Engineering plastics from lignin. XV. Polyurethane films from chain-extended hydroxypropyl lignin

A series of polyurethane (PU) films was prepared from chain-extended hydroxypropyl lignins (CEHPL). In appearance, these films ranged from brittle and dark brown to rubbery and bronze. The thermal, mechanical, and network properties of these PUs were investigated by DMTA and DSC analysis. All films exhibited single T_g's which varied between ?53° and 101°C, depending on lignin content. From swelling experiments, molecular weight between crosslinks (M _c) was determined and found to vary over 2.5 orders of magnitude. The M _c's were related to the change in T_g that accompanied network formation. Stress–strain experiments showed a variation in Young's modulus between 7 and 1300 MPa. Most of the variation in material properties was related to lignin content and to a lesser extent to diisocyanate type, hexamethylene diisocyanate, or toluene diisocyanate. The source of the CEHPL had no effect on the observed properties. From these results it was concluded that the properties of PUs can be controlled and engineered for a wide variety of practical uses.     

Preparation and properties of high molecular weight poly(1-germa-) or poly(1-sila-cis-pent-3-enes)

High molecular weight poly(1,1-dimethyl-1-germa-cis-pent-3-ene), poly(1,1-diphenyl-1-germa-cis-pent-3-ene), poly(1,1-dimethyl-1-sila-cis-pent-3-ene), and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) have been prepared. The thermal stability of these polymers is found to increase with their molecular weight.     

Engineering a pharmacologically superior form of leptin for the treatment of obesity

Leptin plays a central role in the homeostasis of body weight through its regulatory effects on appetite and energy expenditure, yet in trials as a therapeutic agent for the treatment of obesity in humans it has been disappointing. The poor clinical efficacy of leptin results from its short circulating half-life, low potency and poor solubility, necessitating large and frequent doses to obtain even modest clinical benefit. Engineered Fc-leptin immunofusins, consisting of the Fc fragment of an immunoglobulin gamma chain followed by leptin, exhibit improved pharmacological properties with very consistent and potent biological activities. Furthermore, in extending the circulating half-life of the protein in vivo from a few minutes for leptin to many hours for Fc-leptin, these proteins have the potential to reduce drastically the dosage and frequency of administration required to obtain clinical benefit. The results of this study show that the engineered leptin immunofusins described here have significantly enhanced pharmacological properties in comparison with the recombinant leptin that was used in clinical trials. As such, they could represent an important step towards a therapeutically superior form of leptin if the disappointing performance of leptin in early clinical trials was due to its poor pharmacological properties rather than any conceptual weakness in the strategy of using leptin for the treatment of obesity and its related disorders.     

Review of Mechanically Related Failures of Ceramic Capacitors and Capacitor Materials

This paper reviews the brittle fracture behavior of dielectric ceramics such as barium titanate, and describes some of the relationships between defects such as cracks and electrical degradation and failure of multilayer capacitors. Stresses arising from the ferroelectric phase transformation in these dielectric materials are shown to play a part as a driving force for crack growth. In addition, possible contributions to failure from stresses arising from thermal excursions in the capacitor are discussed. Low-voltage failures arising from a short between the electrodes in multilayer capacitors are shown to be related to the growth of cracks in the dielectric. A technique for predicting the onset of these types of failures based upon fracture mechanics techniques is described. Possible effects of the electric field itself in promoting or retarding the growth of cracks are discussed.     

The fatty acids of wax esters and sterol esters from vernix caseosa and from human skin surface lipid

Separation of sterol esters from wax esters in the lipids of vernix caseosa and adult human skin surface was accomplished by column chromatography on MgO. The fatty acids of the sterol esters and wax esters of both samples were separated into saturates and monoenes, and examined in detail by gas liquid chromatography (GLC). The saturated fatty acids of the wax esters of vernix caseosa and of adult human skin surface were remarkably similar. They ranged in chain length from at least C₁₁ to C₃₀, six skeletal types being present: straight even, straight odd, iso, anteiso, other monomethyl branched and dimethyl branched. A large number of patterns of monoenes were observed, each pattern consisting of desaturation of a specific chain at Δ6 or Δ9 plus its extension or degradation products. The mole per cent of the total Δ6 and Δ9 patterns of wax ester fatty acid monoenes of vernix caseosa were 87% and 12%, respectively, and 98% and 1%, respectively, for adult human skin surface lipid. The sterol ester fatty acids of vernix caseosa were much different from those of adult human skin surface: vernix caseosa saturates were largely branched and of lengths greater than C₁₈, whereas the saturates of adult human surface lipid resembled the wax ester fatty acids. Of the vernix caseosa monoene patterns, the mole per cent was 30% Δ6 and 70% Δ9, whereas of the adult human skin surface sterol ester fatty acids 89% were Δ6 and 11% Δ9. Chain extension was particularly pronounced in the sterol ester fatty acid monoenes of vernix caseosa amounting to 7–8 C₂ units in some cases. The fatty acids of the sterol esters of both vernix caseosa and adult human skin surface appear to be derived from the sebaceous gland and from the keratinizing epidermis, but those of the wax esters are from the sebaceous glands only.     

Exploiting border structure in solving large sparse linear systems in bordered triangular form

An elimination strategy for solving sparse linear systems in bordered triangular form is presented. This strategy is designed to exploit certain common structural properties of the borders of such a system. It may also be interpreted as a recursive application of block elimination. The technique is numerically efficient and provides significant reductions in fill-in compared to routine Gaussian elimination. It is applicable in the iterative solution of the large systems of nonlinear equations that arise in the equation-oriented approach to process simulation and design calculations, as well as in other problems of interest to the chemical engineer.     

Fabrication and characterization of planar and channel polymer waveguides. III. Compositional distribution and solute loss in polymer thin films

For many microelectronic and optoelectronic applications, polymer thin films require the addition of small molecules. However, the thin‐film geometry and associated processing techniques will influence the final morphology and compositional distribution of the constituents. It is therefore important that these be examined directly rather than inferred from bulk measurements. As an example system, the concentration and distribution of Disperse Red 1 (DR1) molecules in poly(methyl methacrylate) thin films were examined. Ultraviolet visibility spectroscopy and dynamic secondary ion mass spectrometry indicate that the composition of the molecules decreased dramatically with thermal treatment of the film. The sublimation of the chromophore was observed to occur at temperatures well below the melting point of the small molecule and the glass transition of the pure polymer; this solute loss manifested itself in changes in the glass transition temperature of the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2021–2024, 2002     

The effect of processing conditions upon the nutritional quality of vegetable oils

On the basis of the chemical, physical, and biological criteria used, all of which have been shown to be sensitive indicators of heat damage to oils, it must be concluded that the overall nutritional quality of an oil is not adversely affected by alkali refining, adsorptive decolorizing, or deodorization; that higher temperatures of deodorization (238C) produce oils nutritionally equivalent to those deodorized at lower temperatures (160C); and that the normal processes used in manufacturing edible oils improve the resistance of these oils to heat damage. Presented at the 6th Congress of the International Society for Fat Research, London, 1962.     

Lung lamellar bodies lack certain key enzymes of phospholipid metabolism

Palmitoyl CoA-glycerol-3-phosphate acyltransferase, phosphatidate phosphohydrolase, and phospholipase A were assayed in subcellular fractions of rat lung, including lamellar bodies, the putative site of storage and secretion of lung surfactant. The specific activity of each of these enzymes in lamellar bodies was relatively low and could be entirely accounted for by a small contamination of the lamellar bodies fraction by microsomes, as quantitated by the presence of the microsomal marker reduced triphosphopyridine nucleotide cytochromec reductase. These data indicate that lamellar bodies are not the site of synthesis of the lipid component of pulmonary surfactant by pathways involving these enzymes.     

Zeolite Formation in Class F Fly Ash Blended Cement Pastes

Zeolite formation in Class F fly ash blended cement pastes is under investigation. A Na–P type zeolite and Zeolite Y were synthesized from Class F fly ash and NaOH solution after 2 days of aging at room temperature and 6 days of curing at 80°C. However, no zeolites formed when KOH was used. In additional experiments, a Na–P type zeolite, Zeolite Y, and chabazite developed in cement pastes blended with Class F fly ash and NaOH solution which had been aged 2 days at room temperature and then cured 6 days at temperatures ranging from room temperature to 90°C. Seeding the pastes with natural zeolites was also investigated.