A review of the unique features of HDL apoproteins

The human plasma high density lipoproteins (HDL) are a heterogeneous ensemble of five proteins associated with both neutral and polar lipids. The sequences of all five proteins are known. ApoA-I and apoA-II are the major protein components; apoC-I, apoC-II and apoC-III are the minor protein components. All these apoproteins spontaneously recombine with phospholipids to give stable lipid-protein complexes and freely exchange between the two major HDL subclasses, HDL₂ and HDL₃. In addition, ApoC-I, apoC-II, and apoC-III exchange between HDL and very low density lipoproteins. Furthermore, certain HDL apoproteins are activators for plasma enzymes that are important in lipid metabolism. ApoA-I and apoC-I activate lecithin/cholesterol acyltransferase; apoC-II is an activator of lipoprotein lipase. The regions of apoC-I and apoC-II that are involved in the activation of these enzymes have been localized with synthetic peptides. Studies of synthetic and native fragments of apoA-II, apoC-I, apoC-II, and apoC-III as well as model lipid-binding peptides have identified specific regions with structural features common to lipid-binding proteins. These special properties, which include helical potential, sequences with a critical amphipathic length, and high hydrophobicity of the nonpolar side of the amphipathic helix, are the determinants of HDL structure and metabolism.     

Poly(aryl ether oxadiazoles)

A general method for the preparation of poly(aryl ether oxadiazoles) has been developed where the generation of an aryl ether linkage was the polymer-forming reaction. Two synthetic approaches were investigated based on either an oxadiazole-activated halo displacement with phenoxides or a hydrazide-activated halo-displacement with phenoxides. The hydrazide may be subsequently thermally cyclodehydrated to the oxadiazole heterocyclic. In each case, the negative charge developed in the transition state could be stabilized through a Meisenheimer Complex, analogous to conventional activating groups (e.g., sulfone and ketone), and the electron affinity, as judged by ¹H NMR, was comparable to that of other activating groups. An appropriately substituted diarylfluoro oxadiazole was prepared and polymerized with various bisphenols in an NMP/CHP solvent mixture in the presence of K₂CO₃. High molecular weight poly(aryl ether oxadiazoles) were synthesized with viscosities ranging from 0.44 to 0.76 dL/g and Tg's in the 200°C range. Conversely, the hydrazide activated halo-displacement as a means of preparing poly(aryl ether hydrazides) was not as successful, since it appears that the hydrazide was of sufficient acidity to form a salt with K₂CO₃ preventing solubility and polymerization.     

Rheological and extrusion characteristics of glass fiber-reinforced polycarbonate

An experimental investigation of the rheological properties of glass fiber-reinforced polycarbonate melts and the extrusion of such compounds through capillary and slit dies is presented. The viscosity–shear rate function seems independent of instrument for cone-plate and capillary investigations. The presence of fibers increases the level of the viscosity. Normal stresses at fixed shear stress are also increased by the presence of fibers. The extrudate swell is decreased by the presence of fibers and surface roughness is increased. Fiber orientation increases and surface roughness decreases with increasing extrusion rate.     

Assessing detergent safety: A comparison of a nonphosphate laundry detergent with phosphate detergents

The potential hazard of a carbonate-based, phosphate-free detergent was compared with that of a variety of granular and liquid phosphate detergents. Evaluations were made using methods prescribed by the Federal Hazardous Substances Act (FHSA) and others designed to more closely approximate exposure in actual use. Some phosphate products produced esophageal and gastric mucosal irritation similar to that produced by the nonphosphate detergent, while others caused varying, lesser degrees of injury. The nonphosphate detergent, as well as several phosphate products, was seriously irritating to the unwashed eye at required FHSA test levels. Under more realistic conditions, eye irritation was reduced significantly. Skin irritation by the nonphosphate product was comparable to that by phosphate detergents, and in some cases was lower. In skin irritation tests with human subjects, results with the carbonate detergent were equal to or lower than those obtained with phosphate detergents. The carbonate detergent was found not to be phototoxic, nor a contact- nor photo-sensitizer. Total alkalinity was shown not to correlate with the severity of tissue injury in either test animals or in man. Presented at the AOCS Short Course, “Update on Detergents and Raw Materials,” Lake Placid, New York, June 1971.     

Engineering plastics from lignin. VI. Structure–property relationships of PEG-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Four polyethylene glycols (PEG) of molecular weight 400, 600, 1000, and 4000 were mixed with lignin polyol to incorporate different proportions of soft segment into the network prior to crosslinking. Neither thermal nor mechanical and limited small angle x-ray scattering (SAXS) analysis provided distinct evidence for phase separation and microstructure formation. The study examines the effect of the soft segment in relation to chain length and weight contribution on the thermal and mechanical properties of the final networks. A significant sensitivity of glass transition temperature (T_g), of swelling in DMF, and of the mechanical properties to soft segment content was observed. Some of this sensitivity must, however, be attributed to differences in crosslink density since the polyol to diisocyanate weight ratio was kept constant throughout the synthesis series. The magnitude of the change of the different properties was found to be influenced by both glycol content and glycol molecular weight. The T_g of the network decreased from 105°C to as low as 38°C (HDI), and from 158°C to 70°C (TDI), with incorporation of up to 17.8% glycol, and it was greater with lower molecular weight glycols than with higher ones at any weight fraction. Swelling in DMF increased as expected with soft segment content. Mechanical properties were affected most if HDI and lower molecular weight glycols were used. The uniformity in structure, reduction in brittleness, and considerable improvement in mechanical properties with inclusion of minor PEG contents indicates that lignin-based network polyurethanes can be synthesized with controllable performance characteristics.     

A model for studying LCAT reaction: In vitro cholesterol esterification in pig ovarian follicular fluid

Phosphatidylcholine acyltransferase (lecithin:cholesterol acyltransferase or LCAT; EC 2.3.1.43) activity was found to be present in pig ovarian follicular fluid (POFF), in addition to pig serum (PS). The cholesterol esterification rate in both POFF and PS is linear with incubation time up to 2 hr. The mean absolute rate of POFF-cholesterol esterification was 8.1±0.4 nmoles per ml per hr approximately one-fourth of that in PS. However, the fractional rate (percent of labeled cholesterol esterified per hr) of POFF-cholesterol esterification was similar to that observed in PS. There was little variation of absolute rate of cholesterol esterification in the fluid obtained from different sizes of follicles. Fatty acid or triacylglycerol did not participate in the reaction of cholesterol esterification in POFF. No appreciable change in enzymatic activity was found from storing POFF at 4 C for periods of time up to 24 hr or at −70 C up to 2 months, but activity was lost thereafter. On the other hand, PS showed a much longer period of stability (5 days at 4 C and 9 months at −70 C). A discrepancy between the fatty acid composition of cholesteryl esters formed by the LCAT reaction and the fatty acid composition at the C-2 position of phosphatidylcholine led us to propose a two-step mechanism for the LCAT reaction. It is concluded that the LCAT of POFF, as well as that of plasma, is specific for individual fatty acids rather than for the fatty acid composition of phosphatidylcholine. The fatty acid concentration of lysophosphatidylcholine decreased during prolonged incubation times (6 to 21 hr) suggesting that the increased lysophosphatidylcholine formed as a product of the LCAT reaction may be reused as substrate for the LCAT reaction or for hydrolysis by lysophosphatidylcholine hydrolase. Presented at the AOCS Meeting, New York, May 1977.     

Allelochemical resistance of bald cypress,Taxodium distichum,heartwood to the subterranean termite,Coptotermes formosanus

The heartwood of bald cypress,Taxodium distichum (L.) Rich., resisted feeding attack by the Formosan subterranean termite,Coptotermes formosanus Shiraki. Hexane-extracted heartwood, however, was consumed at > 12 times the amount of sound heartwood eaten. A bioassay usingT. distichum sapwood as a feeding substrate was employed to assess the antitermitic activity of successive hexane, acetone, and methanol extracts of heartwood shavings and isolates derived from the active hexane extract. Two fractions, eluted from the crude hexane extract by liquid chromatography, significantly reduced termite feeding compared to the parent extract, while a third fraction was less active than the original hexane extract. Each fraction contained one major component. All three components were structurally related diterpenes. The two most active heartwood constituents were identified by GC-MS and NMR as ferruginol and manool, while the third and least active, but most prevalent, compound in heartwood was identified as nezukol. Results of bioassays suggest that these allelochemicals act principally as feeding deterrents with accompanying termite mortality due to starvation.     

Particle and Granule Parameters Affecting Compaction Efficiency in Dry Pressing

The slope of density versus log (pressure) represents the efficiency of compaction forming. A high maximum particle packing density of powders increased the pressing efficiency and the compact density. A high granule density favors a high compact density, whereas, a low granule density favors an increase in the pressing efficiency and the elimination of the intergranular pores; an optimum clearly existed. At a very low forming pressure, the compact density using granules containing a binder was lower; but at a higher forming pressure, the binder acted as a lubricant and assisted particle sliding and rearrangement which increased the pressing efficiency and compact density.