Oleogels from Glycerol‐Based Lyotropic Liquid Crystals: Phase Diagrams and Structural Characterization

In the course of our studies on structured reverse lyotropic liquid crystals (LLC) as oleogels, a system was designed with the desired physical and rheology properties for cosmetic and pharmaceutical applications. The aqueous phase was partially replaced by glycerol to minimize bacteriological problems and obtain specific rheology characteristics. The constructed phase diagrams are based on ternary mixtures of glycerol monooleate (GMO), decane, water, and glycerol. The main lyotropic mesophase obtained in this study was reverse hexagonal derived from dilution line 8:2 (72 wt% GMO and 18 wt% decane) and 10 wt% water; or water:glycerol (wt ratios 3:1 and 1:1) mixture. It was found that heat‐cool fluctuation caused formation of new pseudo‐equilibrium structures with mesomorphic transformations to more fluid and less ordered mesostructures. Replacing up to 50 wt% of the water by glycerol significantly increases the gel phase region in the phase diagram, meaning more structural compositional options. The structural parameters were determined using cross‐polarized light microscopy (CPLM), differential scanning calorimeter (DSC), powder X‐ray diffraction (PXRD), and small angle X‐ray scattering (SAXS). Rheological measurements revealed viscoelastic properties of lyotropic liquid crystals with a decrease in the elasticity (G′), plasticity (G″), and complex viscosity (η*), as a function of increasing the glycerol content.     

Transport and solvent sensing characteristics of styrene butadiene rubber nanocomposites containing imidazolium ionic liquid modified carbon nanotubes

Obtaining strong interfacial interaction between filler and polymer matrix is very crucial for the fabrication of polymer nanocomposites with superior performance. Present study is aimed to fabricate high performance styrene butadiene rubber (SBR) nanocomposites with imidazolium type ionic liquid modified multiwalled carbon nanotube (MWCNT). Ionic liquid facilitates the dispersion of MWCNT in rubber matrix and it is obvious from transmission electron microscopy images. Diffusion of toluene through SBR nanocomposite membranes has been investigated as a function of surface modified MWCNT (f-MWCNT) content to analyze the chain dynamics and filler-polymer interactions. O₂ gas barrier effect of nanocomposites with special reference to the filler loading is explored. The substantial improvement in the barrier effect in presence of filler interpreted on the grounds of a theoretical model describing permeability of heterogeneous systems. Finally solvent sensing characteristics of prepared nanocomposites are also analyzed and it is observed that prepared nanocomposites can be used as a flexible solvent sensor.     

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     

The crystal state binding of dithionite to deoxy-hemoglobin

The crystal state binding of sodium ditbionite to deoxyhemoglobinis reported. Dithionite has been used extensively to deoxygenatehemoglobin and myoglobin and there has been considerable interestamong users of dithionite about its effect on protein structureand binding site(s). We have determined that dithionite bindsto deoxygenated hemoglobin crystals at the interface of twomolecules in the crystal lattice. Specific residues involvedin hydrogen bonds or salt interactions with dithionite includeHisll6 and Hisll7 of the ft subunit and Lysl6 of the ß₂subunit of the adjacent hemoglobin molecule. No binding wasobserved at the symmetry related Hisll6 and 117 ß1 residues.We have shown that dithionite does not affect the native hemoglobinstructure or the binding of several allosteric inhibitors tohemoglobin and can be used to mount T state crystals in theair     

Photopolymerizable multifunctional monomers and their evaluation as reactive Bis‐GMA eluents

Bis‐GMA {2,2‐bis[4‐(2′‐hydroxy‐3′‐methacryloyloxy‐propoxy)‐phenyl]‐propane}, TEGDMA <2‐{2‐[2‐(2‐methylprop‐2‐enoyloxy)ethoxy]ethoxy}ethyl‐2‐methylprop‐2‐enoate>, and methyl methacrylate (MMA) are some of the most commonly used monomers in the field of restorative dentistry. These compounds are characterized by having one or two terminal double bonds. Besides the effort to synthesize new monomers, several problems still affect the clinical behavior of contemporary dental materials. In this work, two monomers with three terminal double bonds, 5A13DA and 5A13DMA, were synthesized. Both monomers were used to completely replace TEGDMA as reactive diluent of photopolymerizable dental resin composites containing Bis‐GMA. The effects of 5A13DA and 5A13DMA on flexural properties, double bond conversion, water sorption, solubility, and polymerization shrinkage were evaluated. In addition, both monomers were evaluated as crosslinking agents for methylmethacrylate, resulting in copolymers with enhanced thermal stability. The results obtained suggest that newly synthesized monomers are potential substitutes for TEGDMA in the formulation of dental composites, providing 50% lower volumetric shrinkage than the composite resin used as control and adequate mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46240.     

Do Bumble Bee, <Emphasis Type="Italic">Bombus impatiens</Emphasis>, Queens Signal their Reproductive and Mating Status to their Workers?

Reproduction in social insect societies reflects a delicate balance between cooperation and conflict over offspring production, and worker reproduction is widespread even in species showing strong reproductive skew in favor of the queen. To navigate these conflicts, workers are predicted to develop the means to estimate the queen’s fecundity - potentially through behavioral and/or chemical cues - and to adjust their reproduction to maximize their fitness. Here, we introduced bumble bee, Bombus impatiens, workers to queens of different mating and reproductive status and examined worker reproduction and expression levels of two genes which were previously shown to be sensitive to the presence of the queen, vitellogenin and Krüppel-homolog 1. We further explored whether the queen’s chemical secretion alone is sufficient to regulate worker reproduction, aggression and gene expression. We found that worker ovary activation was inhibited only in the presence of egg-laying queens, regardless of their mating status. Workers reared in the presence of newly-mated queens showed intermediate vitellogenin expression levels relative to workers reared with mated egg-laying and virgin queens. However, none of the whole-body chemical extracts of any of the queen treatment groups affected ovary activation, aggressive behavior, or gene expression in workers. Our findings indicate that only the presence of a freely-behaving, egg-laying queen can fully inhibit worker reproduction. It remains to be determined if workers detect differences in queen mating status and fecundity through differences in the queens’ behavior alone or through the queen’s behavior in concert with fertility signals.     

Application of β-Sitosterol + γ-Oryzanol-Structured Organogel as Migration Barrier in Filled Chocolate Products

Oil migration in filled pralines is a phenomenon that is highly correlated with the occurrence of chocolate bloom. In this study the potential to suppress or prevent oil migration by incorporation of sterol/sterolster-structured organogels was evaluated. Different quantities, 2.5 or 14% (w/w), of gel with structurant levels of either 10 or 25% (w/w) were studied in a layered model system. The gel was either a part of the nougat or of the chocolate phase, or as a separate layer. Samples were monitored regularly for a period of 24 weeks at storage temperatures of 10, 18 and 28 °C. The amount of migrated oil was determined via DSC analysis of a surface sample. The results indicate that, despite the additional oil brought into the system via the oleogel, the level of oil found in the chocolate layer is reduced through the presence of the gel. In particular, the three-layer system and gelled chocolate appear to be promising routes to either suppress oil migration or improve nutritional profiles by incorporation of liquid oils.     

Polysaccharide Biomaterials

An entire new genus of “polymer therapeutics” has emerged with wide applicability, including as mechanical supports, mechanical barriers, artificial tissue/organs, and pro-drug preparations with pharmacological effects. Polysaccharides are a class of biopolymers formed from many monosaccharide units joined together by glycosidic linkages. The physical properties of carbohydrates, such as solubility, gelation, and surface properties, are dictated by the monosaccharide composition, chain shapes, and molecular weight. These macromolecules exhibit good hemocompatibility, are non-toxic, and show unique biological functions, ranging from cell signaling to immune recognition. With few exceptions, they are more economical in comparison with others biopolymers. Polysaccharide-based polymers have been widely proposed as scaffold materials in tissue engineering applications as well as carriers for drug delivery.