Vacuum-u.v. circular dichroism of optically active isotactic poly-α-olefins

Summary Circular dichroism of isotactic samples of poly-(S)-4-methyl-1-hexene and poly-(R)-3,7-dimethyl-1-octene, have been measured in the vacuum ultraviolet spectral region (200-140 nm). The c.d. band at about 160. nm accounts for the optical activity in the visible region and reflects the presence of one screw sense helical conformation of the sample examined.The authors thank Prof. W.C. Johnson, Jr., Department of Biochemistry and Biophysics, Oregon State University, for allowing them to use the vacuum u.v. spectrometer. This work has been partially supported by a N.A.T.O. grant, and by Ministero Pubblica Istruzione (MPI), Roma — Italy.     

Synthesis and Evaluation of Voltage-Gated Sodium Channel Blocking Pyrroline Derivatives Endowed with Both Antiarrhythmic and Antioxidant Activities

Under the hypothesis that cardioprotective agents might benefit from synergism between antiarrhythmic activity and antioxidant properties, a small series of mexiletine analogues were coupled with the 2,2,5,5-tetramethylpyrroline moiety, known for its antioxidant effect, in order to obtain dual-acting drugs potentially useful in the protection of the heart against post-ischemic reperfusion injury. The pyrroline derivatives reported herein were found to be more potent as antiarrhythmic agents than mexiletine and displayed antioxidant activity. The most interesting tetramethylpyrroline congener, a tert-butyl-substituted analogue, was at least 100 times more active as an antiarrhythmic than mexiletine.     

Nanoconfined mixed Li and Mg borohydrides as materials for solid state hydrogen storage

Several mixtures of LiBH₄ and Mg(BH₄)₂ borohydrides in different stoichiometric ratios (1:0, 2:1, 1:1, 1:2, 0:1), prepared by high energy ball milling, have been investigated with X-ray powder diffraction and thermal programmed desorption (TPD) volumetric analysis to test the dehydrogenation kinetics in correlation with the physical mixture composition. Afterwards mixed and unmixed borohydrides were dispersed on high specific surface area ball milled graphite by means of the solvent infiltration technique. BET and statistical thickness methods were used to characterize the support surface properties, and SEM micrographs gave a better understanding of the preparation techniques. It has been observed by TPD volumetric measurements that the confinement of the reactive borohydrides on the nanoporous supports leads to a lower dehydrogenation temperature compared to unsupported borohydrides. Moreover, a further decrease of the dehydrogenation temperature has been observed by increasing the specific surface area of the support and the pores volume and by using the prepared mixtures instead of pure materials. The dehydrogenation process seems to be favoured by the heterogeneous nucleation on the graphite surface of decomposition products or intermediate phases from melted liquid borohydrides.     

The most dangerous flaw orientation in brittle materials and structures

In the present paper a sheet of material is considered. It is loaded by uniaxial tensile stress and contains a random distribution of flaw orientations, with the flaws thought of as flat pre-cracks of comparable length, and with all crack planes being oriented perpendicular to the faces of the sheet. Intuition suggests that the most likely flaw to initiate fracture, which will be termed the “most dangerous defect”, lies orthogonally to the major load axis. The purpose of the present paper is to show that such an assumption is incorrect. Neither the most dangerous defect nor the first increments of crack growth will be oriented perpendicularly to the stress direction (nor will they be co-planar with the orientation of the most critical flaw).     

Reversible Fragmentation and Self‐Assembling of Nematic Liquid Crystal Droplets on Functionalized Pyroelectric Substrates

Investigation on the behavior of nematic liquid crystals on functionalized polar dielectric crystal substrates is accomplished. Very interesting effects can be observed in maneuvering liquid crystal droplets on the substrate surface, driven by electric fields generated by pyroelectric effect. Reversible drops fragmentation and self‐assembling in different configurations can be achieved. The dynamics of the observed phenomena is studied and the repeatability of the process is full assessed.     

Ultrafine,fine, and black carbon particle concentrations in California child‐care facilities

Although many U.S. children spend time in child care, little information exists on exposures to airborne particulate matter (PM) in this environment, even though PM may be associated with asthma and other respiratory illness, which is a key concern for young children. To address this data gap, we measured ultrafine particles (UFP), PM_2.5, PM₁₀, and black carbon in 40 California child‐care facilities and examined associations with potential determinants. We also tested a low‐cost optical particle measuring device (Dylos monitor). Median (interquartile range) concentrations for indoor UFP, gravimetric PM_2.5, real‐time PM_2.5, gravimetric PM₁₀, and black carbon over the course of a child‐care day were 14 000 (11 000‐29 000) particles/cm³, 15 (9.6‐21) μg/m³, 15 (11‐23) μg/m³, 48 (33‐73) μg/m³, and 0.43 (0.25‐0.65) ng/m³, respectively. Indoor black carbon concentrations were inversely associated with air exchange rate (Spearman's rho = ?.36) and positively associated with the sum of all Gaussian‐adjusted traffic volume within a one‐kilometer radius (Spearman's rho = .45) (P‐values <.05). Finally, the Dylos may be a valid low‐cost alternative to monitor PM levels indoors in future studies. Overall, results indicate the need for additional studies examining particle levels, potential health risks, and mitigation strategies in child‐care facilities.     

Model-based multi-objective optimization of beef roasting

A validated mathematical model has been used to perform multi-objective optimization of beef roasting, considering the minimization of both cooking time and weight loss. Simulations were performed using irregular geometrics models of beef semitendinosus muscle and constant oven temperature. Minimum temperature of 72 °C at the coldest point was imposed as a constraint. From model results a compromise situation was encountered, since no operative condition lead simultaneously to optimal values of both objectives, i.e., an increase in oven temperature leads to a decrease in cooking time, between −0.25 and −0.325 min/°C, and an increase in weight loss, between 0.175 and 0.275%/°C. In this sense, not one, but a set of optimal solutions was found in the Pareto sense. Experimental cooking tests were performed, which are in good agreement with model simulations. Furthermore, energy consumption for each optimal solution obtained in the optimization problem was estimated, being lower using low oven temperatures.     

Piperazine and methyldiethanolamine interrelationships in CO2 absorption by aqueous amine mixtures. Part II—Saturation rates of mixed reagent solutions

This work is a companion to a previous article, Part I, published in The Canadian Journal of Chemical Engineering, dealing with CO₂ absorption in aqueous solutions containing a single aminic reagent (specifically methyldiethanolamine (MDEA) or piperazine (PZ)). In this second part, different PZ/MDEA mixtures are experimentally studied and their performances are compared with that of the single reagents. It is indeed well known that small quantities of PZ added to MDEA aqueous solutions are sufficient to obtain a significant improvement in the kinetics of the process. PZ is considered an activator or promoter for MDEA, but the mechanism of this synergy has still not been clearly demonstrated. The aim of this study is an attempt to understand how PZ and MDEA can interact by experimentally analyzing this beneficial mutual effect and by explaining it with the help of a suitable yet not complex model. We believe that the involved chemistry is not more complex than that reported in Part I for the single reagents. According to our findings, it is MDEA that enhances the action of PZ, as opposed to what many authors claim. Moreover, our results seem to rule out the existence of any PZ shuttle effect.     

Catalytic olefin polymerisation at short times: Studies using specially adapted reactors

Despite the fact that the very early stages (several tens of seconds) of catalysed olefin polymerisation processes appear negligibly short with respect to the residence time of most industrial reactors, they are critical in terms of catalyst activation, obtaining good particle morphology, and avoiding irreparable problems caused by particle overheating. The different types of reactors that have been used over the course of the past few years are discussed in this feature article. It is shown that despite the difficulties encountered in finding the perfect experimental tool for this purpose, different configurations of stopped flow reactors can be used successfully to explore different aspects of what happens to the catalyst (supported and molecular) during these critical moments of polymerisation. © 2012 Canadian Society for Chemical Engineering