Solvent‐free synthesis of glycerol carbonate and glycidol from 3‐chloro‐1,2‐propanediol and potassium (hydrogen) carbonate

BACKGROUND: An indirect solvent‐free synthetic approach for obtaining glycerol carbonate and glycidol from glycerol and CO₂ through their more reactive and easily synthesizable derivatives 3‐chloro‐1,2‐propanediol (HAL) and potassium (hydrogen) carbonate has been studied. RESULTS: The reaction is fast with source of carbonation and temperature having a strong influence on the results. A yield of 80% glycerol carbonate together with a simultaneous substantial production of glycidol (0.56 mol mol^?1 glycerol carbonate) are obtained using K₂CO₃ as the carbonation source at 80 °C, a reaction time of 30 min and a 3:1 HAL/K₂CO₃ molar ratio. A lower yield of glycerol carbonate (60%) is obtained from KHCO₃ after 50 min with the other experimental conditions remaining unchanged. In this case, glycidol formation is zero or insignificant. Glycerol is also obtained in high yields, although in much lower amounts from KHCO₃ (～0.59 mol mol^?1 glycerol carbonate independent of operating conditions) than from K₂CO₃ (0.84–1.1 mol mol^?1 glycerol carbonate, depending on experimental conditions). CONCLUSIONS: The proposed synthetic strategy overcomes the currently difficult direct reaction between glycerol and CO₂, leading to the simultaneous synthesis of two valuable chemicals: glycerol carbonate and glycidol. However, glycerol is also obtained in substantial amounts thus decreasing the overall yield of the process. Thus, methods for preventing its formation must be developed for industrial feasibility. Copyright © 2010 Society of Chemical Industry     

Structural features of diamond layers photo-emitting at sub-band gap energies

The photoemission behaviour of a series of diamond-based polycrystalline films irradiated by the second (2.3 eV), third (3.5 eV) and fourth (4.7 eV) harmonics produced by a Q-switched-mode-locked Nd: Yag laser has been investigated and related to the structural and compositional characteristics of the layers. The materials were polycrystalline undoped diamond films as well as Nd- and N-containing diamond films grown by CVD techniques, diamond-like and amorphous carbon layers. The morphological and structural characteristics of the films were investigated by electron microscopy, Raman spectroscopy and electron diffraction. The analysis of the photoemission curves does not evidence any improvement of the emission efficiency in the case of Nd-containing films nor for the diamond films grown in the presence of N_2. The results evidence conversely a strong correlation between the characteristics of the photoemission process at sub-band gap energies and the presence of amorphous sp²-C patches located at the diamond film surfaces. The photoemitting properties of our samples are discussed and rationalized by considering charge emission occurring at the sp²-diamond-vacuum border and the emission process governed by the ratio of amorphous sp²-C to crystalline sp³-C. The rather high values of quantum efficiency measured in the course of the present research at 3.5 and 4.7 eV suggest that a proper distribution of amorphous carbon onto a good quality diamond surface is the key factor for the preparation of efficient and stable photocathode materials.     

Stochastic modeling and analysis of road–tramway intersections

In the last decades, the socio-demographic evolution of the population has substantially changed mobility demand, posing new challenges in minimizing urban congestion and reducing environmental impact. In this scenario, understanding how different modes of transport can efficiently share (partially or totally) a common infrastructure is crucial for urban development. To this aim, we present a stochastic model-based analysis of critical intersections shared by tram traffic and private traffic, combining a microscopic model of the former with a macroscopic model of the latter. Advanced simulation tools are typically used for such kind of analyses, by playing various traffic scenarios. However, simulation is not an exhaustive approach, and some critical, possibly rare, event may be ignored. For this reason, our aim is instead to adopt suitable analytical solution techniques and tools that can support instead a complete, exhaustive analysis, so being able to take into account rare events as well. Transient analysis of the overall traffic model using the method of stochastic state classes is adopted to support the evaluation of relevant performance measures, namely the probability of traffic congestion over time and the average number of private vehicles in the queue over time. A sensitivity analysis is performed with respect to multiple parameters, notably including the arrival rate of private vehicles, the frequency of tram rides, and the time needed to recover from traffic congestion.

     

Redox behavior of gold supported on ceria and ceria-zirconia based catalysts

A series of gold-based catalysts were prepared by deposition precipitation or incipient wetness impregnation on CexZ1-xO2 solid solutions (0.28≤x≤1.00). The morphological and structural characterization of these catalysts were carried out with X-ray diffraction, trans-mission electron microscopy (TEM) analysis and physical adsorption technique, and their redox properties were studied by temperature pro-grammed reduction using both H2 and CO as probe molecules. Two cycles of oxidation/reduction were carried out in order to evaluate the effects of redox aging and gold sintering on the oxygen exchange capability. As observed with other noble metals, gold enhanced and pro-moted the ceria reduction at lower temperatures. Reduction by CO was shown to be dependent on the fine dispersion of gold and to be nega-tively affected by the ageing process more than reduction with hydrogen. This might have implications in reactions like water gas shift and CO-PROX which involve CO as a main reactant.     

Prediction of genomic breeding values for dairy traits in Italian Brown and Simmental bulls using a principal component approach

The large number of markers available compared with phenotypes represents one of the main issues in genomic selection. In this work, principal component analysis was used to reduce the number of predictors for calculating genomic breeding values (GEBV). Bulls of 2 cattle breeds farmed in Italy (634 Brown and 469 Simmental) were genotyped with the 54K Illumina beadchip (Illumina Inc., San Diego, CA). After data editing, 37,254 and 40,179 single nucleotide polymorphisms (SNP) were retained for Brown and Simmental, respectively. Principal component analysis carried out on the SNP genotype matrix extracted 2,257 and 3,596 new variables in the 2 breeds, respectively. Bulls were sorted by birth year to create reference and prediction populations. The effect of principal components on deregressed proofs in reference animals was estimated with a BLUP model. Results were compared with those obtained by using SNP genotypes as predictors with either the BLUP or Bayes_A method. Traits considered were milk, fat, and protein yields, fat and protein percentages, and somatic cell score. The GEBV were obtained for prediction population by blending direct genomic prediction and pedigree indexes. No substantial differences were observed in squared correlations between GEBV and EBV in prediction animals between the 3 methods in the 2 breeds. The principal component analysis method allowed for a reduction of about 90% in the number of independent variables when predicting direct genomic values, with a substantial decrease in calculation time and without loss of accuracy.     

Influence of the refrigeration technique on the colour and phenolic composition of syrah red wines obtained by pre-fermentative cold maceration

The vinification technique called pre-fermentative cold maceration is used to enhance the anthocyans diffusion from the skins to the must, increasing the pigments extraction. For using this technique the application of low temperatures is needed. In this study, two different refrigerating methods (dry ice and cooling of grapes) have been assessed regarding the colour and the phenolic composition of the Syrah wines elaborated by applying pre-fermentative cold maceration. Results showed more intense and stable colours when grapes were previously refrigerated in cold-storage rooms, which showed higher values of chroma and more red-bluish hues. As regards phenolic composition, the cold maceration technique used yields to significant differences among the levels of phenolics, having higher levels of anthocyanins and some non-coloured phenols as flavonols in PR wines. Regarding the colour-composition relationships, it has been highlighted the importance of the co-pigments such as flavonols and cinnamic acids for classify the two groups of samples.     

Genomic information allows for more accurate breeding values for milkability in dual-purpose Italian Simmental cattle

Milkability is a trait related to the milking efficiency of an animal, and it is a component of the herd profitability. Due to its economic importance, milkability is currently included in the selection index of the Italian Simmental cattle breed with a weight of 7.5%. This lowly heritable trait is measured on a subjective scale from 1 to 3 (1 = slow, 3 = fast), and genetic evaluations are performed by pedigree-based BLUP. Genomic information is now available for some animals in the Italian Simmental population, and its inclusion in the genetic evaluation system could increase accuracy of breeding values and genetic progress for milkability. The aim of this study was to test the feasibility and advantages of having a genomic evaluation for this trait in the Italian Simmental population. Phenotypes were available for 131,308 cows. A total of 9,526 animals had genotypes for 42,152 loci; among the genotyped animals, 2,455 were cows with phenotypes, and the other were their relatives. The youngest cows with both phenotypes and genotypes (n = 900) were identified as selection candidates. Variance components and heritability were estimated using pedigree information, whereas genetic and genomic evaluations were carried out using BLUP and single-step genomic BLUP (ssGBLUP), respectively. In addition, a weighted ssGBLUP was assessed using genomic regions from a genome-wide association study. Evaluation models were validated using theoretical and realized accuracies. The estimated heritability for milkability was 0.12 ± 0.01. The mean theoretical accuracies for selection candidates were 0.43 ± 0.08 (BLUP) and 0.53 ± 0.06 (ssGBLUP). The mean realized accuracies based on linear regression statistics were 0.29 (BLUP) and 0.40 (ssGBLUP). No genomic regions were significantly associated with milkability, thus no improvements in accuracy were observed when using weighted ssGBLUP. Results indicated that genomic information could improve the accuracy of breeding values and increase genetic progress for milkability in Italian Simmental.     

Effects of the detailed protein composition of milk on curd yield and composition measured by model micro-cheese curd making of individual milk samples

The effect of the contents of casein (CN) and whey protein fractions on curd yield (CY) and composition was estimated using 964 individual milk samples. Contents of α_S1-CN, α_S2-CN, β-CN, γ-CN, glycosylated κ-CN (Gκ-CN), unglycosylated κ-CN, β-LG, and α-LA of individual milk samples were measured using reversed-phase HPLC. Curd yield and curd composition were measured by model micro-cheese curd making using 25 mL of milk. Dry matter CY (DMCY) was positively associated with all casein fractions but especially with α_S1-CN and β-CN. Curd moisture decreased at increasing β-CN content and increased at increasing γ-CN and Gκ-CN content. Due to their associations with moisture, Gκ-CN and β-CN were the fractions with the greatest effect on raw CY, which decreased by 0.66% per 1-standard deviation (SD) increase in the content of β-CN and increased by 0.62% per 1-SD increase in the content of Gκ-CN. The effects due to variation in percentages of the casein fractions in total casein were less marked than those exerted by contents. A 1-SD increase in β-CN percentage in casein (+3.8% in casein) exerted a slightly negative effect on DMCY (β = ?0.05%). Conversely, increasing amounts of α_S1-CN percentage were associated with a small increase in DMCY. Hence, results suggest that, at constant casein and whey protein contents in milk, the DMCY depends to a limited extent on the variation in the α_S1-CN:β-CN ratio. κ-Casein percentage did not affect DMCY, indicating that the positive relationship detected between the content of κ-CN and DMCY can be attributed to the increase in total casein resulting from the increased amount of κ-CN and not to variation in κ-CN relative content. However, milk with increased Gκ-CN percentage in κ-CN also shows increased raw CY and produces curds with increased moisture content. Curd yield increased at increasing content and relative proportion of β-LG in whey protein, but this is attributable to an improved capacity of the curd to retain water. Results obtained in this study support the hypothesis that, besides variation in total casein and whey protein contents, variation in protein composition might affect the cheese-making ability of milk, but this requires further studies.