Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

Application of an interpenetrating network model to the solid deformation of a quenched isotactic polypropylene film

The molecular orientation and deformation mechanisms of a quenched isotactic polypropylene (iPP) film deformed at temperatures between 303 K and the melting point are studied. At draw temperature T_E less than 400 K where the degree of crystallinity does not change markedly, a linear relationship between molecular orientations of the crystalline and the amorphous phases is revealed and the slope is estimated about 1.82. The interpenetrating network (IPN) model, that takes into account the plastic response of the crystalline (C) network formed by a small portion of crystallites adhered through intercrystalline links and the pseudo-affine deformation of the crystallite enhanced amorphous matrix (CEAM) network, is able to account for inhomogeneous deformation behavior on the mesoscale accompanied with the localized necking in this T_E range. Meanwhile, the initial Young's modulus and the true yield stress exerted by the deformation of the rigid C network exhibit the Arrhenius type of dependence on T_E. The apparent shear modulus of the CEAM network as a function of T_E is discussed in relation to variations in numbers and average molecular weights of the crystalline and the amorphous sequences being manifested by small consecutive endothermic and exothermic peaks in the DSC curve. The IPN model becomes invalid for deformations above T_E=400 K where morphological changes are induced due to melting of crystallites as proved from the DSC measurement.     

Photoelectrochemical decomposition of bio-related compounds at a nanoporous semiconductor film photoanode and their photocurrent-photovoltage characteristics

Photoelectrochemical decomposition of bio-related compounds such as amino acids was investigated with a biophotochemical cell comprising a mesoporous TiO₂ thin film photoanode and an O₂-reducing cathode. It was concluded that a kind of Schottky junction formed at the surface of the TiO₂ (called as liquid junction) induced the photodecomposition followed by generation of photocurrent/photovoltage. Complete photodecomposition was investigated by the CO₂ formation yield. The photocurrent-photovoltage (J-V) characteristics of amino acids and other typical bio-related compounds were investigated, and the short circuit photocurrent (J_sc), open circuit photovoltage (V_oc), and Fill factor (ff) were exhibited. Effect of pH on the photodecomposition of phenylalanine and cysteine were studied; for cysteine alkaline conditions gave a high efficiency, which was interpreted by the high electron-donating ability of the dissociated -S⁻ group. The incident light-to-current conversion efficiency (IPCE) of cysteine was 25% at 350 nm. It was for the first time shown that organic acids gave high internal quantum efficiency (η′) over 8 (=800%) in the photodecomposition; for oxalic acid it was 9.3 (=930%) and for butyric acid 8.2. The alternating current impedance spectroscopy of glycine showed that the cell performance is determined by the chemical reactions at TiO₂ or Pt electrodes.     

Determination of acrylamide in processed foods by LC/MS using column switching

An LC/MS method was developed for the determination of acrylamide (AA) in processed or cooked foods. AA was extracted with a mixture of water and acetone from homogenized food samples after the addition of 13C-labeled acrylamide (AA-1-(13)C) as an internal standard. The extract was concentrated, washed with dichloromethane for defatting, and cleaned up on Bond Elut C18, PSA and ACCUCAT cartridge-columns, and then AA was determined by LC/MS in the selected ion recording (SIR) mode. For the LC/MS analysis, four LC columns were connected in-line and the flow of the mobile phase was switched according to a time-program. Monitoring ions for AA were m/z 72 and 55, and those for AA-1-(13)C were m/z 73 and 56. AA and AA-1-(13)C were determined without interference from the matrices in all samples. The recoveries of AA from potato chips, corn snack, pretzel and roasted tea spiked at the level of 500 ng/g of AA were 99.5-101.0% with standard deviations (SD) in the range from 0.3 to 1.6%. The limits of detection and quantification of the developed method were 9 and 30 ng/g for AA in samples, respectively. The method was applied to the analysis of AA in various processed or cooked food samples purchased from retail markets. High levels of AA were found in potato chips and French-fried potato (467-3,544 ng/g). Fried and sugar-coated dough cakes (karinto) contained 374 and 1,895 ng/g. Corn snacks contained 117-535 ng/g of AA. Roasted foods (such as roasted sesame seed, roasted barley (mugi-cha), roasted tea (hoji-cha), coffee beans and curry powder) contained 116-567 ng/g of AA. Foods made from fish, egg and meat contained lower levels of AA than the plant-based foods. Foods containing much water showed a tendency to have low levels of AA compared with dry foods. The proposed method was applicable to the analysis of AA in variety of processed foods.     

Spectral changes and 1 X N spectral switches in the diffraction of partially coherent light by an aperture

The off-axis and on-axis spectra in the far zone of an aperture for the case in which a particular class of partially coherent light with a broad spectrum is diffracted by an aperture are studied. It is shown that the spectrum in the far zone is generally different from that at the aperture; i.e., the spectrum is split into two or more peaks. Moreover, the spectrum varies with the diffractive angle. For a fixed diffractive angle, the spectral shift, defined as the difference between the frequencies at which the observed spectrum and the spectrum at the aperture take their maximum, shows a gradual change with the change in the coherence at the aperture. However, as the coherence reaches some critical values, the spectral shift exhibits a rapid transition; i.e., spectral switch occurs. The coherence that causes the spectral switch to take place is different for different diffractive angles. Therefore we propose a new kind of 1 x N spectral switch, where N detectors (output ports) are placed at different diffractive angles in the far zone, and the spectral shifts at different detectors are measured. By adjusting the coherence of the aperture (input port) to the desired values, we obtain a rapid transition of the spectral shift in the desired output ports.     

Structurally related peptide agonist, partial agonist, and antagonist occupy a similar binding pocket within the cholecystokinin receptor. Rapid analysis using fluorescent photoaffinity labeling probes and capillary electrophoresis

The molecular basis of ligand binding to receptors provides important insights for drug development. Here, we explore domains of the cholecystokinin (CCK) receptor that are critical for ligand binding, using a novel series of fluorescent photolabile probes, receptor proteolysis, and rapid high resolution separation of peptide fragments by capillary electrophoresis. Each probe incorporated the same fluorophore and a photolabile p-benzoylphenylalanine at the amino terminus of the pharmacophoric domain (residue 24 of CCK-33) of CCK analogues representing full agonist, partial agonist, and antagonist of this receptor. Each was used to label the CCK receptor expressed on Chinese hamster ovary-CCKR cells, with the labeled domain then released by cyanogen bromide cleavage. Capillary electrophoresis with laser-induced fluorescence detection achieved an on-capillary mass sensitivity of 1.6 attomoles (10(-18) mol), with an excellent signal-to-noise ratio. Each of the biologically divergent, but structurally similar probes saturably and specifically labeled the same receptor domain, consistent with conservation of "docking" determinants. This had an apparent mass of 2.9 kDa, most consistent with the first extracellular loop domain. An additional probe having its site of covalent attachment in a different region of the probe (residue 29 of CCK-33) labeled a distinct receptor fragment with differential migration on capillary electrophoresis (third extracellular loop). Identification of the specific receptor residue(s) covalently linked to the amino-terminal probes must await further fragmentation and sequence analysis.     

The relationship of chronic mucin secretion to airway disease in normal and CFTR-deficient mice

In the cystic fibrosis (CF) patient, lung function decreases throughout life as a result of continuous cycles of infection, particularly with Pseudomonas aeruginosa and Staphylococcus aureus. The mechanism underlying the pathophysiology of the disease in humans has not been established. However, it has been suggested that abnormal, tenacious mucus, resulting perhaps from improper hydration from loss of Cl- secretion via the cystic fibrosis transmembrane conductance regulator (CFTR) protein, impairs clearance of bacteria from the CF airway and provides an environment favorable to bacterial growth. If this hypothesis is correct, it could explain the absence of respiratory disease in CFTR-deficient mice, since mice have only a single submucosal gland and display few goblet cells in their lower airways, even when exposed to bacteria. To test this hypothesis further, we induced allergic airway disease in CFTR-deficient mice. We found that induction of allergic airway disease in mice, unlike bacterial infection, results in an inflammatory response characterized by goblet cell hyperplasia, increased mucin gene expression, and increased production of mucus. However, we also found that disease progression and resolution is identical in Cftr-/- mice and control animals. Furthermore, we show that the presence of mucus in the Cftr-/- airway does not lead to chronic airway disease, even upon direct inoculation with S. aureus and P. aeruginosa. Therefore, factors in addition to the absence of high levels of mucus secretion protect the mouse from the airway disease seen in human CF patients.     

Refusal to eat in the elderly

Refusal to eat by the elderly, and subsequent malnutrition, occurs in both institutional and community settings. Causes include physiologic changes associated with aging, mental disorders such as dementia and depression, and medical, social, and environmental factors. Treatment approaches call for management of these causes while considering the roles that medicine, ethics, and culture play in the process.     

Dynamic course of neurological syndromes in very young children with the history of intrauterine growth retardation

90 infants with intrauterine growth retardation (IGR) and 100 normal infants (control group) were followed up from 5 days till 3 years of life. In IGR infants there was a more frequent combination of several neurologic syndromes, an early manifestation of motor disorders (from the very moment of birth), a delay of neuro-psychic development (during the first year of life), a tendency to development of moderate hydrocephalus by the age of 6 months. Autonomic-visceral disorders in them were mostly characterized by the symptoms of abaissement, but not of irritation.