Long‐Aliphatic‐Segment Polyamides: Salt Preparation and Subsequent Anhydrous Polymerization

Long‐aliphatic‐segment polyamides were prepared based on hexamethylenediamine and α,ω‐(CH₂)_x biosynthetic diacids (x = 10, 11, 12). The pertinent monomers (salts) were isolated as solids, thoroughly characterized for the first time, and then submitted to an anhydrous melt prepolymerization technique. The obtained prepolymers exhibited in the range of 5 100–11 800 g · mol^?1, and the molecular weight was further increased by up to 55% through solid‐state finishing. The suggested overall polyamidation cycle was conducted at short melt‐reaction times, so as to avoid any thermal degradation, and was proved efficient, indicating similar reactants polymerizability independently of the methylene content.

     

Anthocyanin profiles of major red grape (Vitis vinifera L.) varieties cultivated in Greece and their relationship with in vitro antioxidant characteristics

A range of fourty‐six red grape (Vitis vinifera spp.) samples, originating from six widely cultivated varieties and covering major parts of the Hellenic vineyard, were assayed for their content in six principal anthocyanin pigments. Representative in vitro antioxidant parameters were also determined, including antiradical activity (A_AR), reducing power (P_R) and hydroxyl free radical scavenging activity (SA_HFR). Quantitative determination using high performance liquid chromatography showed that the prevalent pigment was malvidin 3‐O‐glucoside (average content 82.53 mg per 100 g fresh berry weight), followed by its coumarate derivative (29.26 mg per 100 g), paeonidin 3‐O‐glucoside (10.84 mg per 100 g), petunidin 3‐O‐glucoside (7.80 mg per 100 g) cyanidin 3‐O‐glucoside (5.67 mg per 100 g) and delphinidin 3‐O‐glucoside (1.28 mg per 100 g). The richest variety was Syrah, with total average anthocyanin content of 186.02 mg per 100 g, whereas the Hellenic native variety Xinomavro had the lowest average anthocyanin level (38.70 mg per 100 g). The establishment of correlations of individual and total anthocyanin contents with the values from the antioxidant test was accomplished with linear regression. The links of total anthocyanins were significant with all antioxidant parameters (P < 0.001), but more importantly with SA_HFR (R² = 0.740). Malvidin 3‐O‐glucoside content had the higher correlation with SA_HFR compared with all other anthocyanins (R² = 0.698, P < 0.001).     

Evaluation of the antiradical and reducing properties of selected Greek white wines: correlation with polyphenolic composition

The total hydroxycinnamate (THC) and total flavanol (TF) contents were determined in 26 selected Greek white wines of ‘Appellation of Origin of High Quality’ using well‐established spectrophotometric methodology. Furthermore, two parameters related to the antioxidant capacity of wines, the antiradical activity (A_AR) and the reducing power (P_R), were also determined using the stable DPPH· radical and a ferric reducing power assay respectively. THC content varied from 64.4 to 197.1 mg l^?1 chlorogenic acid equivalents (CGAE), whereas TF content exhibited larger variation, ranging from 3.3 to 205.3 mg l^?1 catechin equivalents (CTE). A_AR and P_R were found to range from 0.47 to 0.60 mM Trolox equivalents (TRE) and from 0.32 to 2.05 mM quercetin equivalents (QE) respectively. Regression analysis at 95% significance level indicated that reducing effects are likely to be exerted by the flavanol fraction (SF < 0.05), as opposed to antiradical efficiency which is primarily affected by the sum of THC and TF contents (SF < 0.05), suggesting that synergistic phenomena account for the overall antioxidant status of white wines. © 2002 Society of Chemical Industry     

Applying the Traditional Solution Melt Polymerization for the in situ Intercalation of Polyamide 6.6‐Clay Nanocomposites

The traditional PA 6.6 production route, i.e. solution melt polymerization followed by extrusion, is applied to the in situ intercalation of PA 6.6/clay nanocomposites. Organoclays of different types are tested and the derived nanocomposites are thoroughly characterized in terms of molecular weight, thermal properties and morphology. Reaction acceleration is found in the presence of fully exchanged organoclays, which is attributed to a chain extension mechanism based on clay SiOH groups. Analysis of the nanocomposites' nanostructure indicates that the applied solution melt polymerization process results in some flocculation of the tested organoclays, which is improved in some cases after extrusion and leads to partially exfoliated nanocomposites.

     

Morphological changes of poly(ethylene terephthalate‐co‐isophthalate) during solid state polymerization

Poly(ethylene terephthalate‐co‐isophthalate) (PETI) prepolymer was submitted to solid state polymerization (SSP) at 184–230°C in a fixed bed reactor, to study the evolution of morphological changes during the process. Short reaction times were selected to investigate crystallization phenomena during nonisothermal (heating) and isothermal SSP phases. More specifically, multiple PETI melting behavior was observed and attributed to secondary crystallization, the rate of which increased significantly with SSP temperature. Reaction time was also found to exert a positive effect on solid‐phase perfection of secondary crystals, leading at each temperature to melting points close to the value of bottle‐grade poly(ethylene terephthalate). Finally, the mass fraction crystallinity of the SSP grades was found to comply with the crystal morphology encountered. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of sulfur dioxide addition in wild yeast population dynamics and polyphenolic composition during spontaneous red wine fermentation from Vitis vinifera cultivar Agiorgitiko

The aim of the present study was to assess the effect of sulfur dioxide addition in the wild yeast population dynamics as well as the polyphenolic composition during spontaneous red wine fermentation from Vitis vinifera cultivar Agiorgitiko. The grapes were crushed and fermentation took place at 21 °C without the addition of any commercial yeast, and with and without the addition of 40 mg L^?1 SO₂. A combination of culture-dependent and culture-independent techniques was used for wild yeast population dynamics assessment and HPLC analysis for the determination of polyphenolic compounds. Regarding the former, the effect of sulfur dioxide addition was only marginal since Saccharomyces cerevisiae strains dominated the fermentation from the first day; strains belonging to Hanseniaspora spp., Lachancea thermotolerans and Metschnikowia pulcherrima species appeared only occasionally. As far as the polyphenolic content was concerned, it was enhanced with sulfur dioxide addition; however, as time progressed, the differences were reduced, suggesting that the time the juice was in contact with the skins was of greater importance than sulfur dioxide addition.     

Browning development in white wines: dependence on compositional parameters and impact on antioxidant characteristics

Browning is a serious problem in relation to white wine quality and mostly affects the sensory attributes, whereas its impact on the dietary value of wines has never been investigated. Browning, however, is well known to be associated with polyphenol oxidation, and therefore it may be accompanied by changes in the antioxidant capacity. On the basis of this consideration, experimental white wines vinified and stored under identical conditions were subjected to accelerated browning, and efforts were made to distinguish compositional parameters that might be related to the extent of browning development. Further, the consequences of browning on the reducing power and antiradical activity were assessed. It was shown that none of the parameters examined (titratable acidity, pH, total SO₂, total polyphenols and total flavanols) play an important role in browning onset, but SO₂ appeared to exert a statistically significant influence (r²=0.6394, P<0.05) on the percentage change in the antiradical activity. Evidence also suggested that browning development might be prominently associated with decreases in both antiradical activity (r²=0.7891, P<0.01) and reducing power (r²=0.6925, P<0.05).     

Production of biodegradable polyesters via enzymatic polymerization and solid state finishing

The synthesis of aliphatic polyesters (PEs) derived from diols (1,4‐butanediol and 1,8‐octanediol) and diacids or their derivatives (diethyl succinate, sebacic acid, 1,12‐dodecanedioic acid, and 1,14‐tetradecanedioic acid) was achieved in order to produce poly(butylene succinate) (PE 4.4), poly(octylene sebacate) (PE 8.10), poly(octylene dodecanate) (PE 8.12), and poly(octylene tetradecanate) (PE 8.14). The herein suggested procedure involved two stages, both sustainable and in accordance with the principles of “green” polymerization. The first comprised an enzymatic prepolymerization under vacuum, in the presence of diphenylether as solvent using Candida antarctica lipase B as biocatalyst, whereas a low‐temperature postpolymerization step [solid state polymerization (SSP)] followed in order to upgrade the PEs quality. In the enzymatically synthesized prepolymers, the range of number–average molecular weight attained was from 3700 to 8000 g/mol with yields reaching even 97%. Subsequently, SSP of PE 4.4 and 8.12 took place under vacuum or flowing nitrogen and lasted 10–48 h, at temperatures close to the prepolymer melting point (T_m ? T_SSP varied between 4°C and 14°C). The solid state finishing led to increase in the molecular weight depending on the prepolymer type, and it also contributed to improvement of the physical characteristics and the thermal properties of the enzymatically synthesized PEs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40820.     

New-onset psoriasis in a maintenance hemodialysis patient

New-onset psoriasis is extremely rare in hemodialysis (HD) patients, and several trials of dialysis therapies (HD and peritoneal dialysis) in psoriasis have indicated remarkable improvement in skin lesions and well-being even in patients without renal impairment. We describe a patient who developed severe psoriasis despite undergoing chronic maintenance hemodialysis for 5 years and was treated successfully with oral cyclosporin A.