Solid-state characterization of polyethylene reactor powders and their structural changes upon annealing

Polyethylene reactor powders prepared under different conditions were characterized using transmission electron microscopy, ¹H nuclear magnetic resonance and X-ray diffraction techniques. The molecular weight of the polyethylene reactor powders was around 1 × 10⁵. A unique domain morphology, quite different from the usual melt- or solution-crystallized lamellar structure, was observed, independent of polymerization temperature (T_poly). Annealing of reactor powders caused the aggregation of these crystalline domains, due to the significant molecular motion of the amorphous chains, before melting. The critical temperature was 20 °C higher than each T_poly, and corresponded to the temperature at the active catalyst site producing the chain growth. The morphologies of powders prepared at the lower T_poly contained smaller crystals that exhibited a constrained monoclinic form. In contrast, only usual orthorhombic crystals of larger size were found within the powder prepared at the higher T_poly. These results suggest that the competitive processes of chain propagation and crystal growth upon polymerization may lead to unique variations of the crystalline and amorphous phases, but with similar intermediate components in the phase that connects them.     

Incorporation of a well-defined polyether side-chain into segmented poly(ether-urethane urea) and examination for blood-compatibility

A new method of introducing a hydrophilic polyether side chain into segmented polyurethane using a polypropylene oxide macromer with 1,3-diol at one chain-end, which behaves as chain extender, is described. In this procedure, a molecular-designed side-chain is incorporated quantitatively and directly into polyurethane biomedical elastomer. The design is also of interest to biomaterials in artificial organs.     

Preparation and characterization of stable dispersions of carbon black and nanodiamond in culture medium for in vitro toxicity assessment

Stable dispersions of carbon black and nanodiamond in culture medium were prepared by adding a pre-mixed dispersion of commercial carbon black or nanodiamond in aqueous bovine serum albumin (BSA) solution to culture medium. Dynamic light scattering revealed that carbon black and nanodiamond dispersions prepared in both NaCl solution and culture medium were highly stable. From DLVO theory and the results of zeta potential measurements, the theoretical effect of the electrostatic interactions between adsorbed BSA molecules was found to be minimal. The asymmetric flow field-flow fractionation measurements revealed that 0.05 or 0.56 mg/mL of BSA molecules were adsorbed on 0.11 or 1.09 mg/mL of carbon black, respectively, indicating 1:2 complexation of BSA with the colloidal particles. In the case of nanodiamond, 0.06 or 0.60 mg/mL of BSA molecules were adsorbed on 0.10 or 1.05 mg/mL of nanodiamond, respectively, indicating 1:2 complexation of BSA, which is the same ratio as in the case of carbon black. The adsorbed BSA molecules served as an effective stabilizing agent for the carbon black and nanodiamond, ensuring dispersion stability for at least 1 week. The preparation of the dispersions can be easily carried out by other researchers for toxicity studies.     

Visible Light Irradiation of [60]Fullerene Causes Killing and Initiation of Transformation in Balb/3T3 Cells

Cell transformation in vitro is a model of carcinogenesis in vivo. Two-stage transformation assay increases the sensitivity of cells to chemicals and permits detection of carcinogens acting as initiating agents. [60]Fullerene (C₆₀) was cytotoxic in BALB/3T3 cells when it was irradiated by visible light, but not without light irradiation. Under conditions when C₆₀ was cytotoxic, it acted as an initiating agent for cell transformation, but it did not act as a complete transforming agent. the initiating activity of visible-light-irradiated C₆₀ was statistically significant in a modified two-stage transformation assay including a procedure for replating cells treated by C₆₀ and light, but it was equivocal in the standard two-stage transformation assay.     

Photooxidative degradation of polyethylene containing flame retardants by monochromatic light

Photodegradation of incombustible polymer materials [high-density (HD) and low-density (LD) polyethylene (PE) containing 0.5 to 2.0 phr of decabromodiphenyl ether (DBDE) or tetrabromobisphenol A (TBA) as a flame retardant] were studied using an Okazaki Large Spectrograph (OLS). Samples were irradiated in air at 23°C with monochromatic light of wavelengths at 260, 280, 300, 320, 340, and 360 nm. Ultraviolet and Fourier transform infrared (FTIR) spectra were taken to estimate the chemical changes caused by photoirradiation. Molecular weight change was followed by gel permeation chromatography (GPC) measurements. It was found that the photostability of PE samples was reduced by the addition of flame retardants. The threshold wavelengths of photodegradation are 320 nm and 360 nm for PE–TBA samples and PE–DBDE samples, respectively. Main-chain scission is favored when the irradiation was carried out with the light of wavelength 300 nm for HDPE–DBDE and HDPE–TBA samples. The most effective irradiation wavelengths for crosslinking are found to be 300 nm and 280 nm for LDPE–DBDE and LDPE–TBA samples, respectively. 1995 John Wiley & Sons, Inc.     

Nedaplatin and 5-FU combined with radiation in the treatment for esophageal cancer

A direct differentiation of the internal and external drug-deposition pattern into hair was made using two fluorescent dyes and fluorescence microscopy after systemic administration to mice or external exposure of untreated hair. Mice (23 days old, C57 and Balb/C) were administered either rhodamine or fluorescein intraperitoneally at varied doses on 3 consecutive days of 3 weeks, and hair was sampled 1 week later. Another group was given 10 mg/kg rhodamine or 100 mg/kg fluorescein and sampled at time points from 5 min to 168 hr. The time courses of external deposition of rhodamine and fluorescein into untreated hair were examined after hair was soaked in 0.1 mg/ml solutions at pH 3, pH 6, and pH 9 aqueous buffer or methanol. The hair was then extracted in pH 6 phosphate buffer or methanol for 24 hr. In vivo accumulation was distinguishable as fluorescent bands along the length of the hair for rhodamine and fluorescein. The pattern of in vivo deposition appears to arise from the rapid accumulation within the cortex and medulla, with little deposition evident in the cuticle. Neither phosphate buffer nor methanol washes affected the intensity of fluorescence in the hair. External loading of rhodamine into the hair resulted in staining of the junctions of cuticle scales. This pattern persisted even after 12 hr of solution exposure. Extraction with pH 6 phosphate buffer or methanol did not remove rhodamine. Fluoroscein followed a similar pattern, with maximum fluorescence when hair was loaded in pH 6 100mM phosphate buffer and nominal staining when loaded in pH 9 100 mM Tris buffer or methanol. Soaking the hair in pH 6 buffer, but not methanol, removed some fluorescein. These results demonstrate that compounds in the circulation can rapidly diffuse into the forming cortex and medulla, where rapid associations occur with elongating intermediate filaments specific to the medulla and cortex. These compounds can become significantly occluded within the mature matrix and are resistant to removal in aqueous or methanolic solutions.     

Photodegradation of rigid PVC formulations. I. Wavelength sensitivity to light-induced yellowing by monochromatic light

Light-induced yellowing of extruded rigid poly(vinyl chloride) formulations containing 0, 2.5, and 5 phr of titanium dioxide under exposure to monochromatic light was studied. Both photoyellowing and photobleaching were observed as wavelength-dependent phenomena in the range of 280–500 nm. Action spectra for yellowing of the different compounds were similar. In the case of the formulation with no titanium dioxide, significant color changes were observed on the back surface of the sample, indicating transmission of the longer wavelength light through the 1-mm thickness of the sample.     

Spiral computed tomography for bilioenteric anastomotic stricture

Spiral computed tomography scanning after intravenous cholangiography (IVC-SCT) was used to assess the anatomy of the biliary tree and anastomosis in a 7-year-old girl with recurrent cholangitis 5 years after surgical excision of a choledochal cyst. The technique clearly visualized the stenosis of the hepaticojejunostomy and hepatic duct and the dilated intrahepatic ducts. IVC-SCT provides a precise, prompt, and accurate image with minimal invasiveness and is especially suitable for the preoperative evaluation of pediatric patients.     

Preparation of long sticky ends for universal ligation-independent cloning: Sequential T4 DNA polymerase treatments

Ligation-independent cloning (LIC) is a useful method for efficient directional cloning of a PCR product. LIC requires a specially designed vector containing a long stretch of sequence that is missing any one of the four nucleotides. When the linearized vector is treated with T4 DNA polymerase, in the presence of the absent base, long single-stranded overhangs are generated that are suitable for cloning. In this study, long and efficient sticky ends for LIC were produced by sequential T4 DNA polymerase treatments at non-specific sequences on a commercially available vector. All restriction enzyme sites become available in the current LIC.     

Comparative studies of glycoprotein Ib in heparin coated and nonheparin coated extracorporeal circulation circuits

Contact between blood and artificial materials has various effects on blood. Impairment of platelet function is an especially important and well known effect, but its precise mechanism is not clearly understood. The authors constructed a circulation model to investigate the effect of extracorporeal circulation on platelet membrane glycoproteins (GPs), especially GP Ib, and to compare the changes in GP Ib in heparin coated (group C) and nonheparin coated (group N) circuits. As determined by flow cytometry, GP Ib in both groups decreased on initiating circulation, but the decrease in group N was significantly larger than that in group C. There was no observed change in GP IIb/IIIa levels in either group. The extent of shear stress induced platelet aggregation significantly decreased during circulation in both groups. Decreases in the extent of shear stress induced platelet aggregation were significantly less with the use of heparin coated circuits. In addition, the amount of GP Ib in the high speed pellet decreased progressively during circulation in both groups. In contrast, the amount of GP Ib in the Triton insoluble (low speed) pellet increased dramatically during circulation. However, expression of GP Ib in the Triton soluble platelet fraction was low in both groups. From the results, it was concluded that the cause of the decrease in platelet function during extracorporeal circulation is attributable to the internalization of GP Ib from the platelet surface inside the platelet. It also can be said that a heparin coated circuit is one effective means of controlling this change.