Photoinitiation of polymerization of styrene by oxotris(dimethyl dithiocarbamato) vanadium(V)

Oxotris(dimethyl dithiocarbamato) vanadium(V) [VO(S₂CN(CH₃)₂)₃] sensitizes the polymerization of styrene when irradiated by light of λ = 365 nm at 25°C. Under the experimental conditions employed, no retardation occurs, and the rate of initiation is independent of monomer concentration. The mean values of the quantum yield of iniiation (?_i) and polymerization (?_o) are 2.85 × 10^?3 and 6.72 respectively. Spectroscopic analysis shows that initiation occurs predominatly through scission of the N,N-dimethyl dithiocarbamate ligand (—SC(S)N(CH₃)₂) with reduction of vanadium(V) to (IV), and VO (S₂CN(CH₃)₂)₂ is the final photolytic product. A reaction mechanism is proposed based on an intramolecular photoredox reaction which leads to the primary formation of SC(S)N(CH₃)₂ radicals and a vanadium(IV) chelate complex. The rellevant kinetic parameters are evaluated. The polystyrene produced shows a photoactivity when irradiated with UV-light.     

Optimal linear approximation in project compression

When the cost of reducing the duration of activities is convex and nonlinear, it may be advisable (to reduce the computing burden) to seek a “satisficing” answer, in which the project is compressed to a desired completion time with a prespecified tolerable relative error. We treat the problem of constructing the optimal first degree interpolating linear spline that guarantees such maximal error and consider various possible refinements.     

X-ray absorption near-edge structure analysis of arsenic species for application to biological environmental samples

Arsenic is an element that is ubiquitous in the environment and is known to form compounds with toxic, even carcinogenic properties. Arsenic toxicity is a function of its chemical form (species). Identification of arsenic species is necessary to accurately determine the transformation and fate of arsenicals as well as the actual risk posed by arsenic contamination. We report X-ray absorption near-edge structure (XANES) measurements of 16 biologically important arsenic compounds. Solid and aqueous standards were studied for differences in XANES spectral features, white line positions, stability during exposure to the beam, and stability between two beam exposures separated by 48 h. Samples containing As(III) (11870.0-11871.7+/-0.5 eV) and As(V) (11872.6-11875.3+/-0.5 eV) were easily distinguished by white line energies and could be further subdivided into a total of seven groups. Valuable examples include As(III)-sulfur compounds (11870.0+/-0.5 eV), arsenobetaine and arsenocholine (11872.6+/-0.5 eV), and a dimethyl arsinyl riboside (11873.3+/-0.5 eV). A growing number of environmental and biological studies use X-ray absorption spectroscopy (XAS) results to complement their more traditional analyses. Results provided here are intended to help make XAS more accessible to new users interested in the study of arsenic in the environment.     

Detection of technical fraud in brickmaking by mineralogical analysis

X-ray diffraction analysis was utilized to investigate the mineralogical composition of red bricks as affected by the used raw materials. The data indicate that the bricks are composed of spinel, hematite, cristobalite, feldspars and quartz. The relative abundance of each of these minerals depends on the nature of the raw materials. Bricks made out of bentonite sediments contain more quar-tz and less feldspars compared with those made out of soil materials. It is suggested that the intensity ratio of quartz reflection at 3.34 Å to that of feldspars at 3.2 Å may be used to distinguish between bentonitic red bricks from those made out of soil materials. Therefore, the law which forbids using soil materials for brickmaking can be implemented on sound legal and technical grounds.     

Fatigue of cold worked ribbed reinforcing bar—a fracture mechanics approach

A theoretical method for the prediction of fatigue life of structural members containing external stress raisers has been developed. The method is based on a linear elastic fracture mechanics approach to fatigue. The theory has been applied to fatigue of Torbar steel in concrete beams. The required parameters for such application were obtained from fatigue tests on samples and finite element analysis of cracked bars. Comparisons between the theory and experimental data taken from other investigations have shown that the theory predicts a reasonable lower limit fatigue life of Torbar in concrete beams. The theory has also successfully predicted the effect of the minimum stress on the fatigue life of this type of bar.     

Fluorescence spectroscopy coupled with factorial discriminant analysis technique to identify sheep milk from different feeding systems

Rapid measurements of milk properties and discrimination of milk origin are necessary techniques for quality control of milk products. The present study was undertaken to evaluate the potential of using front face fluorescence spectroscopy (FFFS) and synchronous fluorescence spectroscopy (SFS) for monitoring the quality of forty-five ewe’s milk samples originating from different feeding systems. Physico-chemical analyses and fluorescence spectra were conducted on samples during lactation periods (the first 11 weeks). The principal component analysis (PCA) separately applied to the physico-chemical and fluorescence spectral data showed only small discrimination between milk samples based on lactation periods and diet compositions. Similar results were obtained by separately applying factorial discriminant analysis (FDA) on each technique. In a second step, concatenation technique were applied to FFF spectra acquired after excitation set at 250, 290, 380 nm and emission set at 410 nm. Results obtained showed a good discrimination among milk samples with regard to feeding systems given to the ewes throughout the lactation periods. In addition, a better discrimination was observed with FFFS than with SFS.     

Influence of Surface Topography on the Tribological Behaviour of Aluminium Alloy 5182 with EDT Surface

Friction is one of the most important parameters in sheet metal forming. Friction conditions are influenced by the texture of the sheet surface, by the surface or coating of the tools and by the lubrication. The aluminium alloy AA 5182 with EDT surface has been studied and tested at various angles between rolling and sliding direction. The friction behaviour observed in experiments at different normal pressures based on Coulomb’s friction law are shown and discussed in this article. Moreover, local surface topography and lubricant distribution in the contact area are described.     

Electrorheological behavior of low filled suspensions of highly anisometric montmorillonite particles

The electrorheological (ER) behavior of modified montmorillonite (MMT) suspensions in polydimethylsiloxane is studied. As established by rotational viscometry, the samples with a dispersed phase concentration from 1 to 8 wt % reveal viscous Newtonian behavior and dramatically change their properties to elastic when electric field is applied. The rheological characteristics of the suspensions over 0–7 kV mm⁻¹ range of electric field strengths are also studied. Novel X-ray diffraction method is developed to evaluate the suspension of the filler in a siloxane medium and to calculate the degree of its exfoliation. The dependence of exfoliation degree, dielectric, and ER characteristics on the type of modifier in the MMT structure is considered. Based on the obtained data, a new model of system behavior with the various types of fillers is proposed and the prospects of utilizing MMT as a filler for ER fluids are demonstrated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47678.     

Impact of simulated solar irradiation on disinfection byproduct precursors

The Sacramento-San Joaquin Delta is the major drinking water source for 23 million California residents. Consequently, many studies have examined disinfection byproduct (DBP) formation in relation to Delta dissolved organic carbon (DOC) concentration. However, DOC characteristics within the Delta are not the same as those entering downstream water treatment facilities. As water is transferred to Southern California through the California Aqueduct, a 714.5 km-open channel, it is exposed to sunlight, potentially altering DBP precursors. We collected water from three sites within the Delta and one nearthe California Aqueduct, representing different DOC sources, and irradiated them in a solar simulator at a dose equivalent to that received during four days conveyance in the aqueduct. Photolytic changes in DOC were assessed by measuring CO2 and organic acid production, fluorescence, and ultraviolet absorbance over time. Trihalomethane (THM) and haloacetic acid (HAA) formation potentials, as well as the distribution of hydrophobic, transphilic, and hydrophilic acid fractions were determined at exposures equivalent to one and four days. Solar irradiation significantly decreased ultraviolet absorbance and fluorescence intensity, produced organic acids, and increased the hydrophilic fraction of waters. These changes in DOC caused a shift in bromine incorporation among the THM and HAA species. Our results are the first to demonstrate the importance of sunlight in altering DOC with respect to DBP formation.     

The potential effect of FOS and inulin upon probiotic bacterium performance in curdled milk matrices

Inulin and fructooligosaccharides were studied for their prebiotic effect upon growth/survival of probiotic bacteria and technological potential in probiotic food processing, via characterization of glycolysis, proteolysis and lipolysis in curdled milk matrices; the ultimate goal is the manufacture of synbiotic cheeses. Prebiotic compounds did not significantly affect growth/viability of all strains studied, except Lactobacillus acidophilus La-5. Proteolysis indices revealed considerable casein degradation in probiotic and synbiotic matrices inoculated with Bifidobacterium lactis B94 and Lactobacillus casei-01; lower values were achieved in those inoculated with L. acidophilus La-5, yet a synbiotic effect was apparent in NPN values. Lipolysis was not extensive over storage, irrespective of matrix type; however, interesting differences in terms of the qualitative free fatty acids profile were observed. CLA isomers, and α-linolenic and γ−linolenic acids were detected upon 15 d of ripening of all inoculated matrices. Principal component analysis was able to discriminate the various matrices according to degree of maturation, throughout the ripening period. Microbiological and biochemical parameters unfolded a very good technological potential, especially of B. lactis B94 and L. casei-01, to produce novel types of functional dairy matrices - although extrapolation to actual cheeses should still be done with care, because e.g. syneresis was not considered.