Carbosilane Metallodendrimers with Cyclopentadienyldichlorotitanium(IV) End Groups

Dendritic polyols of the second and third generation 2G-OH₈ (1), 2G-OH₁₆ (2), and 3G-OH₁₆ (3) were prepared by hydroboration/oxidation of allyl-terminated carbosilane dendrimers and used as supports for the immobilization of cyclopentadienyltrichlorotitanium(IV) complexes via alcoholysis. The reaction of 1–3 with CpTiCl₃ gave metallodendrimers 2G-(OTiCpCl₂)₈ (4a), 2G-(OTiCpCl₂)₁₆ (5a), and 3G-(OTiCpCl₂)₁₆ (6a), respectively, whereas the reaction of 1 and 3 with CpSi^FTiCl₃ (CpSi^F = C₅H₄SiMe₂CH₂CH₂C₈F₁₇) yielded peripherally fluorinated metallodendrimers 2G-(OTiCpSi^FCl₂)₈ (4b) and 3G-(OTiCpSi^FCl₂)₁₆ (6b). All metallodendrimers were characterized by multinuclear NMR spectroscopy. The suggested structures were supported by comparison with model 1-propoxycomplexes 10a,b. To identify side products of the alcoholysis reaction, hydrolytic behavior of the starting trichloro complexes was studied both in solid state and in solution. The main products of hydrolysis in solution were identified as μ-oxocomplexes 8a,b whereas hydrolysis in solid state yielded mainly hydroxycomplexes 7a,b.     

Control of antioxidant beer activity by the mashing process

Beer is considered to be a good source of antioxidants. The composition and the quantity of the antioxidant compounds depend not only on the qualities of the raw materials, but also on the technology processes. Barley and malt represent the main source of antioxidant compounds in beer and the contribution of the hop antioxidants is lower. The influence of the mashing process on the antioxidant activity and polyphenol concentration is crucial. The antioxidant state of the sweet wort and the hopped wort are dependent on the technology processes and the raw materials used. The spontaneous sorption of polyphenols onto wort dregs and the polymerization of catechin and epicatechin lead to decreasing concentrations of individual polyphenols in the final beer. Two methods, based on electron spin resonance were used to determine antioxidant activity. These were the DPPH (2,2‐diphenyl‐1‐picryl‐hydrazyl) assay and the ‘lag time’ assay using free radical spin‐trapping agent PBN (N‐tert‐butyl‐α‐phenylnitrone). HPLC with CoulArray detection was used to measure the concentration of the individual polyphenols. This study focused on the antioxidant compounds and on the correlation of their concentrations with the values of total antioxidant activity depending on the mashing process. A good correlation was found between the decline in the concentrations of DPPH (expressed as ARA2) and concentrations of catechin and epicatechin (in sweet wort samples R² = 0.970, R² = 0.961, respectively, and in hopped wort samples R² = 0.949, R² = 0.956 respectively). Copyright © 2012 The Institute of Brewing & Distilling     

Antioxidant and cell growth activities of beet root pomace extracts

Beetroot (Beta vulgaris) pomace, processing by-product from food industry, was investigated in this work as a starting raw material. The contents of phenolics (1.87–11.98 mg GAE/g of dry weight) and betalains (0.75–3.75 mg betalains/g of dry weight) in the extracts were determinated spectrophotometrically. Some individual phenolic compounds, including ferulic, vanillic, p-hydroxybenzoic, caffeic and protocatehuic acids, were identified and quantified by HPLC. The antioxidative activity of beetroot extracts was tested using DPPH, hydroxyl and superoxide anion radicals by ESR spectroscopy. ${\text{IC}}_{50}^{{}^{\text{<mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/rad"></mglyph>}}\text{OH}}$ (0.05–0.108 mg/ml), $\text{IC}{50}^{{\text{DPPH}}^{\text{<mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/rad"></mglyph>}}}$ (0.183–0.333 mg/ml), and ${\text{IC}}_{50}^{{\text{O}}_2^{\text{<mglyph src="https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/16/entities/rad"></mglyph>}-}}$ (0.198–1.000 mg/ml) were calculated. The regression analysis produced moderate to high correlation coefficients between the scavenging activities and phenolics, and some individual phenolic compounds which indicated that beetroot pomace may be used as functional food ingredient. Cell growth effects were determined in MCF7 and MRC-5 cell lines, using SRB assay. IC₅₀ values were in the range of 362.478–503.525 and 383–587.880 μg/ml in MRC-5 and MCF7, respectively.     

Determination of Total Carbohydrate Content in Beer Using Its Pre-column Enzymatic Cleavage and HPLC-RI

Beside ethanol, carbohydrates are the main source of total energy in beer. While analyses of fermentable carbohydrates are important from the technological point of view, the total content of carbohydrates is relevant in terms of nutrition. A high-performance liquid chromatography (HPLC) method with refractometric (RI) detection was developed for determination of total carbohydrate content in beer. Using enzymatic reaction with amyloglucosidase, the carbohydrates were cleaved to yield glucose and short glucose oligomers of less than 10 units, and separated on HPLC ion exchanger Rezex RSO-Oligosaccharide column in Ag⁺ mode. Optimum parameters were established for the enzymatic sample treatment and for the HPLC separation of reaction products. Calibration curves of glucose, fructose, maltose and simultaneously analyzed glycerol ranged from 0.001 to 0.5 g/100 ml, correlation coefficients of all calibration curves were 0.9999. The instrumental limits of quantification were 0.001 g/100 ml and they were verified using repetitive injections, with coefficient of variation (CV) less than 10 % in five replicates. The method limit of quantification was 0.01 g/100 ml since it was necessary to dilute the beer samples before chromatographic analysis. Recovery of the method in non-alcoholic and alcoholic beer was 98.5 %, and 92.3 %, respectively. Finally, ten non-alcoholic and 15 alcoholic beers from Czech market were analyzed using the method, the average content of total carbohydrates in non-alcoholic and alcoholic beers being 4.21 and 3.70 g/100 ml, respectively. These results are in a good correlation with the real extract of beer, which is on average 4.58 and 4.27 g/100 ml.     

ALIPHATIC C-H BOND RESPONSES IN THE 900-700 cm−1 REGION OF THE FTIR SPECTRA OF COAL TARS

ABSTRACT

Four bituminous coals were comprehensively separated by column chromatography into a number of fractions. Four aromatic hydrocarbon fractions of each tar were analyzed by FTIR spectroscopy, and the 900-700 cm^?1 spectral region was evaluated. This spectral region was found to be composed of at least 14 separate bands, which were resolved by using self-deconvolution and curve-fitting procedures. The bands near 821 cm^?1, 791 cm^?1, and 784 cm^?1 were proposed to originate from rocking vibrations of aliphatic C-H bonds. For the tar samples with a proton aromaticity between 0.21 and 0.37, these bands account for on average 12% of the total integral intensity of the 900-700 cm^?1 region. This percentage cannot likely be neglected in a correct quantitative evaluation of the region and calculation of the aromatic hydrogen concentration. However, a correct resolution of the bands can be very difficult in the FTIR spectra of a complex material, such as coal.     

Very low energy electron microscopy of graphene flakes

Commercially available graphene samples are examined by Raman spectroscopy and very low energy scanning transmission electron microscopy. Limited lateral resolution of Raman spectroscopy may produce a Raman spectrum corresponding to a single graphene layer even for flakes that can be identified by very low energy electron microscopy as an aggregate of smaller flakes of various thicknesses. In addition to diagnostics of graphene samples at larger dimensions, their electron transmittance can also be measured at very low energies.     

A statistical model for the estimation of natural gas consumption

In this paper we present a statistical approach to natural gas consumption estimation of individual residential and small commercial customers. The approach is based on nonlinear regression principles. Parameters are estimated using mainly two real data sets – ordinary (approximately annual) meter readings of almost all customers and additional (approximately monthly) meter readings designed and operated within the frame of cooperation between the Institute of Computer Science of the Czech Academy of Sciences (ICS) and the West Bohemian Gas Distribution Company, a part of the RWE Group (WBG). The model was tested on various data sets. It has broad applicability in many areas of gas industry.     

Thermal stability of magnetron sputtered Si–B–C–N materials at temperatures up to 1700 °C

Thermal stability of deposited Si–B–C–N materials (film fragments or powders without a substrate) in inert gases (He and Ar) up to 1700 °C was investigated using differential scanning calorimetry, high-resolution thermogravimetry and X-ray diffraction measurements. Amorphous Si–B–C–N films were fabricated by dc magnetron co-sputtering of a single B₄C–Si target in two nitrogen–argon gas mixtures (50% N₂ + 50% Ar or 25% N₂ + 75% Ar). It was found that the deposited Si–B–C–N materials can be more stable at high temperatures in the inert atmosphere than the usually used substrates (e.g. SiC or BN). The materials with the compositions (in at.%) Si_32–33B₁₀C₂N_50–51, for which N/(Si + B + C) = 1.1–1.2, retained their amorphous structure up to 1600 °C without any structural transformations and detectable mass changes.     

Digital spectrometer for coincidence measurement of Doppler broadening of positron annihilation radiation

High-resolution digital coincidence Doppler broadening spectrometer equipped with two high-purity Ge detectors and two-channel 12-bit fast digitizer was developed and tested in this work. Two configurations were compared: (i) semi-digital setup which uses active analogue shaping of detector pulses prior to digitization to improve signal-to-noise ratio, and (ii) pure-digital setup which samples detector pulses directly. Software procedure developed for analysis of sampled waveforms, i.e. precise determination of energy of detected photon and rejection of distorted pulses, is described. Performance of digital coincidence spectrometer was compared with traditional analogue setup connected to the same detectors. It was found that digital spectrometer enables to achieve better energy resolution than in traditional analogue setup. Moreover, in digital configuration one has better control over shape of the signal. This allows efficient elimination of undesired distorted or damaged waveforms and to obtain spectrum of better clarity. The superior parameters of new digital coincidence Doppler broadening spectrometer are demonstrated by benchmark measurements of well defined Fe and Al specimens and also by the detection of rare annihilation in flight events.     

Binary oxide ceramics for enhanced phenols degradation under simulated Solar light

Solvothermal synthesis of ZrO₂–TiO₂ binary oxides and pure counterparts at 150°C in water/isopropanol media is presented. Titanium (IV) isopropoxide and zirconium (IV) propoxide were used as precursors. XRD and TEM techniques were used for structural and morphological characterization of obtained samples. XPS spectra of mixed oxide samples were compared in order to correlate composition of samples with surface properties and presence of defects. Relative positions of defect states within band‐gaps of semiconductors were estimated from UCPL spectra. UV‐Vis DRS spectra revealed that both pure oxides experienced red shift of absorption thresholds compared to reference data. Photocatalytic activities of all samples were probed under simulated Solar light on three model compounds: phenol, 4‐chlorophenol (4‐CP) and 2, 4, 6‐trichlorphenol (TCP). Pure TiO₂ showed the highest photocatalytic activity in the case of phenol. However, pure ZrO₂ and binary oxides showed higher photoactivity in degradation of 4‐CP and TCP. The activity of wide band‐gap semiconductors under simulated Solar light in photodegradation of phenol and its derivatives is most probably the consequence of formation of charge transfer complexes between pollutant molecules and semiconductors surface.