Surface and interfacial fourier transform infrared spectroscopic studies of latexes. XIV. Surface phase separation in polystyrene/poly-n-butyl acrylate latex films

This study focuses on the behavior of sodium dioctylsulfosuccinate (SDOSS) in 50/50 w/w % polystyrene/poly(butyl acrylate) (p-Sty/p-BA) latex films. Specifically, mobility and orientation are examined in the context of the film formation by the use of dynamic mechanical thermal analysis and attenuated total reflectance (ATR) Fourier transform infrared (FT-IR) spectroscopy. While for the homopolymer blends of p-Sty and p-BA, two T_g values resulting from a phase separation of p-Sty and p-BA phases are observed, only a single T_g is detected for a copolymer of the same mixture, indicating a single phase within the film. ATR FTIR spectroscopic data indicate that the phase separation of p-Sty and p-BA blends does not occur uniformly across the film. After coalescence, p-Sty particles produce a significant degree of stratification at approximately 1.6 μm from the film surface. At this depth, the polystyrene rings assume preferentially parallel orientation to the film surface. At the same time, the hydrophilic groups of SDOSS surfactant (SO⁻₃Na⁺) are oriented preferentiallyparallel to the surface. Under high relative humidity conditions, water is able to diffuse into the film and swells the surface layers, thus causing them to expand. As a result, the top, predominately poly-n-BA surface becomes “thicker», and p-Sty phase appears to be near 2.3 μm from the surface. The polystyrene rings maintain their preferential parallel orientation to the surface, but the hydrophilic groups of SDOSS are able to diffuse into the film with the water uptake and are thus not present at the filmair interface. © 1996 John Wiley & Sons, Inc.     

Kinetic study of the depolymerization of Bruceton coal

The depolymerization of coals using phenol and p-toluenesulphonic acid, was studied.In this reaction the acid ‘catalyst’ is destroyed, its rate of destruction being different for different coals. A kinetic study of the depolymerization of Bruceton coal under conditions of gradually declining acid concentration has been carried out. Parameters which were monitored include the weight increase of the products, the solubility of the products in benzene-ethanol, the extractability of the products into pyridine, the amount of colloidal material present in the pyridine-extractables, and the molecular weight distribution of the pyridine-soluble products. Under the conditions used, the reaction produces primarily polymeric products from coal. The molecular weight distribution of the pyridine-soluble material seems to undergo no major changes with reaction time.     

Inverting cascade impactor data for size-resolved characterization of fine particulate source emissions

In this paper, the inversion processing of cascade impactor data to construe continuous size distributions within fine particulate matter (PM_2.5) is examined for residential oil furnace and fireplace appliance emissions. Impactor data from tests with these emissions sources are selected for the challenges they pose to comprehending the size distributions of aerosol mass and chemical species. In specific, the oil furnace aerosol offers an opportunity to apply data inversion to study a bimodal lognormal distribution in which much of the aerosol mass is impactor-penetrating nanoparticles . The fireplace emissions on the other hand cover the issue of a chemical size distribution, which is subject to particle loss and characterized by a single lognormal, accumulation mode peak. Computational steps relevant to the application of the data inversion are illustrated in detail. Evaluation of correlation coefficients (0.992) indicates that the inversion model predictions fit the impactor data well. Simulations of systematic measurement error (±10%) at each impactor stage are shown to have a negligible impact on the inversion results for test data. It is concluded that data inversion can be effective when (i) source emissions contain a portion of particles that falls outside the measurement range of cascade impactors, (ii) a mass size distribution of an individual species is determined without the knowledge of the total mass concentration for that species, or when (iii) losses in the particle charger system are significant.     

Employing CRISPR-Cas9 to Generate CD133 Synthetic Lethal Melanoma Stem Cells

Malignant melanoma is a lethal skin cancer containing melanoma-initiating cells (MIC) implicated in tumorigenesis, invasion, and drug resistance, and is characterized by the elevated expression of stem cell markers, including CD133. The siRNA knockdown of CD133 enhances apoptosis induced by the MEK inhibitor trametinib in melanoma cells. This study investigates the underlying mechanisms of CD133’s anti-apoptotic activity in patient-derived BAKP and POT cells, harboring difficult-to-treat NRAS^Q61K and NRAS^Q61R drivers, after CRISPR-Cas9 CD133 knockout or Dox-inducible expression of CD133. MACS-sorted CD133(+) BAKP cells were conditionally reprogrammed to derive BAKR cells with sustained CD133 expression and MIC features. Compared to BAKP, CD133(+) BAKR exhibit increased cell survival and reduced apoptosis in response to trametinib or the chemotherapeutic dacarbazine (DTIC). CRISPR-Cas9-mediated CD133 knockout in BAKR cells (BAKR-KO) re-sensitized cells to trametinib. CD133 knockout in BAKP and POT cells increased trametinib-induced apoptosis by reducing anti-apoptotic BCL-xL, p-AKT, and p-BAD and increasing pro-apoptotic BAX. Conversely, Dox-induced CD133 expression diminished apoptosis in both trametinib-treated cell lines, coincident with elevated p-AKT, p-BAD, BCL-2, and BCL-xL and decreased activation of BAX and caspases-3 and -9. AKT1/2 siRNA knockdown or inhibition of BCL-2 family members with navitoclax (ABT-263) in BAKP-KO cells further enhanced caspase-mediated apoptotic PARP cleavage. CD133 may therefore activate a survival pathway where (1) increased AKT phosphorylation and activation induces (2) BAD phosphorylation and inactivation, (3) decreases BAX activation, and (4) reduces caspases-3 and -9 activity and caspase-mediated PARP cleavage, leading to apoptosis suppression and drug resistance in melanoma. Targeting nodes of the CD133, AKT, or BCL-2 survival pathways with trametinib highlights the potential for combination therapies for NRAS-mutant melanoma stem cells for the development of more effective treatments for patients with high-risk melanoma.     

Identification of the blood-borne somatotroph-differentiating factor during chicken embryonic development

Somatotrophs become a significant population by day 16 of chicken embryonic development. We have previously demonstrated that an earlier induction of GH cell differentiation is possible with the addition of day 16 embryonic serum to cultures of day 12 pituitary cells, an age when somatotrophs are rare. The present study was designed to identify the blood-borne signal(s) responsible for the serum activity, using reverse hemolytic plaque assays to identify individual GH-secreting cells. The activity was found to be a heat-stable, ether-soluble compound(s) that is bound or inhibited by a trypsin-sensitive protein. The extent of GH cell differentiation was greater (P < 0.05; n = 3) in response to the ether phases of heated day 16 (14.1 +/- 0.4% of all cells) and day 12 sera (9.3 +/- 0.4%) than with untreated serum from days 16 and 12 (6.1 +/- 0.4% and 0.82 +/- 0.4%, respectively). Furthermore, ether-extracted day 16 serum was more effective than ether-extracted day 12 serum, which was also different from basal (0.85 +/- 0.4%; P < 0.05). Based on this biochemical profile, the abilities of various steroids to stimulate differentiation were tested. Three steroids were found to stimulate somatotroph differentiation in vitro: 17beta-estradiol, corticosterone, and progesterone. However, the estradiol receptor antagonist, tamoxifen, while abolishing the effect of estradiol, had no effect on the induction of differentiation by day 16 serum. In contrast, RU486, a specific glucocorticoid receptor antagonist in chickens, blocked the stimulatory effects of corticosterone, progesterone, and day 16 serum on somatotroph differentiation. We next tested whether the active compound in day 16 embryonic serum was corticosterone, the predominant glucocorticoid in chickens. Incubation of day 16 serum with corticosterone antiserum, but not control antiserum, suppressed day 16 serum-induced GH cell differentiation. Therefore, we conclude that corticosterone is the blood-borne signal capable of stimulating somatotroph differentiation in vitro. The present findings together with previous reports indicate that somatotroph differentiation during embryonic development may result from an increase in circulating glucocorticoid concentrations.     

Rotor dynamics of a sliding vane turbineRotor dynamik von turbinen mit gleitenden turbinenblaettern

A general mechanical design and performance analysis is presented for a sliding vane turbine. The analysis is general in the sense that it is valid for any stator profile and that there is no restriction on the turbine use. This analysis includes a dynamic force analysis on the vane, rotor dynamics, and vane kinematics. As an example, an eliptical stator sliding vane turbine is considered for the purpose of illustrating the procedure of applying the general analysis and presenting results by graphs as a function of significant design parameters.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.