Curing of epoxy resins with amines

Summary Using determination of the critical molar ratio of functional groups necessary for gel formation with amino groups in excess, network formation was investigated in the reaction of diglycidyl ether of Bisphenol A (DGEBA) and nitrogen-containing epoxy resins — diglycidylaniline and N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane with aromatic or aliphatic amines. It was found that in the case of nitrogen-containing epoxides the crosslinking is accompanied by pronounced cyclization, unlike in systems with DGEBA. Gelation depends on the relative reactivity of the primary and secondary hydrogen atom of the amino group. In the case of nitrogen-containing polyepoxides, the dependence of reactivities of adjacent glycidyl groups is also operative.     

Hydrolysis of fish oils containing polymers of triacylglycerols by pancreatic lipasein vitro

Fish oils containing different levels of polymers of triacylglycerols formed during autoxidation were incubated with pancreatic lipase to establish whether these polymers are substrates for lipase hydrolysis. With oils containing low amounts (less than 4%) of triacylglycerol polymers as substrates, both triacylglycerols and polymers of triacylglycerols were almost completely hydrolyzed, and fatty acid monomers and monoacylglycerols were the major lipid products. Under the same incubation conditions, some triacylglycerols remained intact when highly oxidized oils containing 20 or 30% triacylglycerol polymers were the substrate. The fatty acid composition of these residual triacylglycerols was almost identical to that of triacylglycerols present at the start of the assay. When fish oil containing 30% triacylglycerol polymers was incubated with the lipase, the component triacylglycerols and polymers of triacylglycerols were hydrolyzed at similar rates, and fatty acid dimers were detected as a product. It is concluded that the high molecular weight polymers of triacylglycerols present in oxidized fish oils can be hydrolyzed by pancreatic lipasein vitro.     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Functional and chemical characterization of the aging process of an igniter

The igniter consisting of 34% Mg, 60% KNO₃, 3% KClO₄ and 3% organic binder was subjected to accelerated aging under the conditions of 85% relative humidity at 65°C, 75°C and 85°C, and at 75°C with 92% relative humidity. Chemical aging was followed through formation of Mg(OH)₂ and KNO₂. Functional characterization was accomplished in a device constructed to enable simultaneous determination of the heat of combustion and pressure-time recording of the combustion process of both fresh and aged samples. The maximum acceptable deterioration occured at different times depending upon the conditions. The acceleration factor for every 10°C at 85% relative humidity is on average 2.8, leading to a prediction of shelf life of not more than 4 years at 25°C. At the time when burning characteristics were significantly changed, the mixture suffered only slight chemical changes, with only about 1% Mg(OH)₂ and 0.5% KNO₂ being formed. Thus, no chemical changes should be tolerated in such formulations.     

Multivalent Interactions between an Aromatic Helical Foldamer and a DNA G‐Quadruplex in the Solid State

Quinoline‐based oligoamide foldamers have been identified as a potent class of ligands for G‐quadruplex DNA. Their helical structure is thought to target G‐quadruplex loops or grooves and not G‐tetrads. We report a co‐crystal structure of the antiparallel hairpin dimeric DNA G‐quadruplex (G₄T₄G₄)₂ with tetramer 1 —a helically folded oligo‐quinolinecarboxamide bearing cationic side chains—that is consistent with this hypothesis. Multivalent foldamer–DNA interactions that modify the packing of (G₄T₄G₄)₂ in the solid state are observed.     

Increased HDL Size and Enhanced Apo A-I Catabolic Rates Are Associated With Doxorubicin-Induced Proteinuria in New Zealand White Rabbits

The catabolism and structure of high‐density lipoproteins (HDL) may be the determining factor of their atheroprotective properties. To better understand the role of the kidney in HDL catabolism, here we characterized HDL subclasses and the catabolic rates of apo A‐I in a rabbit model of proteinuria. Proteinuria was induced by intravenous administration of doxorubicin in New Zealand white rabbits (n = 10). HDL size and HDL subclass lipids were assessed by electrophoresis of the isolated lipoproteins. The catabolic rate of HDL‐apo A‐I was evaluated by exogenous radiolabelling with iodine‐131. Doxorubicin induced significant proteinuria after 4 weeks (4.47 ± 0.55 vs. 0.30 ± 0.02 g/L of protein in urine, P < 0.001) associated with increased uremia, creatininemia, and cardiotoxicity. Large HDL2b augmented significantly during proteinuria, whereas small HDL3b and HDL3c decreased compared to basal conditions. HDL2b, HDL2a, and HDL3a subclasses were enriched with triacylglycerols in proteinuric animals as determined by the triacylglycerol‐to‐phospholipid ratio; the cholesterol content in HDL subclasses remained unchanged. The fractional catabolic rate (FCR) of [¹³¹I]‐apo A‐I in the proteinuric rabbits was faster (FCR = 0.036 h^?1) compared to control rabbits group (FCR = 0.026 h^?1, P < 0.05). Apo E increased and apo A‐I decreased in HDL, whereas PON‐1 activity increased in proteinuric rabbits. Proteinuria was associated with an increased number of large HDL2b particles and a decreased number of small HDL3b and 3c. Proteinuria was also connected to an alteration in HDL subclass lipids, apolipoprotein content of HDL, high paraoxonase‐1 activity, and a rise in the fractional catabolic rate of the [¹³¹I]‐apo A‐I.     

The preparation and properties of zinc coordination complexes of poly(4-vinylpyridine-co-n-butyl methacrylate) copolymers

Two poly(4-vinylpyridine-co-n-butyl methacrylate) copolymers containing 14.2 and 30.0 mol% of 4-vinylpyridine residues were prepared by free radical copolymerization reactions. Insoluble complexes were obtained for each copolymer by reaction with zinc chloride. The coordination complexes obtained had a molar ratio of 4-vinylpyridine residues to zinc atoms close to 2 in both cases. The rheological behavior of each of these complexes has been compared to that of the corresponding metal-free copolymers, which were recovered by decomplexation. The metal complexed polymers exhibited much higher glass transition temperatures and much longer high temperature relaxation times than the corresponding uncomplexed copolymers.     

Hardened portland cement pastes of low porosity VI. Mechanism of the hydration process

The hydration of low-porosity portland cement pastes may be divided into three stages. The first stage starts with a fast hydration until 10 to 15% of the cement is hydrated (pre-dormant period), which is followed by a very slow hydration, caused by the formation of a coating on the cement grains (dormant period). After 15 to 20% of the cement is hydrated, the coating is ruptured, and a fast reaction starts, which lasts until about 30% of the cement is hydrated. This is the second stage of the reaction. In the third stage, the hydration slows down, due to retardation by the accumulating hydration products. The mechanism of the third stage is treated quantitatively. The diffusion through the very narrow pores between the hydration products is activated diffusion, and the apparent energy of activation of the diffusion is calculated.