Synthesis and characterization of polyethylene-like polyurethanes derived from long-chain, aliphatic α,ω-diols

Long-chain aliphatic α,ω-diols containing up to 32 consecutive methylene groups were synthesized by several methods and characterized. 1,22-Docosanediol HO-(CH₂)₂₂-OH and 1,32-dotriacontanediol HO-(CH₂)₃₂-OH both exhibited a solid-solid phase transition before melting. The α,ω-diols HO-(CH₂)_m-OH, where m=12, 22, or 32, were reacted in the melt with much shorter aliphatic α,ω-diisocyanates OCN-(CH₂)_n-NCO, where n=4, 6, 8, or 12, producing a series of linear, aliphatic, and increasingly polyethylene-like m,n-polyurethanes. Characterization (by DSC, TGA, and SAXS) of the m,n-polyurethane series showed that when the aliphatic segments were increased, and the hydrogen-bonding densities thus decreased, the polymers displayed physical and thermal properties (for example, solubility and melting temperature) typical of polyethylene.     

Identification of leek-moth and diamondback-moth frass volatiles that stimulate parasitoid,Diadromus pulchellus

Acrolepiopsis assectella andPlutella xylostella frass volatiles, trapped on Tenax GC, were examined by capillary gas chromatography. In both moths, the same three disulfides, dimethyl, dipropyl, and methyl propyl, were the most abundant substances, but in different proportions. The synthetic disulfides elicited the same behavioral response by the parasitoid,Diadromus pulchellus as frass. The plant origin of these substances is discussed.     

Sodium Coordination Environments in Silica Films

The local structure centered on sodium after diffusion in silica (Na-SiO₂ samples) has been determined by means of extended X-ray absorption fine structure (EXAFS) studies. The Na-SiO₂ samples are of particular interest because (i) their sodium content can be varied over a wide range of concentration and (ii) their local structure is representative of that of soda–silica glass. EXAFS analyses reveal the existence of a well-defined local structure involving oxygen, sodium, and silicon neighbors. The Na-O, Na-Na, and Na-Si bonds lengths, which amount to 0.23, 0.30, and 0.38 nm, respectively, do not depend on sodium concentration. This environment closely resembles that found in soda–silica glass. Moreover, it is compatible with the "target site" and "the site memory effect" suggested by recent theories of the ionic conductivity in oxide glasses.     

Surface plasmon resonance evaluation of various aminoglycoside-RNA hairpin interactions reveals low degree of selectivity

Aminoglycoside antibiotics, which are able to selectively bind to RNA, are considered to be an important lead in RNA-targeting drug discovery. In this study, surface plasmon resonance (SPR) was employed to explore the interaction of aminoglycosides with known tobramycin-binding RNA hairpins (aptamers) and an unrelated RNA hairpin. It was established that aminoglycosides have multiple interactions with RNA hairpins. Unexpectedly, the different hairpins showed comparable affinity for a set of related aminoglycosides. The observed absence of selectivity presents an extra hurdle in the discovery of novel aminoglycosides as specific drugs that target defined RNA hairpins.     

A preemptive bound for the Resource Constrained Project Scheduling Problem

The Resource Constrained Project Scheduling Problem is one of the most intensively investigated scheduling problems. It requires scheduling a set of interrelated activities, while considering precedence relationships, and limited renewable resources allocation. The objective is to minimize the project duration. We propose a new destructive lower bound for this challenging ${\mathcal {NP}}$ -hard problem. Starting from a previously suggested LP model, we propose several original valid inequalities that aim at tightening the model representation. These new inequalities are based on precedence constraints, incompatible activity subsets, and nonpreemption constraints. We present the results of an extensive computational study that was carried out on 2,040 benchmark instances of PSPLIB, with up to 120 activities, and that provide strong evidence that the new proposed lower bound exhibits an excellent performance. In particular, we report the improvement of the best known lower bounds of 5 instances.     

A new test for cleaning efficiency assessment of cleaners for hard surfaces

A new test was developed to assess the efficiency of no-wiping hard-surface cleaning. The test allows cleaner comparisons according to their ability to remove greasy soils. The chosen approach minimizes the mechanical forces applied while cleaning so that the interactions between a detergent solution and the soil to be removed can be characterized. For this, immersion cleaning was chosen, with coated stainless steel as substrate and pigmented oils as the model soil. Several parameters were studied in defined ranges using the Experimental Design method and systematic comparisons. The test shows high reliability on degreasing assessments and is there-fore especially suited to optimization of nonionic surfactant mixes. The originality of the test lies in the possibility of keeping a visual trace of the cleaned substrate appearance by imprinting it on a piece of paper. The validation of the test leads to corroboration of several practical observations. Temperature and agitation play a major role in cleaning efficiency. Detergent solution concentration is a more relevant parameter than pH. Sodium carbonate is shown to have a higher buffering effect than pentahydrated sodium metasilicate. The test is easy to set up, highly sensitive, and can be adapted to solve the problems encountered by formulators of detergent cleaners, such as screening the best ethoxylated fatty alcohol mix for better degreasing properties.     

Immunoregulatory functions of paf-acether. VI. Dual effect on human B cell proliferation

The role of paf-acether (paf), a phospholipid cytokine, in the modulation of human B cell function was investigated. Paf, from 1×10⁻⁵ M to 10⁻⁶ M, decreased B cell proliferation induced by both phorbol myristate acetate (PMA) and anti-IgM antibodies (anti-IgM Ab). By contrast, 1×10⁻⁷ M to 1×10⁻⁹ M paf enhanced PMA triggered, but not anti-IgM triggered B cell proliferation. B cell proliferation was modulated between 24 and 72 hr of culture indicating that the effect of paf did not merely reflect a shift in proliferation kinetics. Interestingly, paf also enhanced the spontaneous proliferation of a Burkitt lymphoma-derived B cell line, Raji, which suggests that paf can directly act on B cells. The modulatory effect of paf on peripheral blood B cells was independent of PMA concentration, yet the effect on Raji cells was dependent upon cell density. The data suggest that paf is a potent modulator of B cell function, and may be involved in the control of humoral immune response. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 1989.     

Study of the telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol. Application to the synthesis of a new macromonomer

The telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol initiated by 2,2′-azobisisobutyronitrile was first investigated at 70 °C and the influence of the type of solvent was studied. The results showed that well-defined telomers of DMAEMA could not be synthetized via telomerization of DMAEMA in water or water/acetonitrile mixture since the telomerization reaction is in competition with the nucleophilic addition of thiol onto the monomer. Transfer constants for mercaptoethanol in benzene and acetonitrile were determined by Mayo's and O'Brien's methods. The transfer constant obtained in acetonitrile (0,6) was higher than that obtained in benzene. This difference can be explained by the fact that the thiol was consumed by two reactions: nucleophilic addition and telomerization. The influence of solvents on the polymerization kinetics was enlightened. These results were applied to the synthesis of macromonomers of DMAEMA with isocyanatoethyl methacrylate (IEM). These macromonomers were copolymerized with styrene.     

A STUDY OF SILICONE OIL-IN-WATER EMULSIONS

Emulsions of silicone oil-in water were formed using a Brinkmann Polytron homogenizer with Igepal CO-530 as an emulsifier. Silicone viscosities ranged from 10 to 33,000 mPa.s at 25°C. Rheological characteristics and particle size analyses of silicone oil-in-water emulsions were studied. At high volume fraction of the dispersed phase (70%-75%), silicone oil-in-water emulsions were stable. At lower volume fractions (50%-60%), emulsions formed were less stable and the two phases easily separated in a few days. The emulsions formed with high volume fraction silicone oil show highly non-Newtonian behavior (shear thinning). Emulsions made with low viscosity oils had lower viscosities than those made from high viscosity oils. Relative viscosity-concentration data could be correlated by the Frankel and Acrivos Equation. Increasing the emulsifier concentration of 70% oil-in-water emulsions resulted in a decrease in mean droplet size and an increase in emulsion viscosity. Increasing the intensity of agitation also resulted in higher viscosity and smaller droplet size until a critical energy input above which droplet size increased. Emulsification with low shear mixing provides more control in decreasing mean droplet size with time.     

A bi‐objective approach to reschedule new jobs in a one machine model

We consider a one machine scheduling model, minimizing a classical objective function—either the total completion time or the maximum tardiness—and with two sets of jobs: one with initial jobs already scheduled and one with new jobs that must be inserted in the schedule. As such rescheduling can create a modification of the schedule of the initial jobs, a disruption objective is considered in addition to the original objective. This additional objective can be formulated in four different ways. Such model has been introduced by Hall and Potts, minimizing either a linear aggregation of the two objectives or the initial objective under a constraint giving an upper limit of the disruption objective. In this paper, the aim is to obtain the set of efficient schedules in regard to the two objectives. Algorithms are provided for the eight possible bi‐objective problems and illustrated by some didactic examples.