Synthesis of geranyl acetate by lipase entrap-immobilized in cellulose acetate-TiO2 gel fiber

Lipase from Candida antarctica was entrap-immobilized in cellulose acetate-TiO₂ gel fiber (fiber-immobilized lipase) by the sol-gel method. Syntheses of geranyl acetate and citronellyl acetate catalyzed by the fiber-immobilized lipase were studied in heptane solution. Conversions reached 85% for geranyl acetate after 100 h, and 75% for citronellyl acetate after 80 h, and these values were almost identical to those for syntheses catalyzed by nonimmobilized lipase, although the reaction rate was decreased by immobilization. Compared to those of the non-immobilized lipase and commercially available immobilized lipase (Novozyme 435), the activity of the fiber-immobilized lipase was not particularly affected by changes in reaction conditions, such as bulk water content or substrate concentration. The fiber-immobilized lipase retained a high level of activity after six repeated uses, and almost no enzyme leakage from fiber was observed. However, the reactivity of the fiber-immobilized lipase was depressed at higher temperature, presumably due to dehydration by thermal contraction of the gel fiber.     

Electromyography of Eating Apples: Influences of Cooking, Cutting, and Peeling

ABSTRACT: The mastication of 7 differently prepared apple samples (raw pieces peeled and unpeeled, sliced, grated, cooked pieces with and without peel, and half-cooked pieces, 10 g each) was evaluated using electromyography (EMG). Eleven subjects participated in the EMG recording of both sides of the masseter and temporal muscles while eating samples normally. Only the grated sample reduced the number of chewing strokes and muscle activity before swallowing. In contrast, the thin apple slices produced significantly shorter contraction duration and cycle time only during the 1st 5 chewing strokes. The EMG duration and cycle in subsequent chews, as well as the other parameters, did not significantly differ between slices and pieces. Cooked apples exhibited significantly lower EMG amplitude and muscle activity per chew than their raw counterparts; however, there was no evidence of reduced total muscle activity required for swallowing. Raw and cooked apples with peel yielded significantly greater EMG amplitude and longer duration than those without peel. These findings suggest that appropriate preparation is necessary for people with various mastication abilities: grated for very low ability, cooked for those with weak chewing force, and unpeeled for mastication training.     

To Separate a Particular Ln(III) Selectively Using Solvent Extraction

ABSTRACT

Since a particular trivalent lanthanide (Ln(III)) often plays a unique role in different industrial applications, the development of a selective separation method to get only the requisite Ln(III) would be most convenient. Synergistic extraction with β-diketone (HA) and Lewis base (B), which has been extensively used for the separation of lanthanides, relies on two processes: the extraction with HA as LnA₃ into the organic phase and the complexation of LnA₃ with B as LnA₃B in the organic phase. The variation in the pattern of the extraction constants of LnA₃ across the Ln series correlates with the number of CF₃- group in the β-diketones, and with the stability constants of LnA₃B of different Lewis bases. It is seen that the constants with bipyridyl increase with increasing atomic number, while those with POPO (methylenediphosphonate) and MePhPA (methylphenylphenanthroline carboxamide) decrease with increasing Ln atomic number. Using pivaloyltrifluoroacetone as the β-diketone and MePhPA, the best extractability appeared at Sm(III) among the series. As a conclusion, to get only a required Ln(III), the combination of β-diketone and Lewis base is very important. In addition, the separation of Lns(III) from other metals and the use of new extractants developed recently and reported in literature were referred to find out more effective extractants and selective separation methods.     

Pathophysiology of Preeclampsia: The Role of Exosomes

The pathogenesis of preeclampsia begins when a fertilized egg infiltrates the decidua, resulting in implantation failure (e.g., due to extravillous trophoblast infiltration disturbance and abnormal spiral artery remodeling). Thereafter, large amounts of serum factors (e.g., soluble fms-like tyrosine kinase 1 and soluble endoglin) are released into the blood from the hypoplastic placenta, and preeclampsia characterized by multiorgan disorder caused by vascular disorders develops. Successful implantation and placentation require immune tolerance to the fertilized egg as a semi-allograft and the stimulation of extravillous trophoblast infiltration. Recently, exosomes with diameters of 50–100 nm have been recognized to be involved in cell–cell communication. Exosomes affect cell functions in autocrine and paracrine manners via their encapsulating microRNA/DNA and membrane-bound proteins. The microRNA profiles of blood exosomes have been demonstrated to be useful for the evaluation of preeclampsia pathophysiology and prediction of the disease. In addition, exosomes derived from mesenchymal stem cells have been found to have cancer-suppressing effects. These exosomes may repair the pathophysiology of preeclampsia through the suppression of extravillous trophoblast apoptosis and promotion of these cells’ invasive ability. Exosomes secreted by various cells have received much recent attention and may be involved in the maintenance of pregnancy and pathogenesis of preeclampsia.     

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.     

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.