Improved mechanical properties of poly(ethylene terephthalate) nanocomposite fibers

Improvements in Young's modulus and strength (tenacity) of poly(ethylene terephthalate) (PET) fibers were obtained by drawing unoriented nanocomposite filaments containing low concentrations (<3 wt%) of various organically modified montmorillonites (MMTs) in a second step at temperatures above the glass transition. Prior to melt spinning, solid‐state polymerization was used to rebuild lost molecular weight, due to MMT‐induced degradation, to a level suitable for producing high strength fibers. Greater improvements in mechanical properties occurred when the MMT stacks were intercalated with PET. A nominal 1 wt% loading of dimethyl‐dehydrogenated tallow quaternary ammonium surface modified MMT in drawn PET fiber showed a 28% and 63% increase in Young's modulus and strength, respectively. Relative to an unfilled PET fiber, these results surpassed the upper bound of the rule of mixtures estimate and suggested that both the type of surface modification and concentration of MMT affect the degree of PET orientation and crystallinity. Furthermore, drawability above T_g and elongation at break increased upon the addition of organically modified MMT to unoriented PET fibers, which was a key distinction of this work from others examining similar systems. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Peptide biosensors for the electrochemical measurement of protein kinase activity

The kinase activities are elucidated using the novel redox-active cosubstrate adenosine 5'-[gamma-ferrocene] triphosphate (Fc-ATP), which enables the kinase-catalyzed transfer of a redox active gamma-phosphate-Fc to a hydroxyamino acid. In this report, a versatile electrochemical biosensor is developed for monitoring the activity and inhibition of a serine/threonine kinase, casein kinase 2 (CK2), and protein tyrosine kinases, Abl1-T315I and HER2, in buffered solutions and in cell lysates. The method is based on the labeling of a specific phosphorylation event with Fc, followed by electrochemical detection. The electrochemical response obtained from the "ferrocenylated" peptides enables monitoring the activity of the kinase and its substrate, as well as the inhibition of small molecule inhibitors on protein phosphorylation. Kinetic information was extracted from the electrochemical measurements for the determination of K(m) and V(m) values, which were in agreement with those previously reported. Kinase reactions were also performed in the presence of well-defined inhibitors of CK2, 4,5,6,7-tetrabromo-2-azabenzimidazole, 2-dimethylamino-4,5,6,7-tetrabromo-1H-benzimidazole, and E-3-(2,3,4,5-tetrabromophenyl)acrylic acid as well as the nonspecific kinase inhibitors, staurosporine and N-benzoylstaurosporine. On the basis of the dependency of the Fc signal on inhibitor concentration, K(i) of the inhibitors was estimated, which were also in agreement with the literature values. The performance of the biosensor was optimized including the kinase reaction, incubation with Fc-ATP, and the small molecule inhibitors. Peptide modified electrochemical biosensors are promising candidates for cost-effective in vitro kinase activity and inhibitor screening assays.     

MOISTURE PROFILES IN A MODEL FOOD GEL DURING DRYING: MEASUREMENT USING MAGNETIC RESONANCE IMAGING AND EVALUATION OF THE HCKIAN MODEL

Magnetic resonance imaging (MRI) was used to obtain moisture profiles of a model food gel during drying. A cylinder of gel, 1 cm in diameter, with an initial moisture content of 76% was imaged while drying at room temperature. Moisture profiles were obtained from the imaging data by imaging calibration samples of known moisture content. Signal intensity of the images was found to be highly proportional to solids content. The moisture profiles were compared to profiles predicted by a finite difference solution of Fickian radial diffusion in a cylinder. Actual moisture profiles obtained by MRI were much flatter near the center of the cylinder, with a steeper moisture profile near the edge, compared to the typical parabolic shape of the Fickian model. The Fickian model was found to be an inaccurate predictor of the interior moisture profile of the model food gel, since effective diffusivity was found to not be solely a function of moisture content. The moisture profiles obtained provide for a method to evaluate other mass transfer models, and the methods outlined provide a technique to explore mass transfer within actual food materials during processing.     

Cis-trans isomerization of oleic,linoleic and linolenic acids

The equilibrium composition ofcis andtrans isomers obtained by isomerizing oleic, linoleic, and linolenic acids with selenium or nitrous acid has been studied using gas chromatography and infrared spectroscopy. The oleic/elaidic equilibrium mixture was found to contain 75–80% elaidic acid instead of the generally accepted 66% value. It is felt that the greater accuracy of gas chromatography and infrared analyses over older methods allows this equilibrium to be defined with greater precision. Similar studies on thecis-trans isomerization of linoleic and linolenic acids indicated that their equilibrium mixtures also contained 75–80%trans double bonds. With linoleic acid, thesetrans bonds were shown to be randomly distributed among the double bonds present. Cis-trans isomerization of linoleic or linolenic acids with selenium produced by-products having elution times equivalent to 18∶2, 18∶1, and 18∶0 on a gas chromatograph. No such by-products were observed when oleic acid was isomerized. Apparently some type of hydrogen-transfer reaction accompanies thecis-trans isomerization of polyunsaturated acids with selenium. Presented at the AOCS meeting in Toronto, Canada, 1962.     

Occurrence of 5,9,19-octacosatrienoic, 5,9-hexacosadienoic and 17-hexacosenoic acids in the marine spongeXestospongia halichondroides

The marine spongeXestospongia halichondroides contains 13% 28∶3Δ5,9,19, 27% 26∶2Δ5,9, and 21% 26∶1Δ17 in its total fatty acids. Thecis-5,cis-9,cis-19-octacosatrienoic acid structure is unknown in other living organisms.     

Analysis of triglycerides by consecutive chromatographic techniques. i.cuphea llavia seed fat

The triglycerides ofCuphea llavia var.miniata seed fat were separated according to the number of double bonds/molecule using preparative thin layer chromatography (TLC) on silicic acid impregnated with silver ion. The recovered frac-tions were quantitated by the chromotropic acid technique. Each fraction was then separated ac-cording to mol wt using gas-liquid chromatog-raphy (GLC). This multiple chromatography procedure resolvedC. llavia triglycerides into 17 different components. The triglyceride composition ofC. llavia seed fat was calculated from the above results. Since the fat contains 91.2 mole % decanoic acid, it was expected that each triglyceride molecule would contain at least two molecules of decanoic acid. Results showed this to be generally true, but sev-eral minor component triglycerides not conform-ing to this pattern were found. Presented at the AOCS Meeting in Minneapolis, 1963.     

Isovaleroyl triglycerides from the blubber and melon oils of the beluga whale (Delphinapterus leucas)

The fatty acid compositions of the blubber and melon oils from the beluga whale (Delphinapterus leucas) have been determined by gas liquid chromatography (GLC). The melon oil contains a high level (60.1 mole %) of isovaleric acid, substantial amounts of long chain branched acids (16.9%), and very little polyunsaturated material (0.5%). The blubber oil contains less isovaleric (13.2%), fewer long chain branched acids (2.7%), and appreciable amounts (10.9%) of the polyunsaturated acids typical of marine oils. The blubber and melon oils were also examined for lipid class composition by thin layer chromatography on silicic acid, direct GLC of the hydrogenated oil, and gel permeation chromatography. Both oils are composed almost entirely of triglycerides, which can be separated chromatographically into molecules containing 0, 1 and 2 isovaleric acid moieties. No triisovalerin could be detected. The blubber oil contains 68.9 mole % normal triacyl-, 24.2% diacyl-monoisovaleroyl-, and 7.0% monoacyl-diisovaleroyl-triglycerides (acyl=long chain acid). Monoacyl-diisovalerin constitutes 86.7 mole % of the melon oil. This unusual compound may play a role in the echolocation system of the beluga whale.     

A Drug Screening Pipeline Using 2D and 3D Patient-Derived In Vitro Models for Pre-Clinical Analysis of Therapy Response in Glioblastoma

Glioblastoma is one of the most common and lethal types of primary brain tumor. Despite aggressive treatment with chemotherapy and radiotherapy, tumor recurrence within 6–9 months is common. To overcome this, more effective therapies targeting cancer cell stemness, invasion, metabolism, cell death resistance and the interactions of tumor cells with their surrounding microenvironment are required. In this study, we performed a systematic review of the molecular mechanisms that drive glioblastoma progression, which led to the identification of 65 drugs/inhibitors that we screened for their efficacy to kill patient-derived glioma stem cells in two dimensional (2D) cultures and patient-derived three dimensional (3D) glioblastoma explant organoids (GBOs). From the screening, we found a group of drugs that presented different selectivity on different patient-derived in vitro models. Moreover, we found that Costunolide, a TERT inhibitor, was effective in reducing the cell viability in vitro of both primary tumor models as well as tumor models pre-treated with chemotherapy and radiotherapy. These results present a novel workflow for screening a relatively large groups of drugs, whose results could lead to the identification of more personalized and effective treatment for recurrent glioblastoma.     

Stress and Failure Prediction for the Drying,Tempering, and Cooling of Extruded Durum Semolina

ABSTRACT

This work presents a method to predict the stress and breakage that is caused by the drying of hygros-copic materials. Stresses were predicted for a viscoclasic cylinder with the properties of extruded durum semolina, or pasta noodles. The stresses were calculated as functions of the transient moisture and tem-perature gradients in the material which were predicted for the combined processes of drying, tempering,and cooling. The time and radial position of failure were predicted based on failure data for extruded semolina.

Isotherm data for extruded durum semolina were obtained for temperatures from 40 to 60°C and for relative humidities from 75 to 95%. The results were fit with a modified form of Henderson's equation.Thermal conductivities were measured for temperatures from 30 to 50°C and a moisture range of 12 to 27% (dry basis).

A drying model based on the principles of irreversible thermodynamics; (Fortes, 1978; Fortes and Okos, 1981a, 1981b) was used to successfully predict drying curves for a range of experimental conditions. Transient moisture and temperature profiles were calculated numerically, and a receding evapora-tion front was predicted to exist. Drying was predicted to be a coupled liquid, vapor, and heat transport phenomena.

The drying data were used in a stress analysis of a Maxwell viscoelastic cylinder to predict trends in stress development under various contiitions of combined drying, tempering, and cooling. High temperature-high humidity drying, HTHH, (lOO°C, 65% RH) was compared with low temperature-low humidity drying, LTLH, (53°C, 13% RH). The HTHH drying offered definite advantages in terms of reduced product breakage susceptibility. The reasons for those advantages were increased failure strength and a decreased moisture gradient at the end of drying. In a five-stage drying process, the cooling stage was shown to have a significant impact on the predicted levels of stress and on the strength of the extruded material. Analysis of the model suggested that gradual temperature and humidity transitions from stage to stage in multistage processes were important to product quality.