic and smectic liquid crystals with negative dielectric anisotropy: the effect of terminal chain substitution on thermal and electro-optical properties

Two alkyl (1b and 1c) and four fluoroalkyl derivatives (1d-1f) of 4-arylbutyric acid (1c, 1d and 1e) and 4-arylbutanol (1b, 1f and 1g) [aryl = 2',3'-difluoro-4'-(2-(E-4-pentylcyclohexyl)ethyl)-biphenyl-1-yl] were prepared and investigated in the pure form as nematic materials (1b and 1c) and as additives to a ferroelectric liquid crystal (FLC) host (1d-1f). A comparison of 1b and 1c with the decyl analogue 1a demonstrates the effect of terminal chain modification on thermal and electro-optical properties. The substitution of the -CH₂O- (1b) or -COO- (1c) for -CH₂CH₂- in 1a destabilized the N and SmA phases or completely eliminated the smectic behaviour (1c). Dielectric analysis revealed that the chain modification increased the negative Δε, reduced elastic constant K ₁₁ and moderately decreased rotational viscosity γ₁. The temperature dependence of the key electro-optical parameters was analysed for ester 2, the methyl analogue of 1c, which exhibits a 45 K wide N phase. All four fluoroalkyl derivatives 1d-1f showed enantiotropic SmA phases and 1e also exhibited a monotropic SmC phase. Solutions of 1d-1f in a FLC host (0.2 mmol g^-1) increased the tilt angle Θ (up to 45° for 1g), reduced rotational viscosity γ₁ and the risetime τ. The most dramatic changes were observed for 1g, which contains 15 fluorine atoms.     

Radical production in the radiolysis of liquid benzene

Iodine scavenging techniques have been used to examine the role of the phenyl radical in the radiolysis of benzene with γ-rays. Biphenyl, the main product in the radiolysis of neat benzene, and iodobenzene yields were determined as a function of iodine concentration. The yield of biphenyl in neat benzene is found to be 0.075 molecules/100 eV and independent of dose up to 1 Mrad. The addition of 0.1 mM iodine increases the biphenyl yield to about 0.4 molecules/100 eV. This increase is thought to be due to a reaction of iodine with the phenyl radical–benzene adduct, which apparently has a very long lifetime. Further addition of iodine leads to a decrease in biphenyl to about 0.09 molecules/100 eV at 30 mM iodine. This decrease is accompanied by an increase in iodobenzene from 0.04 to 0.32 molecules/100 eV. It appears that iodine can effectively compete with benzene for scavenging phenyl radicals.     

Concentration dependences of dielectric properties at 105Hz and 106Hz for aqueous solutions of hydroxypropyl cellulose

The concentration dependences of dielectric properties measured at 10⁵ Hz and 10⁶ Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, ε_r', and loss factor, ε_r', were found at the concentrations around the onset of the isotropic-cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in ε_r' and ε_r' were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures.     

The effect of external stimuli on the Bovine Serum Albumin adsorption capacity of poly(acrylamide/maleic acid) hydrogels prepared by gamma rays

The effects of external stimuli such as pH of the buffer solution, ionic strength, temperature and the amount of poly-electrolyte monomer in the hydrogel system on the Bovine Serum Albumin (BSA) adsorption capacity of poly(acrylamide/maleic acid) [P(AAm/MA)] hydrogels were investigated. Poly-electrolyte P(AAm/MA) hydrogels with varying compositions were prepared by irradiating acrylamide/maleic acid/water mixtures with γ rays at ambient temperature. Langmuir type adsorption isotherms were observed for all prepared hydrogels. Increase of ionic strength of the buffer solution from 0.01 to 0.1 mol dm⁻³ decreased the adsorption capacity of hydrogels and zero adsorption was observed in the presence of 0.1 mol dm⁻³ Na⁺ and Ca²⁺ ion in the adsorption medium. The adsorption capacity of hydrogels was found to increase from 0 to 120 mg BSA/g dry gel, by changing external stimuli and hydrogel composition.     

Investigation of thermotropic phase transitions in a triple chain amphiphile forming hexagonal columnar and inverse micellar cubic mesophases: a positron annihilation lifetime study

Positron annihilation lifetime (PAL) measurements were performed between 25 and 100 C in order to study thermotropic phase transformations in an amphiphilic liquid crystal material with three hydrophobic alkyl chains. The lifetime spectra were separated into three exponential components, the long-lived of which is attributed to ortho-positronium (o-Ps) annihilation via pick-off processes. The lifetime of o-Ps, tau3, and its relative intensity, I, as well as the average positron lifetime, tau alpha I3tau3, respond to variations in the structural regularities of the environment. The phase transitions, which have the sequence and temperatures (C) Cr 59 Col(H II) 74 Cub(I II) 85 Iso, are well reflected in abrupt changes of, I3 and Tav. The o-Ps lifetime in the crystalline phase of tau3 = 2.35ns may be interpreted as a crystalline packing coefficient of 0.56 or, alternatively, as o-Ps confined in vacancy-type crystal imperfections with a volume of 0.132 nm3. During melting tau3 increases to 3.05 ns, and this is attributed to the preferential formation of Ps bubbles, with a size of 0.207 nm3, in mobile, liquid-like regions of hydrophobic alkyl chains. The bubble size remains at this value during the H-I transition and increases slightly to 0.216 nm3 during the transformation to the isotropic liquid phase. I3 shows variations during all of the phase transitions, which are attributed to changes in the Ps inhibition rate due to electron/positron mobility, and solvation effects varying as a consequence of different degrees of order of the molecular dipoles.     

Controversy about β-tricalcium phosphate

The calcium phosphate which corresponds to the formula Ca₃(PO)₄ · nH₂O (2<n<3) was isolated from solutions with Ca/P molar ratio 0.2 and pH 7. The compound was characterised by chemical and thermogravimetric analyses, Fourier-transform infrared (FTIR) spectroscopy and X-ray diffraction. The FTIR spectra were compared with spectra of β-tricalcium phosphate (β-TCP) in the atlases for analysis of urinary calculi and other literature data.     

Ortho-positronium lifetimes in nonspherical voids

Experimental values of o-Ps lifetime were compared with model calculations, approximating the voids in a solid by spheres or cuboids. In the case of resorcinol the model of spherical voids is well consistent with the experimental data. For channel-like free volumes the formula, analogous to that for spheres, gives systematically the values of o-Ps lifetime too large. No positronium is found in anthracene, although the radius of free volume is larger than 0.97 Å at which the Ps binding energy should be zero.     

Study of the degradation of gelatin in paper upon aging using aqueous size-exclusion chromatography

We studied the aging behaviour of gelatin used to size paper. Thus far, research on the aging of paper has largely ignored the sizing agent. Degradation of the protein was characterised and the impact of paper components, such as cellulose, and aluminium potassium sulphate was evaluated. Whatman No. 1 filter papers sized with two types of gelatins (A and B) were prepared as model samples. Commercially sized modern papers (Arches) were also studied in order to compare laboratory samples with real artist papers. Both types of papers were artificially aged (80 °C, 50% relative humidity for 35 and 94 days). Historic papers were included in the study in order to compare artificially aged with naturally aged gelatin. The aqueous extracts from the papers were characterised by aqueous size-exclusion chromatography (SEC) using four PL-Aquagel-OH columns and UV photodiode array detection at 220, 254 and 280 nm. Results showed that gelatin undergoes hydrolysis upon aging, type A gelatin showing a faster degradation rate than type B. The result was an increase in the lower-molar-mass fractions, under 50 000 g mol⁻¹, and especially in a characteristic fraction with a peak molecular mass (M_p) of 14 000 g mol⁻¹. A significant decrease in the extraction yields of -, β- and γ-chains occurred after aging. This was attributed to crosslinking, leading to the formation of less-soluble polypeptides with very high molar mass (>800 000 g mol⁻¹). Less than 10% alum had no impact on the degradation rate; higher alum contents accelerated hydrolysis reactions.     

Effect of irradiation on anti-nutrients (total phenolics, tannins and phytate) in Brazilian beans

The Brazilian bean varieties Phaseolus vulgaris L. var. Carioca and Vigna unguiculata (L.) Walp var. Macaçar were irradiated with doses of 0.5, 1.0, 2.5, 5.0 and 10 kGy and subsequently stored at ambient temperature for 6 months. The anti-nutrients phenolic compounds, tannins and phytate were determined to be 0.48 mg g⁻¹ dry basis, 1.8 mg g⁻¹ dry basis and 13.5 μmol g⁻¹ dry basis in the raw non-irradiated Carioca beans and 0.30 mg g⁻¹ dry basis, 0.42 mg g⁻¹ dry basis and 7.5 μmol g⁻¹ dry basis in the raw non-irradiated Macaçar beans. After soaking and cooking a higher content of phenolic compounds and a lower phytate content was observed in both bean varieties. Tannin content was not affected by soaking and cooking of Carioca beans, but higher after soaking and cooking of Macaçar beans. Using radiation doses relevant for food did not effect the content of the anti-nutrients under investigation in both bean varieties.     

Organometallic complexes for nonlinear optics: Part 32: Synthesis, optical spectroscopy and theoretical studies of some osmium alkynyl complexes

The complexes trans-[Os(CCPh)Cl(dppe)₂] (1), trans-[Os(4-CCC₆H₄CCPh)Cl(dppe)₂] (2), and 1,3,5-{trans-[OsCl(dppe)₂(4-CCC₆H₄CC)]}₃C₆H₃ (3) have been prepared. Cyclic voltammetric studies reveal a quasi-reversible oxidation process for each complex at 0.36–0.39 V (with respect to the ferrocene/ferrocenium couple at 0.56 V), assigned to the Os^II/III couple. In situ oxidation of 1–3 using an optically transparent thin-layer electrochemical (OTTLE) cell affords the UV–Vis–NIR spectra of the corresponding cationic complexes 1⁺–3⁺; a low-energy band is observed in the near-IR region (11 000–14 000 cm⁻¹) in each case, in contrast to the neutral complexes 1–3 which are optically transparent below 20 000 cm⁻¹. Density functional theory calculations on the model compounds trans-[Os(CCPh)Cl(PH₃)₄] and trans-[Os(4-CCC₆H₄CCPh)Cl(PH₃)₄] have been used to rationalize the observed optical spectra and suggest that the low-energy bands in the spectra of the cationic complexes can be assigned to transitions involving orbitals delocalized over the metal, chloro and alkynyl ligands. These intense bands have potential utility in switching nonlinear optical response, of interest in optical technology.