Thermal polymerization of methyl linolenate,alpha- and beta-eleostearates

Summary The rates of polymerization of alpha and beta eleostearates agree with second order kinetics, as would be expected for a bimolecular Diels-Alder addition. The all-trans, beta isomer reacts faster than thecis, trans, trans alpha isomer, in agreement with knowncis, trans effects on diene activity. The polymerization of normal linoleate follows an apparent first order reaction. It is suggested that conjugation is the slow rate determining monomolecular reaction, as has been proposed for the non-conjugated linoleate isomers. Paper No. 177, Journal Series, Research Laboratories, General Mills Inc. Presented at the 28th fall (Paul Bunyan) meeting of the American Oil Chemists’' Society, Oct. 12, 1954, Minneapolis, Minn.     

Designing biomass supply chains within planetary boundaries

The design of sustainable supply chains, which recently emerged as an active area of research in process systems engineering, is vital to ensure sustainable development. Despite past and ongoing efforts, the available methods often overlook impacts beyond climate change or incorporate them via standard life cycle assessment metrics that are hard to interpret from an absolute sustainability viewpoint. We here address the design of biomass supply chains considering critical ecological limits of the Earth—planetary boundaries—which should never be surpassed by anthropogenic activities. Our method relies on a mixed-integer linear program that incorporates a planetary boundaries-based damage model to quantify absolute sustainability precisely. We apply this approach to the sugarcane-to-ethanol industry in Argentina, identifying the optimal combination of technologies and network layout that minimize the impact on these ecological boundaries. Our framework can find applications in a wide range of supply chain problems related to chemicals and fuels production, energy systems, and agriculture planning.     

Sustainable end-of-life vehicle recycling: R&;D collaboration between industry and the U.S. DOE

Approximately 15 million cars and trucks reach the end of their useful life in the United States each year. More than 75% of the materials from end-of-life vehicles are profitably recovered and recycled by the private sector; automotive materials recycling is a success story. To achieve greater fuel efficiency and safety, today’s cars incorporate an increasing share of innovative light-weight materials. While these materials greatly enhance efficiency during vehicle use, they can present special challenges for recycling. These challenges will persist as automotive designs and the mix of materials used in vehicles continue evolving to further improve safety and performance. To meet the challenges of automotive materials recycling, the U.S. Department of Energy has recently expanded its collaborative research with industry in this area. This article discusses this collaborative government/industry approach to sustainable end-of-life vehicle recycling. For more information, contact Edward J. Daniels, Argonne National Laboratory, 9700 S. Cass Avenue, Building 362, Room C393, Argonne, IL 60439-4815; (630) 252-5279; fax (630) 252-1342; e-mail edaniels@anl.gov.     

Physicochemical properties of calcific deposits isolated from porcine bioprosthetic heart valves removed from patients following 2-13 years function

The purpose of this study was to characterize the physicochemical properties of calcific deposits that cause the failure of tissue-derived heart valve bioprostheses. This was done in an effort to understand the mechanism of pathologic biomineralization in the cardiovascular system and potentially prevent deterioration of bioprostheses. Calcific deposits taken from 10 failed bioprosthetic valves that had been implanted in patients for 2-13 years were characterized by chemical analysis, x-ray diffraction, FTIR spectroscopy, scanning electron microscopy, polarized light microscopy, and solubility measurements. The combined results identified the biomineral as an apatitic calcium phosphate salt with substantial incorporation of sodium, magnesium and carbonate. The average Ca/PO4 ratio for this "young" pathologic biomineral was approximately 1.3, considerably lower than approximately 1.7 found in mature atherosclerotic plaque biomineral and mature skeletal biomineral, both of which approximate hydroxyapatite in composition. Deproteinated calcific deposits from bioprostheses had thermodynamic solubilities comparable to those of both atherosclerotic plaque, typical pathologic biomineral and hydrolyzed octacalcium phosphate (OCP, Ca4H(PO4)3 x 2.5 H2O), a proposed precursor phase to biomineral apatite. This later finding, together with chemical composition and structural details of the bioprosthetic deposits themselves, supports a mechanism of cardiovascular calcification in which OCP plays a crucial role in the formation of the final apatitic phase. This suggests an approach toward prevention of bioprosthetic tissue calcification through control of the formation of the kinetically favored OCP precursor and/or its transformation into bioapatite.     

Molecular structures and conformational studies of triarylcyclopropyl and related nonsteroidal antiestrogens

Molecular structures and conformational characteristics of a series of 1,1-dichloro-2,2,3-triarylcyclopropanes (DTACs), which were reported previously to be distinctly antiestrogenic and inhibitors of the estrogen-receptor-positive MCF-7 human breast cancer cells in culture, are reported. In addition, structural and conformational features of the DTACs were compared to the first-known nonsteroidal antiestrogen, MER25, and the clinically useful antiestrogen Tamoxifen. The molecular structures of four DTAC compounds were determined by X-ray diffraction. Crystallographic structures show that the DTAC molecules have nearly the same relative conformation for the three aryl rings which is designated as a "nonpropeller" conformation in contrast to the observed "propeller" conformation for the three rings in all known triarylethylenes. Systematic conformational searches were performed to find the conformational preferences of DTACs, MER25, and Tamoxifen using idealized model compounds built from their respective crystal structure. Energy-minimization and conformational-search studies demonstrated that all DTAC molecules have a common, single global minimum energy conformer for their central core containing the dichlorotriarylcyclopropyl system, which is similar to that found in their crystal structures. Conformational search of MER25 showed that the molecule can assume a number of low-energy conformers of which two, one anti (A1) and one gauche (G1A), have about the same energy. The anti conformation is similar to the one observed in its crystal structure and resembles the estrogenic E-isomer of Tamoxifen, while the lowest energy gauche conformer of MER25 resembles more closely the antiestrogenic Z-isomer of Tamoxifen. NMR spectroscopic analysis of MER25 showed that the molecule exists predominantly in the anti conformation in solution. A comparative review of the structural features and bioactivities of Tamoxifen, DTACs, and MER25 provides a possible explanation for their low estrogen receptor binding affinity which is common to these compounds together with their antiestrogenic activity.     

Observer agreement on interpreting colposcopic images of CIN

The purpose of this work was to study intraobserver and interobserver variation in the interpretation of colposcopic images of cervical intraepithelial neoplasia (CIN). Twenty-three experienced colposcopists were asked to assess colposcopic images presented on slides and to select the biopsy site. Eleven cases were independently interpreted twice with an interval of 2-3 months by all observers. No information about the cytological classification was available. In each case the "majority assessment" was considered as the standard, being "no CIN" in 2 cases, CIN I in 4 cases, CIN II in 3 cases, and CIN III in 2 cases. Intraobserver concordance was 66.7%, the kappa value was 0.54. Interobserver agreement was found to be 52.4 and 51.0% in the first and second sessions, respectively, while the mean kappa values were 0.41 and 0.33, respectively. In selecting the site for biopsy, 77.4% of all observers agreed while the same site was selected in 85.3% of cases by the individual colposcopist in the two sessions. Overall, CIN I and II interpretations revealed lower levels of agreement than no CIN or CIN III interpretations. It is concluded that observer variability in interpreting colposcopic images and selecting the site for biopsy is in the same range as observer variation in other subjective diagnostic tests such as cytology and histopathology. This variation should be taken into account in the colposcopical management of patients with abnormal cytology.     

The myth of Eve: molecular biology and human origins

It has been proposed that modern humans descended from a single woman, the "mitochondrial Eve" who lived in Africa 100,000 to 200,000 years ago. The human immune system DRB1 genes are extremely polymorphic, with gene lineages that coalesce into an ancestor who lived around 60 million years ago, a time before the divergence of the apes from the Old World monkeys. The theory of gene coalescence suggests that, throughout the last 60 million years, human ancestral populations had an effective size of 100,000 individuals or greater. Molecular evolution data favor the African origin of modern humans, but the weight of the evidence is against a population bottleneck before their emergence. The mitochondrial Eve hypothesis emanates from a confusion between gene genealogies and individual genealogies.     

Effects of regional stimulation using a miniature stimulator implanted in feline posterior biceps femoris

The effects of placement of a miniature implantable stimulator on motor unit recruitment were examined in the posterior head of cat biceps femoris. The implantable stimulator (13-mm long x 2-mm diameter) was injected either proximally near the main nerve branch, or distally near the muscle insertion, through a 12-gauge hypodermic needle. Glycogen-depletion methods were used to map the distribution of fibers activated by electrical stimulation. Muscle fibers were found to be depleted at most or all proximodistal levels of the muscle, but the density of depleted fibers varied transversely according to the stimulus strength and proximity of the device to the nerve-entry site. Thus, muscle cross sections often had a "patchy" appearance produced because different proportions of depleted fibers intermingled with undepleted fibers in different parts of the cross section. In other preparations, the force of muscle contraction was measured when stimuli of varying strengths were delivered by the stimulator positioned at the same proximal or distal sites within the muscle. Devices placed close to the nerve-entry site produced the greatest forces. Those placed more distally produced less force. As stimulus current and/or pulse width increased, muscle force increased, often in steps, until a maximum was reached, which was usually limited by the compliance voltage of the device to less than the force produced by whole nerve stimulation.     

An unusual case of Creutzfeldt-Jakob disease

A patient with histopathologically verified sporadic Creutzfeldt-Jakob disease (CJD) presented initially with diplopia, sleep disturbances, and L-dopa-responsive parkinsonism. After more than a year of slow progression, he did not become demented, and failed to fulfill the clinical criteria for possible CJD. No clinical examinations currently proposed to detect CJD showed the disease. CJD should be in the differential diagnosis of "parkinson plus" syndromes until a different etiology has been found or a histopathologic examination performed.     

Visualization and quantification of myocardial mass at risk using three-dimensional contrast echocardiography

To investigate possible biochemical mechanisms underlying the "toxic gain of function" associated with polyglutamine expansions, the ability of guinea pig liver tissue transglutaminase to catalyze covalent attachments of various polyamines to polyglutamine peptides was examined. Of the polyamines tested, spermine is the most active substrate, followed by spermidine and putrescine. Formation of covalent cross links between polyglutamine peptides and polyamines yields high-M(r) aggregates--a process that is favored with longer polyglutamines. In the presence of tissue transglutaminase, purified glyceraldehyde-3-phosphate dehydrogenase (a key glycolytic enzyme that binds tightly to the polyglutamine domains of both huntingtin and dentatorubral-pallidoluysian atrophy proteins) is covalently attached to polyglutamine peptides in vitro, resulting in the formation of high-M(r) aggregates. In addition, endogenous glyceraldehyde-3-phosphate dehydrogenase of a Balb-c 3T3 fibroblast cell line overexpressing human tissue transglutaminase forms cross-links with a Q60 polypeptide added to the cell homogenate. Possibly, expansion of polyglutamine domains (thus far known to occur in the gene products associated with at least seven neurodegenerative diseases) leads to increased/aberrant tissue transglutaminase-catalyzed cross-linking reactions with both polyamines and susceptible proteins, such as glyceraldehyde-3-phosphate dehydrogenase. Formation of cross-linked heteropolymers may lead to deposition of high-M(r) protein aggregates, thereby contributing to cell death.