Studies on peroxidized lipids. VI. Fluorescent products derived from the reaction of primary amines,malonaldehyde and monofunctional aldehydes

Monofunctional aldehydes such as acetaldehyde,n-propylaldehyde,n-butylaldehyde,n-hexylaldehyde,n-heptylaldehyde and benzaldehyde affected the reaction between primary amines and malonaldehyde. While the reaction of primary amines and malonaldehyde at pH 7 produced fluorescent 4-methyl-1,4-dihydropyridine-3,5-dicarbaldehydesIa-f, the reaction of the primary amines, malonaldehyde and the aldehydes listed above gave fluorescent 4-substituted 1,4-dihydropyridine-3,5-dicarbaldehydesIIa-j. The primary amines used for this reaction included alkylamines, amino acids and alkanolamines. The optimal ratio of the amine, malonaldehyde and the aldehyde was 1:2:1–2, at which compoundsII were produced quantitatively. Peroxidized lipids which may contain malonaldehyde and other aldehydes could react with the primary amines to produce highly fluorescentII. Fluorescence spectra ofII showed excitation maxima at 386–403 nm and emission maxima at 444–465 nm in phosphate similar to those ofI. The spectra of these 1,4-dihydropyridinesI andII were roughly similar to those of lipofuscin pigment, but they exhibited different characteristics in acid and alkaline media from those of lipofuscin pigment. CompoundsII may be useful as model compounds to elucidate the chemical structure of lipofuscin pigment.     

{beta}-sheet folding of fragment (16-36) of bovine pancreatic trypsin inhibitor as predicted by Monte Carlo simulated annealing

A tertiary structure prediction is described using Monte Carlosimulated annealing for the peptide fragment corresponding toresidues 16–36 of bovine pancreatic trypsin inhibitor(BPTI). The simulation starts with randomly chosen initial conformationsand is performed without imposing experimental constraints usingenergy functions given for generic interatomic interactions.Out of 20 simulation trials, seven conformations show a sheet-likestructure—two strands connected by a turn—althoughthis sheet-like structure is not as rigid as that observed innative BPTI. It is also shown that these conformations are mostlylooped and exhibit a native- like right-handed twist. Unlikethe case with the C-peptide of RNase A, no conspicuous -helicalstructure is found in any of the final conformations obtainedin the simulation. However, the lowest-energy conformation doesnot resemble exactly the native structure. This indicates thatthe rigid ß-sheet conformation of native BPTI merelycorresponds to a local minimum of the energy function if thefragment with residues 16–36 is isolated from the nativeprotein. A statistical analysis of all 20 final conformationssuggests that the tendency for the peptide segments to formextended ß-strands is strong for those with residues18–24, and moderate for those with residues 30–35.The segment of residues 25–29 does not tend to form anydefinite structure. In native BPTI, the former segments areinvolved in the ß-sheet and the latter in the turn.A folding scenario is also speculated from this analysis.     

Gastric carcinoma in young adults

Among 47 blood donors tested positive with HCV EIA 2.0 Abbott, 27 (57.4%) also reacted with four ?third-generation' EIAs. The presence of anti-HCV antibodies was confirmed with 3 different immunoblot assays in 16 of 27 sera (34.0%) while 10 samples (21.3%) had indeterminate profile with antibodies usually directed against structural core antigen. Anti-HCV core IgM response was found in 12 of 47 sera (25.5%) and HCV viremia detected by the polymerase chain reaction (PCR) procedure was observed in 15 samples (31.9%). A comparative study of the different markers confirmed a good correlation between a strong antibody response in EIAs and immunoblot assays and the presence of HCV RNA in the serum; only 2 immunoblot indeterminate samples were PCR positive. An association was observed between IgM antibodies against "core' epitopes and HCV RNA carriage: all IgM-positive sera were found positive by PCR. However, the direct detection of viral genome remains the best method for identifying HCV carriers in the blood donor population.     

Combined processing of polypropylene film by coextrusion and zone-annealing

In order to improve the mechanical properties of polypropylene film, a new processing combining extrusion and zone-annealing has been applied. It was found that there are suitable conditions for each step in the combined processing. When the coextrusion draw ratio was low, the total draw ratio and modulus could be increased by the zone-annealing subsequently done. The highest modulus was obtained when the film was coextruded at extrusion draw ratio 4 and then zone-annealed at 120°C under 7 kg/mm². The value was 12 GPa in Young's modulus or 17 GPa in dynamic modulus. The peak temperature of α_c dynamic dispersion for the combinedly processed film was 109°C, which is higher by 10°C than that for the as-coextruded film. Four drawing methods were compared in dynamic viscoelasticity. These methods are the coextrusion, zone-drawing/zone-annealing, two-step coextrusion, and the combined processing by coextrusion and zone-annealing. The highest dynamic modulus for each method was arranged in the above order. The combined processing indicated the most effective improvement in mechanical properties, because it is believed that lamellae in the original film were broken by cooperating interaction of shear stress, compression, and tension on coextrusion and then the superstructure with a high crystallinity and a high molecular orientation was formed on zone-annealing.     

Esterification of n‐butyric acid with n‐butyl alcohol and transesterification of (R, S)‐phenylethanol by lipase immobilized on cellulose acetate–TiO2 gel fibre

Lipase (EC 3.1.1.3) was immobilized on cellulose acetate–TiO₂ gel fibre by the sol–gel method. The immobilized lipases were used for esterification of n‐butyric acid with n‐butyl alcohol and enantioselective acylation of (R, S)‐phenylethanol using vinyl acetate as an acyl donor. Compared with native lipase, the activity of the immobilized lipase was stable and relatively unaffected by the water content of the solvent and the substrate concentration. The data indicate that the lipases are immobilized on the fibre surface and that enzyme activity is influenced by bound water. However, the thermal reactivity and enantioselectivity of the immobilized lipase were less than those of native lipase. This may not reflect thermal inactivation of the enzyme but rather significant thermal contraction of the gel fibre by cellulose crystallization, resulting in liberation of bound water and a decrease in the amount of enzyme which is available for the reaction. Copyright © 2001 Society of Chemical Industry     

Effect of surface structure of porous silica microballoons on dynamic mechanical properties of amine cured epoxy resin composites

Dynamic mechanical properties were studied for epoxy resin filled with porous silica microballoons with varying surface area, pore radius, pore volume and adsorbed water. The glass transition temperature (T_g) of the composites is 12–14°C lower than the T_g of the unfilled epoxy resin. This T_g depression is attributed to the preferential adsorption of curing agents on the porous silica microballoons. Tg of the composite increases with increase in the adsorbed water on fillers. The storage modulus has a distinct correlation with the Hg-surface area of silica microballoons, which corresponds to the sum of the surface area of pores with radii larger than about 4 nm. Tan δ_c tan δ_m decreases with increasing Hg-surface area.     

An electrochemical oxygen separator using an ion-exchange membrane as the electrolyte

An electrochemical oxygen separator based on oxygen reduction at an air cathode and oxygen evolution at an anode has been developed. The device features use of an ion-exchange membrane (Nafion 117) as the sole electrolyte and an air cathode mainly made of carbon.The anode was formed by chemically plating platinum (3.7 mgcm^–2) on one side of the Nafion 117 membrane. The air cathode was bonded to the other side of the membrane by spraying a slurry of graphitized furnace black loaded with platinum, followed by hot-pressing. The addition of a Nafion solution and a PTFE dispersion to the slurry was essential. The ultimate loading of platinum for the cathode was 0.2 mg cm^–2. An electrochemical oxygen separator with a working area of 100 cm² was constructed. When the separator was used as an oxygen concentrator it could be operated at 200 mA cm^–2 and produced 70.9 cm³ min^–1 of oxygen with a purity of 98.4%. When the separator was used as a circulation-type oxygen removal system it reduced the oxygen concentration of a 10-dm³ chamber to less than 0.02% within 70min. When the separator was used as a flow-through-type oxygen remover, air with an oxygen concentration of 0.02% was produced at 100 cm³ min^–1.     

Epoxy Networks Modified by a New Class of Oligomeric Silsesquioxanes Bearing Multiple Intramolecular Rings Formed through Si?O?C Bonds

Summary: A new class of silsesquioxane (SSO), containing species with two to nine Si atoms bearing multiple intramolecular rings formed through Si? O? C bonds, was synthesized as a glassy powder. It was characterized by UV‐MALDI‐TOF MS, ²⁹Si NMR and FT IR. Solutions containing different amounts of SSO in the diglycidyl ether of bisphenol A (DGEBA), were homopolymerized in the presence of (4‐dimethylamino)pyridine (DMAP) as initiator, leading to SSO‐modified epoxy networks. SSO species were covalently bonded to the epoxy network without any evidence of phase separation. The SSO addition provoked an increase in the elastic modulus in the glassy state explained by an increase in the cohesive energy density. The SSO addition gave also place to an increase in the intensity of tan δ and a decrease in both the glass transition temperature and the elastic modulus in the rubbery state. This was explained by a decrease in crosslink density associated with the flexibility of SSO structures. DMAP was much more effective than other usual initiators (like benzyldimethylamine, BDMA), in increasing the crosslink density of the resulting epoxy network. This led to high values of the glass transition temperature and the elastic modulus in the rubbery state.

Schematic representation of the chemical structure of the most significant species containing three Si atoms, present in the silsesquioxane.     

High‐performance polymer‐stabilized blue‐phase LCD with low driving voltage

We have developed a polymer‐stabilized blue‐phase LCD in which the diffraction wavelength of blue‐phase liquid crystal is in the ultraviolet region and which is driven at a low voltage of V₁₀₀ = 27 V. Prototypes of 3.4‐in polymer‐stabilized blue‐phase LCDs were made, which include a highly reliable crystalline oxide semiconductor. We succeeded in fabricating not a test cell but a display having a contrast ratio higher than 1000 : 1 for the first time in the world.