Single‐step synthesis of a radically polymerizable 1,1′‐bi‐2‐naphthol derivative for asymmetric catalysis

A new polymerizable 1,1′‐bi‐2‐naphthol derivative for polymer‐supported catalytic asymmetric synthesis is presented. The synthesis is conducted within a single reaction step, which is a major advantage over other approaches presented in the literature. The ligand‐bearing polymer is prepared through copolymerization with N‐isopropylacrylamide. Preliminary experiments on the utility in catalytic asymmetric alkylation reactions reveal the accessibility and activity of the polymer‐attached catalysts. The stereoselectivity of the reaction is found to be somewhat lower than for reactions performed in the presence of free 1,1′‐bi‐2‐naphthol, and thus requires further optimization. The enantiomeric excess of the reaction products was determined via ¹H NMR spectroscopy after chiral derivatization with (R)‐α‐methylbenzyl isocyanate. © 2015 Society of Chemical Industry     

Short communication: Repeatability of intravenous glucose tolerance test traits in young Holstein-Friesian cattle

Few studies have compared individual variability of an intravenous glucose tolerance test (ivGTT) obtained daily in young cattle. The objective of this study was to evaluate the repeatability of glucose traits and insulin responses derived from ivGTT during 3 consecutive days in Holstein-Friesian cattle (bulls: n = 4, steers: n = 3, heifers: n = 3). Blood collections were performed from min 0 (basal concentrations) to min 63 (last measurement). Additional estimates included maximal concentration for glucose and insulin, glucose half-life time (GHLT), and glucose and insulin area under the curve. Glucose traits showed higher repeatability when compared with insulin responses. On average, the glucose trait and insulin response with the lowest coefficient of variation was GHLT (0.7%) and insulin area under the curve (21.3%), respectively. In addition, a general linear model with repeated measures was used to test for significant differences in glucose and insulin concentrations over time at different trial days. Both glucose and insulin concentrations were influenced by time point but not by trial day or time point × trial day. The results from this study showed that individual insulin responses were more variable than glucose traits. The high repeatability of GHLT evidenced the strict regulatory glucose disposal mechanisms occurring in young Holstein-Friesian cattle, whereas insulin responses showed high variability despite controlled management and nutritional practices.     

Reduction of the elongation at break of thermoplastic polyolefins through melt blending with polylactide and the influence of the amount of compatibilizers and the viscosity ratios of the blend components on phase morphology and mechanics

The objective of this work is the synthesis of a polypropylene/ethylene‐propylene‐rubber (TPO)/polylactide (PLA)/compatibilizer (PVM) blend to reduce the elongation at break of TPO by blending TPO with brittle PLA. Three TPO types with different viscosities were melt blended with PLA and an ethylene/n‐butylacrylate/glycidyl methacrylate terpolymer (PVM) as reactive compatibilizer. All blends had a constant PLA amount of 30 wt%. Two parameters were varied in the experiments, viscosity of the TPO types, and amount of PVM used in the blends. Both parameters played important roles in reducing the nominal elongation at break compared to pure TPO foils and influencing the phase morphology of extruded blend foils. The nominal elongation at break could be reduced by 100‐150% through blending TPO with PLA and PVM. Characterization regarding the blend morphology, especially the size and shape of the dispersed PLA phase in the TPO matrix was done by Environmental Scanning Electron Microscopy (ESEM) images. Investigations of the morphology showed that size and shape of dispersed PLA phases are dependent on the viscosity ratios of the blend components and on the amount of compatibilizer in the blend. AFM images of the polymer blends reveal soft rubbery layers around the dispersed PLA phases. POLYM. ENG. SCI., 56:905–913, 2016. © 2016 Society of Plastics Engineers     

Analysis of microRNAs in Exosomes of Breast Cancer Patients in Search of Molecular Prognostic Factors in Brain Metastases

Brain metastases are the most severe tumorous spread during breast cancer disease. They are associated with a limited quality of life and a very poor overall survival. A subtype of extracellular vesicles, exosomes, are sequestered by all kinds of cells, including tumor cells, and play a role in cell-cell communication. Exosomes contain, among others, microRNAs (miRs). Exosomes can be taken up by other cells in the body, and their active molecules can affect the cellular process in target cells. Tumor-secreted exosomes can affect the integrity of the blood-brain barrier (BBB) and have an impact on brain metastases forming. Serum samples from healthy donors, breast cancer patients with primary tumors, or with brain, bone, or visceral metastases were used to isolate exosomes and exosomal miRs. Exosomes expressed exosomal markers CD63 and CD9, and their amount did not vary significantly between groups, as shown by Western blot and ELISA. The selected 48 miRs were detected using real-time PCR. Area under the receiver-operating characteristic curve (AUC) was used to evaluate the diagnostic accuracy. We identified two miRs with the potential to serve as prognostic markers for brain metastases. Hsa-miR-576-3p was significantly upregulated, and hsa-miR-130a-3p was significantly downregulated in exosomes from breast cancer patients with cerebral metastases with AUC: 0.705 and 0.699, respectively. Furthermore, correlation of miR levels with tumor markers revealed that hsa-miR-340-5p levels were significantly correlated with the percentage of Ki67-positive tumor cells, while hsa-miR-342-3p levels were inversely correlated with tumor staging. Analysis of the expression levels of miRs in serum exosomes from breast cancer patients has the potential to identify new, non-invasive, blood-borne prognostic molecular markers to predict the potential for brain metastasis in breast cancer. Additional functional analyzes and careful validation of the identified markers are required before their potential future diagnostic use.     

Impact of the coating process on the molecular structure of starch‐based barrier coatings

Molecular analysis of starch structure can be used to explain and predict changes in physical properties, such as water vapor and oxygen barrier properties in packaging materials. Solution casting is a widely used technique to create films from starch formulations. This study compared the molecular properties of these standard films with those of experimental coatings applied to paper in laboratory‐scale and pilot‐scale trials, with all three techniques using the same starch formulation. The results revealed large differences in molecular structure, i.e., cross‐linking and hydrolysis, between films and coatings. The main differences were due to the shorter drying time allowed to laboratory‐scale coatings and the accelerated drying process in pilot trials owing to the high energy output of infrared dryers. Furthermore, surface morphology was highly affected by the coating technique used, with a rougher surface and many pinholes occurring in pilot‐scale coatings, giving lower water vapor permeability than laboratory‐scale coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41190.     

Optimization of a Continuous Precipitation Process to Produce Nanoscale BaSO4

The effect of supersaturation, reaction temperature, and mixing intensity on particle size was investigated. Sterical stabilization of barium sulfate suspensions was applied to prevent formation of agglomerates. This allowed a reactant ratio of 1:1, thus maximizing product yield. The local supersaturation is strongly affected by the mixing intensity that can be characterized by Reynolds numbers. The significant decrease in particle size was observed by increasing the Reynolds number from 600 to 8000. A higher reactant concentration leads to a higher degree of supersaturation, and finer particles are precipitated. The particle size can be reduced with increasing reactant concentration. The degree of supersaturation increases with temperature reduction, i.e., the particle size will be reduced at low temperature. In addition, nucleation and growth kinetics are changed in a way that reduces the particle size. The optimized lab‐scale process is capable of producing over 1 kg h^–1 of nanoscaled BaSO₄ with a median diameter of 75 nm.