A simple model for the semicontinuous heterophase polymerization: Ethyl methacrylate as a case example

A simple but comprehensive model considering homogeneous and micellar nucleation, coagulation, entry of radicals to particles and to micelles and radicals' exit from particles, is presented. The model is validated, in a starved semicontinuous heterophase polymerization of ethyl methacrylate, at three monomer addition rates. The model accurately describes the overall and instantaneous conversion, the average particle density and diameter, and the number and weight average molar masses evolutions over time. It is found that even though the average number of radicals is much smaller than 0.5, the system is not 0-1. An empirical function was used to describe the gel effect. The homogeneous nucleation was the prevailing mechanism for particle formation and large exit rates of radicals were observed. POLYM. ENG. SCI., 60: 223–232, 2019. © 2019 Society of Plastics Engineers     

GOLPH3 Regulates EGFR in T98G Glioblastoma Cells by Modulating Its Glycosylation and Ubiquitylation

Protein trafficking is altered when normal cells acquire a tumor phenotype. A key subcellular compartment in regulating protein trafficking is the Golgi apparatus, but its role in carcinogenesis is still not well defined. Golgi phosphoprotein 3 (GOLPH3), a peripheral membrane protein mostly localized at the trans-Golgi network, is overexpressed in several tumor types including glioblastoma multiforme (GBM), the most lethal primary brain tumor. Moreover, GOLPH3 is currently considered an oncoprotein, however its precise function in GBM is not fully understood. Here, we analyzed in T98G cells of GBM, which express high levels of epidermal growth factor receptor (EGFR), the effect of stable RNAi-mediated knockdown of GOLPH3. We found that silencing GOLPH3 caused a significant reduction in the proliferation of T98G cells and an unexpected increase in total EGFR levels, even at the cell surface, which was however less prone to ligand-induced autophosphorylation. Furthermore, silencing GOLPH3 decreased EGFR sialylation and fucosylation, which correlated with delayed ligand-induced EGFR downregulation and its accumulation at endo-lysosomal compartments. Finally, we found that EGF failed at promoting EGFR ubiquitylation when the levels of GOLPH3 were reduced. Altogether, our results show that GOLPH3 in T98G cells regulates the endocytic trafficking and activation of EGFR likely by affecting its extent of glycosylation and ubiquitylation.     

Involvement of GPx-3 in the Reciprocal Control of Redox Metabolism in the Leukemic Niche

The bone marrow (BM) microenvironment plays a crucial role in the development and progression of leukemia (AML). Intracellular reactive oxygen species (ROS) are involved in the regulation of the biology of leukemia-initiating cells, where the antioxidant enzyme GPx-3 could be involved as a determinant of cellular self-renewal. Little is known however about the role of the microenvironment in the control of the oxidative metabolism of AML cells. In the present study, a coculture model of BM mesenchymal stromal cells (MSCs) and AML cells (KG1a cell-line and primary BM blasts) was used to explore this metabolic pathway. MSC-contact, rather than culture with MSC-conditioned medium, decreases ROS levels and inhibits the Nrf-2 pathway through overexpression of GPx3 in AML cells. The decrease of ROS levels also inactivates p38MAPK and reduces the proliferation of AML cells. Conversely, contact with AML cells modifies MSCs in that they display an increased oxidative stress and Nrf-2 activation, together with a concomitant lowered expression of GPx-3. Altogether, these experiments suggest that a reciprocal control of oxidative metabolism is initiated by direct cell–cell contact between MSCs and AML cells. GPx-3 expression appears to play a crucial role in this cross-talk and could be involved in the regulation of leukemogenesis.     

Margarine-Like Emulsions Prepared with Coconut and Palm Oils: Analysis of Microstructure and Freeze–Thaw Stability by Differential Scanning Calorimetry

The objective was to study the microstructure and freeze–thaw stability of margarine-like emulsions formulated with vegetable fats using differential scanning calorimetry. Emulsions were prepared with 20% w/w dispersed aqueous phase and a continuous lipid phase composed by coconut oil (CO) and/or palm oil (PO) plus polyglycerol polyricinoleate (PGPR) as emulsifier. Mean temperature (T_M) and crystallization enthalpy (ΔH_c) were obtained from the exothermic peaks corresponding to freezing of aqueous phase. Successive cooling–heating–cooling cycles were applied to analyze changes in the exothermic peak. The emulsion prepared with CO (without PO) and 1% w/w PGPR in lipid phase showed higher water droplets size (T_M = −44.8 ± 0.1 °C) and lower quantity of stabilized aqueous phase (ΔH_c = 28.9 ± 1.2 J g⁻¹) prior to application of temperature cycles, while coalescence and (presumably) water transfer processes occurred during the treatment. The use of 2% w/w PGPR was sufficient to accomplish full stabilization of aqueous phase (T_M = −45.9 ± 0.1 °C; ΔH_c = 42.6 ± 0.3 J g⁻¹) before and after the freeze–thaw treatment. The total or partial (50%) substitution of CO by PO in emulsions with 1% w/w PGPR also improved the stability of the system, exhibiting slight microstructural changes. This enhanced stability would be linked to reduced water droplets size because of more rapid crystallization of lipid phase and immobilization of aqueous phase after emulsion preparation. In conclusion, it is possible to obtain margarine-like emulsions prepared with CO and/or PO using relatively low emulsifier concentration and maintaining a desired microstructure after freeze-thawing if the percentage ratio of both fats is controlled.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.     

Influence of carboxymethylation on the gelling capacity,rheological properties,and antioxidant activity of feruloylated arabinoxylans from different sources

Feruloylated arabinoxylans (FAX) are gelling polysaccharides presenting antioxidant activity (AC) and potential application as delivery systems. The influence of carboxymethylation on the gelling capacity, rheological properties, and AC of FAX from wheat flour (FAX1) and maize distillers grains (FAX2) was analyzed. The degree of substitution of carboxymethyl groups was 0.27 and 1.77 for carboxymethylated FAX1 (CFAX1) and FAX2 (CFAX2), which presented a change in M _n from 446 to 362 kDa and from 120 to 180 kDa, and a loss in FA content from 1.05 to traces and from 10.13 to 0.12, respectively, after carboxymethylation. G′ value at the end of rheological tests for FAX1 (71 Pa) and FAX2 (726 Pa) was higher than the corresponding G″ value. In contrast, G″ value for CFAX1 (0.35 Pa) and CFAX2 (0.03 Pa) was higher than the respective G′ value, indicating that they do no form gels. The AC increased in CFAX1 in relation to FAX1 from 4.49 to 8.30 mmol Trolox equivalent antioxidant capacity (TEAC) kg⁻¹, respectively, while it decreased in CFAX2 with regard to FAX2 from 11.31 to 9.43 mmol TEAC kg⁻¹, respectively. Carboxymethylation could be a path to design FAX derivatives offering alternative potential applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48325.     

Solid‐phase extraction of phenolic compounds with poly[metalloprotoporphyrin IX]

A highly insoluble metalloporphyrin polymeric material was used as sorbent for the solid‐phase extraction of phenolic compounds. Substantial quantities of phenols (40 to 60 mg/g polymer) were absorbed from aqueous solution comparing satisfactorily with other extraction methods. The polymeric phase presented similar K_SPE values for the hydrophobic compounds tested such as p‐chlorophenol, BPA, p‐nitrophenol, and a significant lower value for the more hydrophilic p‐aminophenol and cresol. Several metallic complexes of protoporphyrin IX (Co²⁺, Cu²⁺, Ni²⁺, Zn²⁺, and Fe³⁺) have been tested. The analytes were extracted with high recoveries at acid and neutral pH values, whereas at pH 10 low recoveries were obtained. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3038–3043, 2001     

An improved algorithm for the three‐fluid‐phase VLLE flash calculation

The VLLE flash is important in water and hydrocarbons mixtures, hydrocarbon and CO₂ rich mixtures, and hydrocarbon methane rich mixtures that are encountered in reservoir performance and recovery studies. A robust VLLE flash algorithm is proposed. The equilibrium and mass balance equations are solved as a constrained minimization problem. An inverse barrier function is used to handle the inequality constrains to solve for the phase fractions. It warrants always arriving to the solution. The challenging cases analyzed showed that the initialization procedure proposed, together with successive substitution iteration in the outer loop, is a good method for a stable VLLE flash algorithm, even near critical points. Whenever the result is in the region outside the three‐phase physical domain, the solution suggests that the system has fewer phases. In one of the cases analyzed, a region with three liquid phases was encountered and the algorithm found two different solutions with positive phase fractions. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3081–3093, 2015