Effects of static axial strain on the tensile properties and failure mechanisms of self-assembled collagen fibers

Collagen fibers form the structural units of connective tissue throughout the body, transmitting force, maintaining shape, and providing a scaffold for cells. Our laboratory has studied collagen self-assembly since the 1970s. In this study, collagen fibers were self-assembled from molecular collagen solutions and then stretched to enhance alignment. Fibers were tested in uniaxial tension to study the mechanical properties and failure mechanisms. Results reported suggest that axial orientation of collagen fibrils can be achieved by stretching uncrosslinked collagen fibers. Stretching by about 30% not only results in decreased diameter and increased tensile strength but also leads to unusual failure mechanisms that inhibit crack propagation across the fiber. It is proposed that stretching serves to generate oriented fibrillar substructure in self-assembled collagen fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1429–1440, 1997     

The solubility of methane in aqueous solutions of monoethanolamine,diethanolamine and triethanolamine

The solubility of methane in 3 kmol/m³ solutions of monoethanolamine, diethanolamine, and triethanolamine was measured from 25° to 125°C and pressures up to about 13 MPa. Measurements were also made for the solubility of methane in water at 25° to 125°C and pressures up to 18 MPa in order to confirm the accuracy of the experimental technique. It is demonstrated that methane is more soluble (in terms of mole fraction) in the amine solution than in pure water. Furthermore, the solubility is an increasing function of the size of the alkanolamine. The solubility data were modeled using a Henry's-law approach and the results summarized in terms of salting-in coefficients.     

Isomeric Carborane Neuromuscular Blocking Agents

We synthesized a family of neuromuscular blocking agents (NMB) based on decamethonium, but containing a carborane cluster in the methylene chain between the two quaternary ammonium groups. The carborane cluster isomers o-NMB, m-NMB, and p-NMB were tested in animals for neuromuscular block and compared with agents used clinically: rocuronium and decamethonium. All three isomers caused reversible muscle weakness in mice as determined by grip strength and inverted screen tests, with a potency rank of p-NMB > rocuronium > decamethonium > m-NMB > o-NMB. The mechanism of action of the compounds was determined by using the in vitro rat phrenic nerve hemi-diaphragm preparation and electrophysiologic measurements in cells. Neostigmine reversed hemi-diaphragm weakness caused by the three isomers and rocuronium, but not succinylcholine. In electrophysiologic recordings of currents through acetylcholine receptor channels, the carborane compounds did not activate channel activity but did inhibit channel activation by acetylcholine. These results demonstrate that the carborane neuromuscular blocking agents are non-depolarizers in contrast to the depolarizing action of the parent compound.     

Dynamics of diffusion with reversible binding in microscopically heterogeneous membranes: General theory and applications to dermal penetration

Essentially all biological membranes and tissues exhibit microscopic heterogeneity in the form of cellular, lamellar or other organization, and molecular diffusion in these materials is frequently slowed by binding to elements of the microstructure (“trapping”). This paper addresses situations where binding is describable as a linear reversible process at the microscale, with forward (“on”) and reverse (“off”) rate constants k_f(x) and k_r(x) that vary with position. Very commonly it is tacitly assumed that the macroscopically observable binding behavior should follow the same rate law with the substitution of appropriate effective (tissue-average) rate constants and . This assumption is probed theoretically for spatially periodic microstructures using a judicious application of numerical calculations and asymptotic analysis to prototypical one-dimensional transport problems. We find that smooth microscopic variations produce an anomalous macroscopic exchange between free and bound solute populations that is not well described by a single pair of forward and reverse rate constants, i.e., violates the usual paradigm. In contrast, discontinuous variations (as in two-phase composite media) are evidently well described by the usual paradigm. For the latter case we derive simple and general algebraic equations giving and , and generalize them to any three-dimensional unit cell representing the tissue microstructure. Validity of the formulas is demonstrated with reference to a concrete example describing molecular diffusion through the stratum corneum (barrier) layer of skin, comprising lipid (intercellular) and corneocyte (cellular) phases. Our analysis extends coarse-graining (homogenization, effective transport) theory for irreversible trapping systems to the reversible case.     

Effects of alkyl substitution on the physical properties and gas transport behavior in selected poly(R-phenoxyphosphazenes)

A systematic preparation of alkyl substituted phenoxyphosphazene polymers was performed and their gas transport properties determined. In this study, phosphazenes substituted with 4-methylphenol, 4-ethylphenol, and 4-isopropylphenol are reported. An additional polymer substituted with 4-tert-butylphenoxy-1-ethanol also was synthesized in this work. Data derived for these materials, including chemical, thermal and gas transport characterization, were compared to previous reports discussing poly[bis-phenoxyphosphazene] and its analog with tert-butyl substitution: poly[bis-(4-tert-butylphenoxy)phosphazene]. The tert-butyl moiety influences orderly chain packing, presumably through steric hindrance that can influence aromatic π-stacking. For the new poly[(alkylphenoxy)phosphazenes], semicrystallinity is maintained and the added steric bulk serves to decrease the polymer glass transition temperature (Tg) and increase both permeability and selectivity for the gas pairs: O₂/N₂ and CO₂/CH₄. Removal of the tert-butyl moiety from the immediate vicinity of the backbone through a flexible spacer serves to depress the Tg as compared to poly[bis-(4-tert-butylphenoxy)phosphazene], but provides no performance enhancement for gas transport.     

The role of particle size of particulate nano-zinc oxide wood preservatives on termite mortality and leach resistance

Historically most residential wood preservatives were aqueous soluble metal formulations, but recently metals ground to submicron size and dispersed in water to give particulate formulations have gained importance. In this study, the specific role nano-zinc oxide (ZnO) particle size and leach resistance plays in termite mortality resulting from exposure to particulate ZnO-treated wood was investigated. Southern yellow pine (SYP) sapwood impregnated with three concentrations of two particle sizes (30 and 70 nm) of ZnO were compared to wood treated with soluble zinc sulphate (ZnSO₄) preservative for leach resistance and termite resistance. Less than four percent leached from the particulate nano-ZnO-treated specimens, while 13 to 25% of the zinc sulphate leached from the soluble treated wood. Nano-ZnO was essentially non-leachable from wood treated with 5% formulation for the 30-nm particle size. In a no-choice laboratory test, eastern subterranean termites (Reticulitermes flavipes) consumed less than 10% of the leached nano-ZnO-treated wood with 93 to 100% mortality in all treatment concentrations. In contrast, termites consumed 10 to 12% of the leached ZnSO₄-treated wood, but with lower mortality: 29% in the 1% treatment group and less than 10% (5 and 8%, respectively) in the group of wood blocks treated with 2.5 and 5.0% ZnSO₄. We conclude that termites were repelled from consuming wood treated with nano-ZnO, but when consumed it was more toxic to eastern subterranean termites than wood treated with the soluble metal oxide formulation. There were no differences in leaching or termite mortality between the two particle sizes of nano-ZnO.     

Simulation of the injection process in resin transfer molding

A simulation based on Darcy's law for modeling mold filling in resin transfer molding has been developed. The simulation uses a new Flow Analysis Network (FAN) technique to predict and track the movement of the free-surface, and a finite element method to solve the governing equation set for each successive flow front location. A variety of element types have been incorporated into the simulation, enabling modeling of flow for a variety of conditions of industrial interest including runner distribution systems, “2.5-D” shell geometries, and fully 3-D flows. The FAN technique developed here has two main benefits: it enables conservation of mass, even for highly distorted element shapes, and also, allows elements of different dimension to be simultaneously used in a single simulation. At present, the simulation predicts flow front position as a function of time, and the pressure distribution during the filling process for a number of inlet gating conditions. A number of examples are presented and discussed to highlight the simulation's capabilities, including the filling of a complex automotive part.     

Formation polarity dependent improved resistive switching memory characteristics using nanoscale (1.3 nm) core-shell IrOx nano-dots

ABSTRACT: Improved resistive switching memory characteristics by controlling the formation polarity in an IrOx/Al2O3/IrOx-ND/Al2O3/WOx/W structure have been investigated. High density of 1 × 1013/cm2 and small size of 1.3 nm in diameter of the IrOx nano-dots (NDs) have been observed by high-resolution transmission electron microscopy. The IrOx-NDs, Al2O3, and WOx layers are confirmed by X-ray photo-electron spectroscopy. Capacitance-voltage hysteresis characteristics show higher charge-trapping density in the IrOx-ND memory as compared to the pure Al2O3 devices. This suggests that the IrOx-ND device has more defect sites than that of the pure Al2O3 devices. Stable resistive switching characteristics under positive formation polarity on the IrOx electrode are observed, and the conducting filament is controlled by oxygen ion migration toward the Al2O3/IrOx top electrode interface. The switching mechanism is explained schematically based on our resistive switching parameters. The resistive switching random access memory (ReRAM) devices under positive formation polarity have an applicable resistance ratio of > 10 after extrapolation of 10 years data retention at 85°C and a long read endurance of 105 cycles. A large memory size of > 60 Tbit/sq in. can be realized in future for ReRAM device application. This study is not only important for improving the resistive switching memory performance but also help design other nanoscale high-density nonvolatile memory in future.     

Increasing the firmness of wax-based oleogels using ternary mixtures of sunflower wax with beeswax:candelilla wax combinations

Oleogels were prepared with 5% wax in soybean oil using mixtures of beeswax (BW) and candelilla wax (CLW) with ratios of 10:90, 30:70, 50:50, and 60:40 BW:CLW, and the same series where 10% of the total wax was substituted with sunflower wax (SFW). The hypothesis that SFW would increase the firmness of the oleogels without affecting the melting properties was tested. Firmness of one-wax oleogels decreased from SFW > CLW > BW. Oleogels with 50:50 BW:CLW and 60:40 BLW:CLW had equal firmness to pure 5% SFW oleogels. SFW significantly increased oleogel firmness and reduced the softening that occurred between 4°C and 22°C. Increased firmness was also found with rice bran wax and behenyl-behenate (C44) addition, but not with wax esters with chain lengths ranging from 30 to 40 carbons (C30 to C40). By differential scanning calorimetry, SFW significantly decreased the melting point of oleogels with 10:90 and 30:70 BW:CLW mixtures but significantly increased the melting point of those with 50:50 and 60:40 BW:CLW mixtures. However, the solid fat content melting curves were not significantly influenced by SFW addition. These results indicate that mixed wax oleogels had greater hardness and elasticity, and that the long chain wax esters contributed by SFW helped to improve the strength of oleogels without negatively affecting their melting properties.     

Formation of hydrophilic starch coatings on polyethylene films

Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent‐extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03–0.05 mg per cm² of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water‐wet PE surfaces, air‐dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch‐coated film surfaces showed that starch was deposited as particles less than 1 μm in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface‐deposited starch in all experiments contained 90–100% amylose; and exhibited the same V_h X‐ray diffraction pattern, indicative of helical inclusion complex formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1781–1788, 2002; DOI 10.1002/app.10589