Structure of poly(vinyl alcohol)-iodine complex formed in the amorphous phase of poly(vinyl alcohol) films

The effect of syndiotactivity of poly(vinyl alcohol) (PVA) both on the formation and thermal stability of the complex formed in the amorphous phase of PVA films is investigated, and then a model of the complex is presented. The amount of the complex formed in syndiotacticity-rich PVA is much larger than that formed in atactic PVA under a given iodine-soaking condition, and the former complex has a higher thermal stability in the soaking solution than the latter. The complex formed in the amorphous phase is proposed to have such a structure as that in which a linear polyiodine I₅^? or I₅^? with a 3.1 A? periodicity is enveloped by four PVA segments of syndiotactic configuration with extended conformation. In this model, these four PVA chains participating in a complex are supposed to be fixed by interchain hydrogen bonds. The observed X-ray meridional intensity curve of iodinated PVA film can be explained by a series of two I₅^?. © 1993 John Wiley & Sons, Inc.     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Thermal and flow properties of oils from salmon heads

Thermal and flow properties of unrefined oils from the heads of red or pink salmon were evaluated. Major thermal degradation of the salmon oils occurred between 200 and 450°C. Red and pink salmon oils were completely decomposed at 533 and 668°C, respectively. The phase transition of salmon oils occurred over a wide range of temperatures. The melting points of −69.6 to −0.36°C and −64.7 to 20.8°C were observed for red and pink salmon oils, respectively. The enthalpy was 40 j/g for red salmon oil and 39 j/g for pink salmon oil. Specific heat capacity ranges of 0.8 to 1.6 and 1.3 to 2.3 j/g/°C were observed for red and pink salmon oils, respectively. Both salmon oils exhibited Newtonian flow behavior. Red salmon oil required higher magnitudes of energy (kj·mol⁻¹) to flow than pink salmon oil. The viscosity of salmon oils was temperature-dependent and could be predicted by the Arrhenius equation.     

The effect of supercooling on crystallization of cocoa butter-vegetable oil blends

The solid fat content (SFC), Avrami index (n), crystallization rate (z), fractal dimension (D), and the pre-exponential term [log(γ)] were determined in blends of cocoa butter (CB) with canola oil or soybean oil crystallized at temperatures (T _Cr) between 9.5 and 13.5°C. The relationship of these parameters with the elasticity (G′) and yield stress (σ^*) values of the crystallized blends was investigated, considering the equilibrium melting temperature (T _M ^o) and the supercooling (i.e., T _Cr ^o−T _M ^o) present in the blends. In general, supercooling was higher in the CB/soybean oil blend [T _M ^o=65.8°C (±3.0°C)] than in the CB/canola oil blend [T _M ^o=33.7°C (±4.9°C)]. Therefore, under similar T _Cr values, higher SFC and z values (P<0.05) were obtained with the CB/soybean oil blend. However, independent of T _Cr TAG followed a spherulitic crystal growth mechanism in both blends. Supercooling calculated with melting temperatures from DSC thermograms explained the SFC and z behavior just within each blend. However, supercooling calculated with T _M ^o explained both the SFC and z behavior within each blend and between the blends. Thus, independent of the blend used, SFC described the behavior of G′_eq and σ^* and pointed out the presence of two supercooling regions. In the lower supercooling region, G′_eq and σ^* decreased as SFC increased between 20 and 23%. In this region, the crystal network structures were formed by a mixture of small β′ crystals and large β crystals. In contrast, in the higher supercooling region (24 to 27% SFC), G′_eq and σ^* had a direct relationship with SFC, and the crystal network structure was formed mainly by small β′ crystals. However, we could not find a particular relationship that described the overall behavior of G′_eq and σ^* as a function of D and independent of the system investigated.     

A biomarker of n−3 compliance in patients taking fish oil for rheumatoid arthritis

Dietary fish oil supplements have been shown to have benefits in rheumatoid arthritis (RA), other inflammatory diseases, and in cardiovascular disease. As with any medical advice, variability will exist with regard to adherence and consequent biochemical or pharmacophysiologic effects. The aim was to explore the utility of plasma phospholipid EPA as a measure of n−3 PUFA intake and response to standardized therapeutic advice given in an outpatient or office practice setting, to increase dietary n−3 PUFA, including a fish oil supplement. Patients with early RA were given verbal and written advice to alter their dietary n−3 PUFA intake, including ingestion of 20 mL of bottled fish oil on juice daily. The advice included instructions to increase n−3 PUFA and to avoid foods rich in n−6 PUFA. Every 3 mon, blood samples were obtained for analysis of plasma phospholipid FA. Plasma phospholipid EPA was used as the primary index of n−3 PUFA intake. A diverse response was seen, with about one-third of patients achieving a substantial elevation of plasma phospholipid EPA over the 12-mon study period. A third had little change, with the remainder achieving intermediate levels. Data obtained longitudinally from individual patients indicated that substantial elevations of EPA (>5% total plasma phospholipid FA) could be maintained for more than 3 yr. Plasma phospholipid EPA is a convenient measure of adherence to advice to take a dietary n−3 PUFA-rich fish oil supplement. This measure may prove a useful adjunct to intention to treat analyses in determining the effect of dietary fish oil supplements on long-term outcomes in arthritis and other chronic inflammatory diseases. It may also provide a guide to the effectiveness of therapeutic and preventive messages designed to increase n−3 PUFA intake.     

Transformations of sulphur compounds in high-sulphur coals during reduction in the potassium/liquid ammonia system

The two types of high-sulphur coals Mequinenza and Illinois No. 6, in the initial form and subjected to potassium/liquid ammonia reduction, were analysed by atmospheric pressure-temperature programmed reduction (AP-TPR) method. It has been shown that preliminary demineralisation was beneficial for AP-TPR measurements because of the removal of calcium compounds. The reduction of sulphides and disulphides in the potassium/liquid ammonia system was found to lead to formation of aromatic and aliphatic thiols. The presence of the latter is better manifested in the AP-TPR kinetograms when the measurements are performed in the presence of a special reducing mixture. It has been shown that the coal reduction in the potassium/liquid ammonia system apart from transformations of non-thiophene sulphur groups also leads to breaking up of the C-S bonds in some thiophene systems.     

Classification of vegetable oils by high-resolution <Superscript>13</Superscript>C NMR spectroscopy using chromatographically obtained oil fractions

¹³C NMR spectra of oil fractions obtained chromatographically from 109 vegetable oils were obtained and analyzed to evaluate the potential use of those fractions in the classification of vegetable oils and to compare the results with the NMR analysis of complete oils. The oils included the following: virgin olive oils from different cultivars and regions of Europe and north Africa; “lampante” olive, refined olive, refined olive pomace, hazelnut, rapeseed, high-oleic sunflower, corn, grapeseed, soybean, and sunflower oils; and mixtures of virgin olive oils from different geographical origins. Oils were divided into two sets of samples. The training set (98 samples) was employed to select the variables that resulted in significant discrimination among the different oil classes. By using stepwise discriminant analysis, more than 98% of correct validated assignments were obtained; these results were confirmed when applied to the test set (11 blind samples). Results suggest that the use of oil fractions considerably increases the discriminating power of NMR in the analysis of vegetable oils.     

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl- and 1,2-diacyl glycerophospholipids in Japanese oysterCrassostrea gigas (Thunberg)

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl-, and 1,2-diacyl-sn-glycero-3-phosphoethanolamine (EPL) andsn-glycero-3-phosphocholine (CPL) of Japanese oysterCrassostrea gigas were analyzed by selectedion monitoring gas chromatography/mass spectrometry using electron impact ionization. The characteristic fragment ions, [RCH=CH+56]⁺ due to the alkenyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkenylacylglycerols, [R+130]⁺ due to the alkyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkylacylglycerols, [RCO+74]⁺ due to the acyl residues in thesn-1 and/orsn-2 positions of diacylglycerols, and [M−57]⁺ being indicative of the corresponding molecular weight, were used for structural assignments. For alkenylacyl EPL and CPL, 19 and 16 molecular species were determined, respectively. Two molecular species, 18∶0alkenyl-22∶6n−3 and 18∶0-alkenyl-22∶2-non-methylene interrupted diene (NMID), amounted to 53.2% and 47.9%, respectively. The alkylacyl EPL and CPL consisted of 16 and 20 molecular species, respectively, and the prominent components were 18∶0alkyl-22∶2NMID, 20∶1alkyl-20∶1n−11 (27.4%) and 20∶1alkyl-20∶2NMID (16.3%) in the former, and 16∶0alkyl-20∶5n−3 (23.0%) and 16∶0alkyl-22∶6n−3 (21.6%) in the latter. For the diacyl EPL and CPL, 14 and 51 molecular species were determined, respectively. The major molecular species were 18∶0–20∶5n−3 (37.4%), 16∶0–20∶5n−3 (14.2%) and 18∶1n−7–22∶2NMID (13.2%) in the former, and 16∶0–20∶5n−3 (33.4%) and 16∶0–22∶6n−3 (22.3%) in the latter. It was found that there were significant differences in the molecular species between the alkylacyl and diacyl EPL and the alkylacyl and diacyl CPL; the number of molecular species was larger in CPL than in EPL, while the number of total carbons and double bonds of the major molecular species were larger in the EPL than in the CPL. Alkenylacyl EPL were similar to alkenylacyl CPL in molecular species composition.     

Plant Cyanogenesis of <Emphasis Type="Italic">Phaseolus lunatus</Emphasis> and its Relevance for Herbivore–Plant Interaction: The Importance of Quantitative Data

Quantitative experimental results on the antiherbivorous effect of cyanogenesis are rare. In our analyses, we distinguished between the total amount of cyanide-containing compounds stored in a given tissue [cyanogenic potential (HCNp)] and the capacity for release of HCN per unit time (HCNc) from these cyanogenic precursors as a reaction to herbivory. We analyzed the impact of these cyanogenic features on herbivorous insects using different accessions of lima beans (Phaseolus lunatus L.) with different cyanogenic characteristics in their leaves and fourth instars of the generalist herbivore Schistocerca gregaria Forskål (Orthoptera, Acrididae). Young leaves exhibit a higher HCNp and HCNc than mature leaves. This ontogenetic variability of cyanogenesis was valid for all accessions studied. In no-choice bioassays, feeding of S. gregaria was reduced on high cyanogenic lima beans compared with low cyanogenic beans. A HCNp of about 15 μmol cyanide/g leaf (fresh weight) with a corresponding HCNc of about 1 μmol HCN released from leaf material within the first 10 min after complete tissue disintegration appears to be a threshold at which the first repellent effects on S. gregaria were observed. The repellent effect of cyanogenesis increased above these thresholds of HCNp and HCNc. No repellent action of cyanogenesis was observed on plants with lower HCNp and HCNc. These low cyanogenic accessions of P. lunatus were consumed extensively—with dramatic consequences for the herbivore. After consumption, locusts showed severe symptoms of intoxication. Choice assays confirmed the feeding preference of locusts for low over high cyanogenic leaf material of P. lunatus. The bioassays revealed total losses of HCN between 90 and 99% related to the estimated amount of ingested cyanide-containing compounds by the locusts. This general finding was independent of the cyanogenic status (high or low) of the leaf material.