Small and large scale segmental motion in polymers: estimating cooperativity length by ordinary relaxation experiments

We derive a suitable expression for estimating the size of the cooperatively rearranging regions (CRRs) in supercooled polymer melts by fitting data worked out by ordinary relaxation experiments carried out in isothermal conditions. As an example, the average CRR size in poly(n‐butyl methacrylate) in proximity to the glass transition temperature is derived from a stress relaxation experiment performed by means of an atomic force microscopy setup. Good agreement is found with results in the literature derived from measurements of temperature fluctuations (the so‐called Donth method). The temperature dependence of the CRR size is explored for poly(butadiene); in this case the segmental relaxation function is derived through a novel method for the analysis of the efficiency with which free induction decay echoes are refocused in ¹H NMR experiments. It is found that the CRR size increases upon cooling. The results derived from the analysis of the NMR data are found to be in satisfactory agreement with those worked out from broadband dielectric spectroscopy data in the literature. © 2015 Society of Chemical Industry     

Chromium (VI) removal by methylated biomass of Spirulina platensis: The effect of methylation process

Biosorption of heavy metals is an interesting approach to treat industrial wastewaters by an environmentally friendly system. Spirulina platensis biomass, an effective biosorbent for cations, cannot be used to adsorb chromate due to its negatively charged surface close to neutral conditions; therefore, methylation of biomass was performed to increase its adsorption capacity under these conditions. Batch adsorption tests carried out varying both Cr(VI) and methylated biomass concentrations showed that 2–4 g l^?1 of biosorbent were able to remove Cr(VI) with efficiency ≥80%, while higher Cr(VI) levels (43–50 mg l^?1) showed low removal efficiency. The model of Langmuir was shown to describe the adsorption phenomenon better than the Freundlich one. The values of the overall adsorption capacity of methylated biomass suggested that increased biosorbent availability does not necessarily correspond to larger amount of adsorbed metal. FT-IR spectra of dried and methylated biomass of S. platensis allowed us monitoring the efficiency of the methylation process through the analysis of CH and COO^? vibrational stretching modes, taken as diagnostic of this process.     

Integrated development of CFRP structures for a topless high performance vehicle

When modern saloon cars are re-engineered as convertibles (or roadsters) it is typical for them to lose 50% or more of the body’s torsional rigidity. Consequently the vehicles rarely handle quite as crisply, nor do they ride as well as the coupes from which they derived. This paper highlights the fundamental contributions of advanced composites in achieving the desired value of handling of the Murcièlago Roadster without penalizing the overall weight of the vehicle. To compensate for the absence of the roof structure, the vehicle was strongly redesigned by introducing new structural members and reinforcing existing critical components. A new all-carbon/epoxy composite sub-frame, which spans the entire engine bay, is comprised of elliptical tubular members, and it is the first of its kind in a production vehicle. Engineering of the sub-frame, from preliminary design to manufacturing decisions, is the focus of this paper, and is achieved through a Building Block approach that sets the program within the Integrated Product Development (IPD) strategy that the Advanced Composites Division of Automobili Lamborghini S.p.A. employs for its technology demonstrators. The strategy consists in a concurrent analytical and experimental development of the product, from the initial conceptual design and coupon testing, through the stages of element and subcomponent engineering, to final component manufacturing.     

Effect of inulin as a prebiotic to improve growth and counts of a probiotic cocktail in fermented skim milk

Inulin was used as a prebiotic to improve quality of skim milk fermented by pure cultures of Lactobacillus acidophilus, Lactobacillus rhamnosus, Lactobacillus bulgaricus and Bifidobacterium lactis, binary co-cultures with Streptococcus thermophilus, or a cocktail containing all them. Inulin supplementation to pure cultures lowered the generation time, with particular concern to S. thermophilus and L. acidophilus. The generation time of all micro-organisms decreased in the following order: mono-cultures, co-cultures, cocktail. It was demonstrated a synergism between S. thermophilus and the other strains and a bifidogenic effect of inulin. Enumerations of L. rhamnosus in cocktail markedly decreased compared to co-cultures likely because of greater competition for the same substrates. The results of this work highlight the industrial potential of the cocktail, mainly in terms of fermentation acceleration.     

Removal of exhausted oils by adsorption on mixed Ca and Mg oxides

Adsorption tests were performed on two different exhausted oils to reduce their polluting and health hazard potential: a "water-insoluble oil", utilised for automotive engine lubrication, and an "emulsified" oil, used as coolant for metal-cutting tools. Dolomite, a low-cost recovery material, was used to prepare two effective adsorbents: (a) a mixed Ca and Mg oxide obtained by thermal decomposition of dolomite at 1800 degrees C, and (b) an activated material obtained by submitting this product to chemical treatment with HCl. Preliminary tests carried out with an excess of the former material showed that the insoluble oil was adsorbed with lower yield (Y = 0.40) than the soluble (emulsified) oil (Y = 0.60). The material activation with HCl remarkably improved the adsorption of soluble oil organic fraction (Y > 0.90), while only a little increase in the removal yield was observed for the insoluble oil (Y = 0.44). The results presented and discussed in this work pointed out that the products of dolomite calcination can successfully replace the conventional adsorbing materials in the removal of organic pollutants, with particular concern to exhausted soluble oils, which cannot usually be recycled, thus reducing the operational costs of their treatment.     

Extraction of phenolic compounds from Vitex agnus-castus L.

The primary objective of this study was to valorized Vitex agnus-castus residues in terms of phenolic compounds. The effects of extraction time (30–360 min), solid to liquid ratio (0.1–0.3 g_DryBiomass/ml_Solvent), type of solvent and different tissue types (leave, roots and seeds) on total polyphenols, o-diphenols, total flavonoids and anthocyanins were evaluated. The highest total polyphenol (31.5 mg_{CaffeicAcidEquivalent}/g_DryBiomass) and o-diphenol (12.4 mg_{CaffeicAcidEquivalent}/g_DryBiomass) contents were obtained from methanolic extract of leaves after 180 min using a solid/liquid ratio of 0.1 g_DryBiomass/ml_Solvent, while total flavonoids, reached a maximum value of 19.4 mg_{CatechinEquivalent}/g_DryBiomass after 360 min under the same conditions. Roots of V. agnus-castus were found to be a good source of anthocyanins with the highest yield of 0.62 mg_{MalvidinEquivalent}/g_DryBiomass using ethanol as a solvent (180 min and 0.2 g_DryBiomass/ml_Solvent). The maximum antiradical power (178.5 μl_extract/μg_DPPH) was exhibited by the methanolic leave extract obtained after 360 min at solid/liquid ratio of 0.3 g_DryBiomass/ml_Solvent.     

Xylitol crystallization from culture media fermented by yeasts

Among sugar substitutes, an important role is played by xylitol, an aliphatic pentitol provided with some interesting properties which make it a high value product for pharmaceutical, odontological and food industries. Its production by biotechnological methods is based on fermentation of agro-industrial residues and could potentially compete with the traditional chemical way. However, crystallization is an important stage of xylitol production, since in many respects it determines the yield and quality of the target product. In the present work tests were made in order to determine the best conditions to clarify fermented media, which were then subjected to isothermal crystallization in the presence or in the absence of residual xylose and varying xylitol concentration as well as cooling temperature (−10 ≤ T_c ≤ 15 °C). Besides, the kinetics of xylitol crystallization from fermented solutions was investigated as function of the initial solution supersaturation and cooling temperature. The effect of the presence of residual xylose on the rate of crystallization was also evaluated. The best clarifying treatment was found to be 20 g l⁻¹ activated charcoal at room temperature for 1 h. The study of xylitol crystallization revealed the positive effect of the presence of residual xylose, which ensured a 1.6-fold increase in the crystallization yield (from 0.27 to 0.42).     

The volatile fraction profiling of fresh tomatoes and triple concentrate tomato pastes as parameter for the determination of geographical origin

Two unsupervised pattern recognition techniques such as stepwise linear discriminant analysis (SLDA) and Soft Independent Modeling of Class Analogy (SIMCA) were used to classify tomato samples in categories corresponding to the cultivation areas. The same approach was used for triple concentrated pastes for discrimination between two different Italian production areas. Accordingly, HS-SPME-GC-MS with 85 ??m carboxen/polydimethylsiloxane fiber was used for the determination of the volatile fraction in tomatoes and triple concentrate tomato pastes samples. Ethyl isobututanoate was used as internal standard for semiquantitative analysis and the concentration data (??g/kg) of 38 compounds for tomatoes and of 32 compounds for triple concentrates were used in following chemometric analysis. Sixteen and three variables were selected by forward stepwise LDA for tomatoes and pastes, respectively. SLDA and SIMCA models showed respectively 96% and 94% in term of prediction ability for tomatoes. The two supervised techniques provided 100% and 97% in prediction of the production areas of tomato pastes, respectively.     

Impact of diet supplemented with microencapsulated condensed tannins on cow milk nutritional profile

Feed production systems should consider more sustainable solutions to reduce the pressure on earth's finite resources. In this work, we investigated the effect of microencapsulated condensed tannins (MCTs)-enhanced diet on the cow milk characteristics. The diet reduced the urea content, while preserved and the n-3 and n-6 portion of fatty acids. Aside from the rising of vitamin C level, MCTs had a negative effect on the amount of B group vitamins. MCTs may be considered a promising feed supplement that offers a good trade-off in terms of milk chemical quality while increasing the environmental sustainability of cattle livestock.     

Quality assessment of bed sediments of the Po River (Italy)

Comprehensive and contemporary evaluations of physical, chemical and toxicological endpoints have been performed on bed sediments of the Po River, the major Italian watercourse. Two extensive sampling campaigns were conducted in summer and winter low-flow conditions. Composite sediment samples were collected from ten reaches of the main river: the first was located in the upper region (ambient control), and the others downstream of the confluences of nine principal tributaries. The two sampling programs were paralleled by contemporary investigations on the macroinvertebrate community. The particle-size composition along the Po River showed a relatively uniform distribution of fine sand, a progressive downstream decrease of coarse sands and a corresponding increase of fine materials. The levels of polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), extractable organo halides (EOX), Cd, Cr, Cu, Hg, Ni, Pb and Zn were determined in sediment fine particles (< 63 microm), and showed marked changes across the ten river reaches. Their longitudinal trends, as those of organic carbon and total nitrogen, were very similar and largely independent of the survey season. Sediment quality benchmarks were used to evaluate sediment chemistry, and, although the overall level of contamination was from moderate to low, the reaches located downstream of the tributaries Dora Riparia, Dora Baltea, Lambro and Oglio were considered to be at risk. Sediments were tested for toxicity on Oncorhynchus mykiss, Ceriodaphnia dubia, Raphidocelis subcapitata and Vibrio fischeri. The toxicity tests were conducted both with sediment extracts and whole samples. Sediment extracts showed toxic potentials that were consistent with the spatial distribution of contaminants. Whole-sediment toxicity showed moderate/low effects which also included false positives and negatives. Alterations of the macroinvertebrate community were found for many kilometers downstream of Dora Riparia, and with a seasonal dependence, also in other reaches of the Italian river. Principal component analysis (PCA) was used to describe the longitudinal and temporal changes of the Po River, and allowed the selection of the most useful and discriminating indicators.