Electrochemical hydrodehalogenation of polychloromethanes at silver and carbon electrodes

The reductive dehalogenation of CCl₄, CHCl₃, CH₂Cl₂ and CH₃Cl has been investigated by cyclic voltammetry and controlled-potential electrolysis at Ag, glassy carbon (GC) and graphite electrodes in dimethylformamide (DMF) + 0.1 M Et₄NClO₄ in the absence and presence of a proton donor. In particular, the study was focused in the evaluation of the intermediates and final products of the reduction process and how their distribution could be affected by tuning relevant chemical and electrochemical parameters. In general, depending on the value of the applied potential, all polychloromethanes (PCMs) can be partially or completely dechlorinated, methane being exclusively formed in the latter case. The nature of the electrode material and the proton availability of the medium affect drastically the distribution of reduction products. The results point out that at both types of electrode, reduction of PCMs takes place through two competing reaction pathways both leading to methane. One reaction route involves a sequence of reductive dehalogenation steps, with the removal of one chlorine atom at a time, whereas the other is based on hydrogenolysis of carbenes and bypasses the intermediacy of partially dechlorinated PCMs. The presence of a proton source affects substantially the hydrodehalogenation efficiency, enhancing the concentration of intermediate PCMs and the final yield of methane. The silver electrode exhibits an extraordinary electrocatalytic effect resulting in remarkable positive shifts of the reduction potentials of all PCMs with respect to GC. The Ag surface strongly affects the kinetics of the dissociative electron transfer to CH_nCl_(4−n) (n = 0–3) as well as the reactivity of the intermediate radicals, carbanions and carbenes.     

Capital-energy substitution in manufacturing for seven OECD countries: learning about potential effects of climate policy and peak oil

The simultaneous influence of increasing oil scarcity, greenhouse gas control and renewable energy targets will result in a future of sustained energy prices. Whether modern economies can find a smooth path away from fossil fuels is a fundamental socio-economic and political question, which according to standard economics depends to a large extent on the degree of substitution between energy and capital. We study this issue by modelling the manufacturing sector with a translog cost function in seven OECD countries using the EU-KLEMS database for the period 1970–2005. After a literature survey, different production structures accounting for input substitution, returns to scale and technical change are estimated, and substitution elasticities are derived. Our results indicate a general complementarity or weak substitution relationship between energy and capital, suggesting that an increase in energy price, e.g. due to climate policy or scarcer fossil fuels, will likely reduce capital inputs, which might lead to a lower output of manufacturing.     

GTV<Emphasis Type="SmallCaps">cut</Emphasis> for neuro-radiosurgery treatment planning: an MRI brain cancer seeded image segmentation method based on a cellular automata model

Despite of the development of advanced segmentation techniques, achieving accurate and reproducible gross tumor volume (GTV) segmentation results is still an important challenge in neuro-radiosurgery. Nowadays, magnetic resonance imaging (MRI) is the most prominent modality in radiation therapy for soft-tissue anatomical districts. Gamma Knife stereotactic neuro-radiosurgery is a minimally invasive technology for dealing with inaccessible or insufficiently treated tumors with traditional surgery or radiotherapy. During a treatment planning phase, the GTV is generally contoured by experienced neurosurgeons and radiation oncologists using fully manual segmentation procedures on MR images. Unfortunately, this operative methodology is definitely time-expensive and operator-dependent. Delineation result repeatability, in terms of both intra- and inter-operator reliability, can be achieved only by using computer-assisted approaches. In this paper a novel semi-automatic seeded image segmentation method, based on a cellular automata model, for MRI brain cancer detection and delineation is proposed. This approach, called GTVcut, employs an adaptive seed selection strategy and helps to segment the GTV, by identifying the target volume to be treated using the Gamma Knife device. The accuracy of GTVcut was evaluated on a dataset composed of 32 brain cancers, using both spatial overlap-based and distance-based metrics. The achieved experimental results are very reproducible, showing the effectiveness and the clinical feasibility of the proposed approach.     

Interactions between anthocyanins and organic food molecules in model systems

The interactions between different glucosidic anthocyanins (pelargonin, cyanin, delphinin, malvin and petunin) and some organic compounds (lactic, galacturonic, tannic, phenolic and sinapic acids; pyrogallol, furfural, pectin, cellulose, hydrolitic lignin) which are present in food‐stuffs were investigated at pH 3.0–4.3 and 25 °C. The interactions were monitored by means of u.v.‐VIS spectra and their different behaviours were highlighted by following changes in absorbance over a range of wavelengths (Δλ and ΔA). Significant effects on absorbance were detected and are discussed in terms of the phenomenon of co‐pigmentation.     

Colour-difference measurement: The sensitivity of various instruments compared

Because of the progress in electronic technology and the increasing importance of colour quality control in various branches of industry, over the last decades several colour-measuring instruments have been developed, each one with its own design features; the lack of standardization among them might be an obstacle to the spread of colour quality control as a means for product qualification. Colour-difference measurements taken with 11 different models of spectrophotometers [four with 45 (circumferential)/0 geometry and the others with diffuse geometry] were compared with the aim of analyzing their correlation and dispersion. In order to cover different colour-space regions, measurements were taken on test panels painted with four saturated basic hue (red, yellow, green, and blue) acrylic products gradually modified by adding white or black paint. Basic statistical analyses made on colour-difference values (ΔE*_ab, ΔL*, Δa*, and Δb*) resulted in a high correlation among the examined instruments, but a certain variability, particularly as far as certain hues are concerned.     

The pleistocene clastic deposits of the latium coast—Italy

Close to the present Latium coast, at Rio Torto, in the area between Pomezia and Ardea, about 35 km to the South of Rome, there are vast sandy deposits of continental and marine origin that may be associated with ancient coast lines. The extent and thickness of these deposits vary widely and are used as sources for extracting aggregate materials that are successfully used in preparing cement mortars. Field surveys and laboratory tests have helped identify these products as belonging to a paleogeographic environment and to define both their volume and their geographic location. The results obtained have allowed characterization of the sands from a technical point of view and to define their fields of utilization keeping account of their location and their mining availability.     

Synthesis,fluorescence emission spectra and chiroptical properties of copolymers of N-vinylcarbazole and optically active fumarates

Optically active (?)menthylethylfumarate (2) and (?)dimenthylfumarate (3) have been synthesised and free radically copolymerized with N-vinylcarbazole (1). Copolymers of (1) and (2) exhibit a strong tendency to alternation in agreement with earlier conclusions from studies of copolymerization of (1) with diethylfumarate. Surprisingly the much more hindered, but symmetrical fumarate, (3) yields copolymers which always have carbazole monomer contents in excess of the 1:1 alternating ratio. Chiroptical measurements indicate significant induced optical activity in the carbazole chromophores of all the copolymers obtained but, in accord with the predominance of alternating structures, there is no real evidence for any sequence-determined maximum in induced circular dichroism. Fluorescence emission spectra of all copolymer samples exhibit significant asymmetric broadening on the long wavelength (low energy) side of the normal carbazole monomeric emission. This broadening is exhibited even by poly (1-co-2) samples for which the monomer compositions strongly indicate alternating sequences and must, therefore, represent interaction between carbazole segments. Accordingly, and in contrast to widely held assumptions, it is concluded that excimer-like emission may be exhibited by alternating copolymers of N-vinylcarbazole. Further evidence for electronic interactions between non-nearest neighbour carbazole units is provided by u.v. absorption and ¹H-n.m.r. spectra of appropriate copolymers.     

Composition and stability of phytochemicals in five varieties of black soybeans (Glycine max)

Phytochemical compositions of five varieties of black soybeans (Glycine max) and their stabilities at room temperature, 4 and −80 °C over 14 months were determined by HPLC systems with electrochemical (ECD) and UV detectors. Polyphenol profiling was carried out by a liquid chromatography–electrospray ionisation-mass spectrometry (LC–ESI-MS) with orbitrap as a mass analyser in both positive and negative ion modes, and polyphenols in aglycone forms were quantified by HPLC–ECD. Five different varieties of black soybeans (G. max) contained 249–405 μg/g dry wt of γ-tocopherol and 6.76–14.98 μg/g dry wt of lutein. Major polyphenols in black soybeans (G. max) were daidzein (193–288 μg/g dry wt) and genistein (145–223 μg/g dry wt), mainly present as glucosides and acetyl glucosides. No significant decrease was found in total phenols of black soybeans (G. max) stored at room temperature, 4 or −80 °C for 14 months. On the other hand, lutein and γ-tocopherol degraded significantly within a month of storage at room temperature (p < 0.01), whereas they remained stable up to 6 months at 4 °C and up to 14 months at −80 °C. The current study indicates that black soybeans (G. max) are rich source of γ-tocopherol and phenols (isoflavones, flavonols, flavan-3-ols, proanthocyanidins and anthocyanin) and that the levels vary depending upon varieties. In addition, storage at low temperature is recommended to reduce the loss of fat-soluble phytochemicals in black soybeans (G. max) over an extended period of time.