Thermo-oxidative degradation of polyolefins observed by isothermal long-term DTA

Isothermal differential thermal analysis (DTA) is well known for measuring thermal stability of polyolefins by determining the oxidative induction time at elevated temperatures. Oxidative induction time, measured up to 7,000 hours and over a temperature range from 240°C to 120°C, has been used to study the stability of polybutene-1 and crosslinked polyethylene in the melt state. The Arrhenius plots of DTA results show that straight line extrapolation from high to low temperatures is not possible. Thermoanalytically measured oxidation induction times and mechanical failure in oven aging experiments agree for polybutene and crosslinked polyethylene, Measurements of molecular weight and of mechanical properties of polybutene-1 during the induction period of oven aging experiments at low temperatures revealed that molecular weight and tensile properties are not sensitive indicators for the beginning of aging. The state of deterioration can be estimated easier by measurement of residual lifetime in the isothermal DTA experiment. Diffusion processes of stabilizers in polyolefins, as well as the consumption of stabilizer at elevated temperatures, especially during the induction period also was observed by DTA. Finally the extraction of stabilizer by hot water was measured by isothermal DTA.     

Testing a short-term feeding trial to assess compositional and histopathological changes in hearts of rats fed vegetable oils

Male, female and castrated rats, three wk of age, were fed a low-fat diet for 14 wk followed by high-fat diets (20% by weight) for one wk containing graded levels of erucic acid from 1 to 50%, to evaluate the effect of short-term feeding and interaction of male sex hormones on formation of heart lesions. Some rats within each group were returned to the low-fat diet for one wk after the test period. For comparison, one group of three-wk-old male rats was fed the high fat 50% erucic acid diet for 15 wk. Erucic acid depressed growth rate and food consumption and increased cardiac lipidosis and triglycerides proportional to the erucic acid content of the diet. There were no sex differences, and the effects disappeared once rats were returned to the low-fat diet for one week. There was a significance (P<0.05) in the incidence of myocardial necrosis among male rats fed increased levels of erucic acid for one week, but the response was not linear to the increase in dietary erucic acid. Furthermore, the response was much less than in males fed the 50% erucic acid diet continually for 15 weeks. These results suggest that the short-term model is not a suitable substitute for the long-term feeding trial to test the cardiopathogenicity of a vegetable oil. The significantly lower incidence in myocardial lesions in female and castrated male rats compared with male rats suggests involvement of sex hormones. However, the process appears to be long term, since changes in cardiac lipids and their fatty acid pattern between sexes became evident after one wk on diet but was significant only after long-term feeding. Deceased.     

Quantitating heart lipids: Comparison of results obtained using the Iatroscan method with those from phosphorus and gas chromatographic techniques

The precision and accuracy of the Iatroscan method was evaluated by comparing the results obtained with established phosphorus and gas chromatographic techniques. A complete lipid class analysis of rat heart lipids was chosen in order to evaluate the performance of the Iatroscan method for biological samples which contained both neutral lipids and phospholipids. A partial scan and repeat development with chloroform/methanol/water (68.5∶29∶2.5) was introduced to achieve consistently good separations of the phospholipids on the Chromarods in the Iatroscan method. The results showed that the precision of the Iatroscan method for some lipid classes was comparable to that of phosphorus or gas chromatographic techniques, while for other lipid classes it was lower. Compared to the data obtained using the phosphorus method, the Iatroscan data were generally similar, while the gas chromatographic method generally gave lower values. These findings, together with the advantages of time required for analysis, size of sample, and universality of detection, suggest that the Iatroscan is a valuable complementary method for complex lipid analyses.     

Fluoroscopic MR imaging at 0.064 Tesla

The authors developed a system for ultrafast magnetic resonance imaging (MRI) protocols at low field. The system design permits the acquisition of the raw data in the background while the reconstruction and display steps repeat as fast as they can in the foreground. The performance speeds depends partly on the desired use. By collecting raw data at a rate of 20 ms per echo with an echo delay of 9 ms, a complete data cycle for a 128x64 image takes 1.28 s. However, once half of that data is incorporated into the reconstruction, the image appears complete. Using this set of parameters the authors were able to get the rate of the recon/display loop to paint about two times per completed raw data cycle, showing an entirely new image at least once per second with an apparent frame rate of two per second. Interleaving of two or three orthogonal scans reduces the speed of update but provides better information. The authors discuss the system design for rapid scan/recon/display and demonstrate the image quality available at low field strength with scan times below one second.     

Low-field 3-DFT MRI: conceptual, analytical, and experimental aspects

Three-dimensional Fourier transform (3-DFT) magnetic resonance imaging (MRI) offers advantages in terms of signal-to-noise (S/N) per unit of time for the case where a large number of slices is desired. This advantage is enhanced when the relaxation time, T(1 ), is short. Because time limitations in 3-DFT imaging force the use of short time intervals, TR, between excitations of a slice, lesion contrast is often undesirable at mid-and high-field strength even when the S/N is good. At low fields, where T(1) values are short, high S/N and contrast can both be achieved with 3-DFT MR images. The conceptual and analytical aspects of low-field 3-DFT MRI are presented and demonstrated at 640 G.     

Microstructure and origin of cross-tie fibrils in crazes

Crazes were grown in thin films of polystyrene (PS) at various temperatures and the resulting craze fibril microstructures were examined using low-angle electron diffraction (LAED). A quasi-regular array of cross-tie fibrils pull the main fibrils away from the tensile axis by an angle ± /2°. As a result, the LAED patterns from crazes grown at temperatures T<50°C exhibited split diffraction lobes centred about the equatorial axis of the LAED pattern. It was found that decreased with increasing crazing temperature and that the split lobes could no longer be resolved at the highest temperatures. Diffuse meridional diffraction spots due to scattering from the quasi-regular array of cross-tie fibrils were seen in the LAED patterns from crazes grown at low temperatures. The spacing of the cross-tie fibrils, R, determined from these patterns, was found to increase with the crazing temperature. A new model of craze widening was proposed that accounts for the formation of cross-tie fibrils by allowing some of the entangled polymer strands which bridge two fibrils in the active zone to survive fibrillation. Cross-tie fibrils are created when several such strands pile up locally, and the craze/bulk interface bypasses the pile-up.     

Healing Effect of Controlled Anti‐Electromigration on Conventional and High‐Tc Superconducting Nanowires

The electromigration process has the potential capability to move atoms one by one when properly controlled. It is therefore an appealing tool to tune the cross section of monoatomic compounds with ultimate resolution or, in the case of polyatomic compounds, to change the stoichiometry with the same atomic precision. As demonstrated here, a combination of electromigration and anti‐electromigration can be used to reversibly displace atoms with a high degree of control. This enables a fine adjustment of the superconducting properties of Al weak links, whereas in Nb the diffusion of atoms leads to a more irreversible process. In a superconductor with a complex unit cell (La_2?x Ce_x CuO₄), the electromigration process acts selectively on the oxygen atoms with no apparent modification of the structure. This allows to adjust the doping of this compound and switch from a superconducting to an insulating state in a nearly reversible fashion. In addition, the conditions needed to replace feedback controlled electromigration by a simpler technique of electropulsing are discussed. These findings have a direct practical application as a method to explore the dependence of the characteristic parameters on the exact oxygen content and pave the way for a reversible control of local properties of nanowires.     

Biocompatible nano-gallium/hydroxyapatite nanocomposite with antimicrobial activity

Intensive research in the area of medical nanotechnology, especially to cope with the bacterial resistance against conventional antibiotics, has shown strong antimicrobial action of metallic and metal-oxide nanomaterials towards a wide variety of bacteria. However, the important remaining problem is that nanomaterials with highest antibacterial activity generally express also a high level of cytotoxicity for mammalian cells. Here we present gallium nanoparticles as a new solution to this problem. We developed a nanocomposite from bioactive hydroxyapatite nanorods (84?wt %) and antibacterial nanospheres of elemental gallium (16?wt %) with mode diameter of 22?±?11?nm. In direct comparison, such nanocomposite with gallium nanoparticles exhibited better antibacterial properties against Pseudomonas aeruginosa and lower in-vitro cytotoxicity for human lung fibroblasts IMR-90 and mouse fibroblasts L929 (efficient antibacterial action and low toxicity from 0.1 to 1?g/L) than the nanocomposite of hydroxyapatite and silver nanoparticles (efficient antibacterial action and low toxicity from 0.2 to 0.25?g/L). This is the first report of a biomaterial composite with gallium nanoparticles. The observed strong antibacterial properties and low cytotoxicity make the investigated material promising for the prevention of implantation–induced infections that are frequently caused by P. aeruginosa.     

Real-time patch-cram detection of intracellular cGMP reveals long-term suppression of responses to NO and muscarinic agonists

Cyclic GMP (cGMP) is a crucial intracellular messenger in neuronal, muscle, and endocrine cells. The intracellular concentration of cGMP is regulated by various neurotransmitters, including acetylcholine (ACh) and nitric oxide (NO). While much is known about the biochemical steps leading to cGMP synthesis, little is known about cGMP kinetics in intact cells. Here, we use "patch-cramming," in which an excised, inside-out membrane patch containing cyclic nucleotide-gated ion channels is used as a biosensor, to obtain the first real-time measurements of cGMP in intact cells. Patch-cramming experiments on neuroblastoma cells show that both muscarinic agonists and NO rapidly elevate cGMP. NO elicits cGMP responses repeatedly without decrement, whereas responses to muscarinic agonists exhibit a profound and prolonged desensitization. Remarkably, muscarinic agonists also cause long-term (>30 min) suppression (LTS) of cGMP responses elicited by NO. Biochemical measurements reveal that rat sympathetic neurons also exhibit LTS of cGMP, suggesting that LTS is a widespread mechanism that may contribute to synaptic plasticity.