Two azo substituted achiral bent-core mesogens have been synthesized. Optical polarizing microscopy and synchrotron X-ray scattering studies of both compounds reveal the existence of the thermotropic uniaxial and biaxial nematic and three smectic phases at different temperatures in these single component small molecule systems. The transition from the uniaxial to biaxial nematic phase is confirmed to be second order. The transitions from the biaxial nematic to the underlying smectic phase and between the smectic phases have barely discernible heat capacity signatures and thus are also second order.

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The dye sunset yellow (SY) forms columnar aggregates via pi-pi stacking in aqueous solutions. These aggregates develop orientational and translational order at elevated concentrations to exhibit the nematic (N) and columnar (C) mesophases. Positional-order correlation lengths of the aggregates in the directions parallel and perpendicular to the stacking direction were measured as functions of temperature, concentration, and ionic content of solutions with synchrotron x-ray scattering in magnetically aligned samples. Average length of aggregates (i.e., the number of SY molecules in an aggregate) grows monotonically with concentration while their effective transverse separation decreases. The scission energy, E , determined from the Arrhenius thermal evolution of the longitudinal correlation length, is found to be 4.3+/-0.3 kBT and 3.5+/-0.2 kBT , in the N and C phases, respectively. Temperature and concentration dependence of E suggests that chromonic aggregation is not an isodesmic process. The aggregate length decreases with decreasing pH when HCl is added to the solution.

Ceramide-1-phosphate, the phosphorylated form of ceramide, gained attention recently due to its diverse intracellular roles, in particular in inflammation mediated by cPLA(2)alpha. However, surprisingly little is known about the physical chemical properties of this lipid and its potential impact on physiological function. For example, the presence of Ca(2+) is indispensable for the interaction of Cer-1-P with the C2 domain of cPLA(2)alpha. We report on the structure and morphology of Cer-1-P in monomolecular layers at the air/water solution interface in the absence and presence of Ca(2+) using diverse biophysical techniques, including synchrotron x-ray reflectivity and grazing angle diffraction, to gain insight into the role and function of Cer-1-P in biomembranes. We show that relatively small changes in pH and the presence of monovalent cations dramatically affect the behavior of Cer-1-P. On pure water Cer-1-P forms a solid monolayer despite the negative charge of the phosphomonoester headgroup. In contrast, pH 7.2 buffer yields a considerably less solid-like monolayer, indicating that charge-charge repulsion becomes important at higher pH. Calcium was found to bind strongly to the headgroup of Cer-1-P even in the presence of a 100-fold larger Na(+) concentration. Analysis of the x-ray reflectivity data allowed us to estimate how much Ca(2+) is bound to the headgroup, approximately 0.5 Ca(2+) and approximately 1.0 Ca(2+) ions per Cer-1-P molecule for the water and buffer subphase respectively. These results can be qualitatively understood based on the molecular structure of Cer-1-P and the electrostatic/hydrogen-bond interactions of its phosphomonoester headgroup. Biological implications of our results are also discussed.

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A polycarbazole–gold nanocomposite is synthesized based on two polymerization techniques, i.e., emulsion and interfacial using aqueous gold chloride and non‐aqueous carbazole monomer solutions. Use of gold chloride as an oxidant for carbazole not only provides a new chemical synthesis for polycarbazole conducting polymer but also allows the formation of conducting nanocomposite in one simple step. Polymerization of carbazole and further growth of the polymer along with gold nanoparticles are governed by the redox reaction between carbazole and Au cations. Two different morphologies of polymers and two different sizes (with narrow size distribution) of gold nanoparticles are obtained depending on the polymerization routes. Structural and thermal properties of the nanocomposites are studied using SEM/TEM, FT‐IR, XRD, and TGA. XRD of nanocomposites depicts the amorphous nature of the polymer and the highly phase selective crystalline nature of gold. Nanocomposites with improved properties show better dispersion in common organic solvents and potential for various technological applications. magnified image

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Background Environmental factors, such as weather extremes, have the potential to cause adverse effects on plant biomass quality and quantity. Beyond adversely affecting feedstock yield and composition, which have been extensively studied, environmental factors can have detrimental effects on saccharification and fermentation processes in biofuel production. Only a few studies have evaluated the effect of these factors on biomass deconstruction into biofuel and resulting fuel yields. This field-to-fuel evaluation of various feedstocks requires rigorous coordination of pretreatment, enzymatic hydrolysis, and fermentation experiments. A large number of biomass samples, often in limited quantity, are needed to thoroughly understand the effect of environmental conditions on biofuel production. This requires greater processing and analytical throughput of industrially relevant, high solids loading hydrolysates for fermentation, and led to the need for a laboratory-scale high solids experimentation platform. Results A field-to-fuel platform was developed to provide sufficient volumes of high solids loading enzymatic hydrolysate for fermentation. AFEX pretreatment was conducted in custom pretreatment reactors, followed by high solids enzymatic hydrolysis. To accommodate enzymatic hydrolysis of multiple samples, roller bottles were used to overcome the bottlenecks of mixing and reduced sugar yields at high solids loading, while allowing greater sample throughput than possible in bioreactors. The roller bottle method provided 42–47% greater liquefaction compared to the batch shake flask method for the same solids loading. In fermentation experiments, hydrolysates from roller bottles were fermented more rapidly, with greater xylose consumption, but lower final ethanol yields and CO2 production than hydrolysates generated with shake flasks. The entire platform was tested and was able to replicate patterns of fermentation inhibition previously observed for experiments conducted in larger-scale reactors and bioreactors, showing divergent fermentation patterns for drought and normal year switchgrass hydrolysates. Conclusion A pipeline of small-scale AFEX pretreatment and roller bottle enzymatic hydrolysis was able to provide adequate quantities of hydrolysate for respirometer fermentation experiments and was able to overcome hydrolysis bottlenecks at high solids loading by obtaining greater liquefaction compared to batch shake flask hydrolysis. Thus, the roller bottle method can be effectively utilized to compare divergent feedstocks and diverse process conditions.