Preliminary investigation of bioadvantaged polymers as sustainable alternatives to petroleum-derived polymers for asphalt modification

Due to recent volatility in the petroleum market, the possibility of using sustainable alternative materials as substitutes has gained great interest and viability. The purpose of this research is fourfold: to demonstrate how bioadvantaged polymers are produced using non-food soybean oil and showcase their economic and environmental value; to evaluate how they perform rheologically in asphalt against commonly used petroleum-derived polymers; to optimize the formulation of the bioadvantaged polymer for warm climate regions pavement applications based on the grading results, and to verify the modification effects of optimized bioadvantaged polymer by running performance grade tests. The study on economic and environmental implications demonstrated that poly(styrene-acrylated epoxidized soybean oil) (PS-PAESO) is more cost-effective, environmentally friendly, and safer to produce than styrene-butadiene (SB) polymer. The commercially produced petroleum-derived SB diblock polymer was used for comparison, while the laboratory produced bioadvantaged polymers were targeted at 1.25 MDa molecular weight of PS-PAESO diblock copolymers that consist of PAESO with various polystyrene (PS) molecular weights and contents. The effectiveness and rheological performance of the polymer modified asphalt binders were evaluated through binder investigations. Rheology test results indicated that the bioadvantaged polymers improved the stiffness, elasticity, and rutting resistance of the neat asphalt binder. Best-fit prediction models were developed through response surface modeling to optimize the PS-PAESO formulation in terms of PS content and molecular weight and the models were verified to be highly accurate based on the grading results. It was found that lower polystyrene content in PS-PAESO polymer could be beneficial in the improvement of critical high temperatures.     

The effect of annealing on the structure of cobalt modified iron oxide particles. Part II

A new high coercivity cobalt modified iron oxide particle series has been prepared by annealing in a nitrogen atmosphere. The dependence of coercivity (Hc), Hc-aging, temperature dependence of Hc, and magnetic tape properties have been studied as a function of annealing temperature. X-ray photoelectron spectroscopy (XPS) has been used to correlate the changes in magnetic properties to the cobalt concentration gradient near the particle surface. As in Part I of the study, most of the changes observed are consistent with diffusion of cobalt from the surface into the particle core.     

Polarization-optical investigation of normal and shear stresses in flow of polymers

A method has been suggested for calculating the first difference of normal stresses characterizing the flow of polymers at high shear stresses. The calculations are based on the results of rheooptical measurements in a slit of rectangular cross section. It has been found, for several samples of high molecular weight polybutadienes and polyisoprenes, that the flow behavior of the representatives of the given polymer homologous series having different molecular weights is characterized by a general relationship between the first normal stress differences and the shear stresses in those cases where the polymers are characterized by narrow molecular weight distributions. It has also been established that the first normal stress difference sharply increases in the region of shear stresses which immediately precedes the spurt—a jumpwise increase of the flow rate at a certain critical value of shear stress; while for polymers of wide molecular weight distribution the increase of the normal stress difference in the region of high values of shear stresses is retarded. Equilibrium swell of the extrudate has been measured and the first normal stress difference determined by the rheo-optical method has been found to agree satisfactorily with the values calculated from the swelling ratios according to theoretical models.     

Probing the Role of Chirality in Phospholipid Membranes

Nucleotides, amino acids, sugars, and lipids are almost ubiquitously homochiral within individual cells on Earth. While oligonucleotides and proteins exist as one natural chirality throughout the tree of life, two stereoisomers of phospholipids have separately emerged in archaea and bacteria, an evolutionary divergence known as “the lipid divide”. Within this review, we focus on the emergence of phospholipid homochirality and compare the stability of synthetic homochiral and heterochiral membranes in vitro. We discuss chemical probes designed to study the stereospecific interactions of lipid membranes in vitro. Overall, we aim to highlight studies that help elucidate the determinants of stereospecific interactions between lipids, peptides, and small molecule ligands. Continued work in understanding the drivers of favorable interactions between chiral molecules and biological membranes will lead to the design of increasingly selective chemical tools for bioorthogonal labeling of lipid membranes and safer membrane-associating pharmaceuticals.     

Trefoil peptide protection of intestinal epithelial barrier function: cooperative interaction with mucin glycoprotein

BACKGROUND & AIMS: Goblet cells secrete a combination of trefoil peptides and mucin glycoproteins to form a continuous gel on the mucosal surface. The functional effects of these products remain uncertain. METHODS: Trefoil peptides and/or mucin glycoproteins were added to Transwell monolayers of the human colonic cancer-derived T84 cell line. Intact monolayers permitted penetration of < 4% of the inert marker [3H]mannitol at 4 hours. Exposure to the toxic lectin phytohemagglutinin (1 mg/mL), oleic acid (8 mmol/L) and taurocholic acid (12 mmol/L), or Clostridium difficile toxin A (0.7 microgram/mL) resulted in loss of barrier function with 36%, 62%, and 45% of [3H]mannitol penetration, respectively. RESULTS: Addition of recombinant human intestinal trefoil factor in physiological concentrations (1-5 micrograms/microL) resulted in attenuation of the damage to monolayer integrity by up to 52%. Protection was enhanced (up to 95%) by the copresence of human colonic mucin glycoproteins. Similar effects were observed when rat intestinal trefoil factor or human spasmolysin, another human trefoil peptide, were added alone or in the presence of human mucin glycoproteins. Conversely, mucin glycoproteins isolated from the rat colon or stomach facilitated protection when added with human spasmolysin or human intestinal trefoil factor. CONCLUSIONS: Trefoil peptides and mucin glycoproteins protect gastrointestinal mucosa from a variety of insults.     

Improvement of growth hormone response to stimulation in primary aldosteronism with correction of potassium deficiency

Potassium depletion frequently occurs in primary aldosteronism and has been implicated as the cause of the impaired carbohydrate tolerance frequently associated with this syndrome. Glucose, insulin, and growth hormone regulation were studied in a 42-yr-old, male patient with an aldosterone-secreting adenoma when the patient was potassium-depleted and again after potassium repletion. Potassium repletion was documented by serial body potassium measurements, with an increase in body potassium from 2400 mEq to 2850 mEq after 400 mg spironolactone and 80 mEq supplemental potassium chloride were administered daily for 7 days. Potassium repletion resulted in improvement of the patient's glucose tolerance test, with a decrease in the peak glucose level from 184 mg/100ml to 130 mg/100ml and an increase in the peak insulin level from 46 muU/ml to 85 muU/ml. Intravenous administration of arginine resulted in a subnormal insulin response of 28 muU/ml in the base-line test and an increase to 59 muU/ml after potassium stores were repleted. Growth hormone response to arginine infusion was also initially minimal at 12.5 ng/ml, increasing markedly to 26 ng/ml after potassium replenishment. Insulin-induced hypoglycemia resulted in a depressed growth hormone response of 8 ng/ml when the patient was potassium-deficient, but a normal response of 30 ng/ml after potassium repletion. These observations demonstrate that impairment of both insulin and growth hormone responses to stimulation occur in primary aldosteronism with potassium depletion. These abnormalities may be reversed by potassium repletion.     

Extensional stresses during polymer flow in ducts

During the flow of high molecular weight, narrow-, and broad-distribution polybutadienes and polyisoprenes rheo-optical measurements were conducted of extensional stresses acting along the flow axis in the preentrance and entrance regions of the duct and of their subsequent relaxation in the duct. The extensional stresses increase in the preentrance region, reach their maximum values at a distance of two or three tenths of the duct width from its edges, and then relax. The position of the maximum extensional stress is independent of polymer characteristics, shear stresses in the duct, and shape of the entrance and dimensions of the rectangular duct. The dependence of the maximum extensional stress on the shear stress of the duct wall can be assumed to be linear for small values. The length of the stress relaxation zone depends on the shear stress at the duct wall and the molecular mass distribution. It is independent of the molecular masses in narrow-distribution polymers. For the polymers investigated, a generalized dependence was obtained for the reduced duct length over which the extensional stresses relax to zero from the reduced deformation rate. This dependence takes into account the characteristic polymer relaxation times and the value of the molecular mass of the chain between the fluctuation entanglement. A considerable decrease in the duct's length-to-width ratio leads to an increase in the maximum values of the extensional stresses. A decreases in the duct entrance angle causes a reduction in the rate of increase of extensional stresses, the maximum values, and the acceleration of the relaxation processes in the duct. A decrease in the ratio of the width of the preentrance region to the duct width leads to a reduction in the maximum in extensional stresses. It is shown that one of the causes for the instability of the polymer flow in the ducts can be the rupture of polymers due to their extension in the preentrance and entrance regions. Calculations were done that describe satisfactorily the relationship between the values of the maximum extensional stresses and the shear rate and stresses on the duct wall.