Interaction of CETP inhibitory peptide and lipoprotein substrates in cholesteryl ester transfer assay: relationship between association properties and inhibitory activities

In a previous study, CETP inhibitory peptide (3 kDa) was isolated from hog plasma. The peptide, synthesized chemically according to the amino acid sequence of the 3-kDa peptide (designated P₂₈), showed CETP inhibitory activity both in vitro and in vivo [Cho et al. (1998) Biochim. Biophys. Acta 1391, 133–144]. We report herein further unique features of P₂₈ when it was associated with the cholesteryl ester (CE)-donor and-acceptor lipoproteins. Lipoprotein substrates with P₂₈ present in both HDL (as a CE-donor) and LDL (as a CE-acceptor) served as poor substrates, with CE-transfer activity decreased up to 60% compared to normal substrates without P₂₈. P₂₈ was found to be located in HDL fractions of hog plasma and showed the same electromobility as that visualized by PAGE on 7% polyacrylamide gel under nondenaturing conditions. Addition of apolipoprotein A-1 (apoA-1) or apoB antibody to a normal CE-transfer mixture did not alter CE-transfer activity. However, addition of apoA-1 or −B antibody to a CETP-inhibition mixture decreased the inhibitory activity of P₂₈ by ca. 20%. Western blot analysis revealed that P₂₈ was associated only with human and hog HDL among several lipoproteins purified from human, hog, and rabbit. CFTP-inhibition assays with various lipoprotein substrates revealed that P₂₈ exhibited substrate-specific inhibitory activity. The inhibitory activity of P₂₈ was highly dependent on the type of lipoprotein substrate (whether CE-donor or-acceptor); P₂₈ inhibited CE transfer from HDL to LDL, but it did not inhibit CE transfer from HDL to HDL.     

Synthesis and physicochemical characterization of amphiphilic block copolymer self‐aggregates formed by poly(ethylene glycol)‐block‐poly(ϵ‐caprolactone)

Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using ¹H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (K_v) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006     

Faceting of High-Angle Grain Boundaries in Titanium-Excess BaTiO3

The grain boundaries in BaTiO₃ with excess Ti of 0.5, 0.3, and 0.1 at.% sintered at 1300° or 1250°C have been examined by scanning electron microscopy (SEM), electron backscattered diffraction pattern (EBSP), and transmission electron microscopy (TEM). In the 0.1% Ti-excess specimen, large grains growing abnormally form high-angle grain boundaries when they impinge on each other as verified by EBSP. A large fraction of these grain boundaries are faceted with hill-and-valley shapes. In the 0.5% Ti-excess specimen, large grains growing abnormally are elongated in the directions of their {111} double twins. These grains often form flat grain boundaries parallel to their {111} planes with the fine matrix grains, and the grain-boundary segments between the large impinging grains with high misorientation angles are often also parallel to the {111} planes of one of the grains. These grain boundaries are expected to be singular. Most of the grain boundaries between the randomly oriented fine-matrix grains in the 0.3 at.% Ti-excess specimen are also faceted with hill-and-valley shapes at finer scales when observed under TEM. The facet planes are parallel to {111}, {011}, and {012} planes of one of the grain pairs and are also expected to be singular. These high-angle grain boundaries lying on low index planes of one of the grain pairs are similar to those observed in other oxides and metals.     

Memory effect of locally ordered α-phase in the melting and phase transformation behavior of β-isotactic polypropylene

Structural changes in β-isotactic polypropylene (β-iPP) during the heating were studied by means of differential scanning calorimetry and real-time in situ X-ray diffraction using a synchrotron source. Crystalline phase transformation and the memory effect caused by residual nuclei of α-iPP were observed during the heating of β-iPP. The memory effect observed in β-iPP during heating and crystallization is believed to be due to the existence of locally ordered α-from in the melt. The effect of local α-form order was probed by studying the behavior under heating of samples with a range of thermal histories. Samples were heated above the equilibrium melting temperature of iPP to remove all residual local order and the memory effect associated with this local order. The samples crystallized isothermally at different temperatures exhibited a significantly different melting and phase transformation behavior during heating. β-iPP is found to be an excellent material for the study of polymorphism, phase transformations, and characteristic memory effects in semicrystalline polymers.     

Distribution of Matrix Cracks in a Uniaxial Ceramic Composite

Conventional shear-lag analyses of matrix cracking and debonding in uniaxial composites loaded in tension predict that the matrix stress varies only very slowly with position except near existing cracks. It therefore follows that the location of subsequent cracks is very sensitive to minor local variations in matrix strength, leading to significant statistical variation in crack spacing. This question is investigated using a discrete random process model of a composite and by direct experimental measurements of crack spacing. In the limit of a completely homogeneous composite, it is shown that the crack spacing distribution tends to an inverse square distribution between the theoretical maximum spacing and half that value. The random process model recovers this behavior in the limit and exhibits an approximately Weibull distribution of crack spacings when the matrix strength has significant variance. The theoretical predictions are compared with experimental results obtained for a unidirectional ceramic-matrix composite (SiC fibers in a calcium aluminosilicate matrix). The experimental results exhibit features similar to those predicted by the model and are compatible with a matrix strength whose standard deviation is of the order of 40% of the mean strength. An important point is that, with this magnitude of strength variation, the material exhibits a significant size effect and it is essential to take this into account in estimating the mean crack spacing from the corresponding mean matrix properties.     

Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Oxidative coupling of methane over Na+-ZrO2-C1-/Al2O3 catalysts

Oxidative coupling of methane (OCM) was carried out over Na⁺-ZrO₂-Cl /A1[₂O₃ catalysts in a temperature range from 1023 to 1123 K. The catalysts were prepared by impregnating the α- or γ-Al₂O₃ supports with sodium carbonate and/or zirconyl chloride. The OCM activity was examined using the catalysts prepared by three different preparation procedures. The best catalyst was the one prepared by subsequent impregnation of sodium carbonate-preimpregnated γ-Al₂O₃ with a mixed solution of sodium carbonate and zirconyl chloride. It was found that preimpregnated sodium played an important role in reducing the combustion activity of the γ-Al₂O₃. The catalyst with an optimal composition showed the highest C₂ selectivity and yield of 40.8% and 15.1%, respectively. From the X-ray diffraction analysis it was found that tetragonal ZrO₂ was formed and that NaCl existed in the catalysts with relatively high sodium contents.     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Thermal runaway prevention in catalytic packed bed reactor by solid temperature measurement and Control

Magnetic crystallite thermometry has been used to measure the average nickel crystallite temperature in packed bed reactors during ethane hydrogenolysis, an exothermic reaction. The technique is based on the temperature dependence of the magnetic moment of dispersed nickel catalysts. Measurement of the average catalyst temperature is very useful for reactor control because of its shorter time constant compared with exit fluid temperature. Bed temperature control based on the exit fluid temperature, which has often been used as a control variable, is too slow to protect thermal runaway of the bed. The advantage of short time constant by measuring the average catalyst temperature has been incorporated with enhanced feedback control system to control the bed temperature and prevent the thermal runaway of the catalyst bed. An enhanced feedback control structure with supervisory action performed better than the classical proportional-integral control in runaway prevention when the two control schemes were compared with each other on the basis of the trippoint (incipient thermal runaway).     

Fabrication of a gradient refractive index preform using laminar shear mixing

A gradient refractive index rod was successfully prepared by a new fabrication method using laminar shear mixing, and a graded index polymer optical fiber that satisfied IEEE1394b was obtained from the method. To fabricate the gradient refractive index rod, a liquid monomer mixture with a relatively low refractive index was placed in a prepared cylindrical glass reactor and a transparent polymer rod with a higher refractive index was introduced at the center of the reactor. The reactor and the polymer rod were then rotated concurrently with a small rotating speed difference to generate a Couette flow in the liquid phase. The centrifugal force generated by rotation and the polymer diffusion into the liquid monomer mixture developed a graded concentration profile in a radial direction. The Couette flow could reduce the concentration fluctuation in a tangential direction. In addition, the graded index profile could be controlled by the copolymer composition of the rod and its diameter. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1100–1104, 2005