Effect of High‐Intensity Ultrasound on the Crystallization Behavior of High‐Stearic High‐Oleic Sunflower Oil Soft Stearin

The objective of this research was to evaluate the effect of high‐intensity ultrasound (HIU) and crystallization temperature (T_c) on the crystallization behavior, melting profile, and elasticity of a soft stearin fraction of high‐stearic high‐oleic sunflower oil. Results showed that HIU can be used to induce and increase the rate of crystallization of the soft stearin with significantly higher SFC values obtained in the sonicated samples, especially at higher T_c. SFC values were fitted using the Avrami model, and higher k_n and lower n values were obtained when samples were crystallized with sonication, suggesting that sonicated samples crystallized faster and through an instantaneous nucleation mechanism. In addition, the crystal morphology, melting behavior, and viscoelasticity were significantly affected by sonication.     

Piezoelectric Droplet Generator for the Calibration of Particle‐Sizing Instruments

Using a piezoceramic tube and a continuous glass capillary, droplets in a diameter range between 10 μm and 100 μm can be generated. This corresponds to a volume of up to 0.6 pl. The velocity of the generated droplets depends on droplet size but is constant for each diameter. The liquid can be dosed as single droplet, as an accumulation of droplets or as a chain of droplets in a frequency range between 1 Hz up to 3 kHz. The lifetime of the droplets depends on droplet size and the chemical and physical properties of the dispersed liquid. In addition, for water droplets the humidity of the air near the droplet trajectory influences the lifetime of the droplets.     

The High‐Pressure Characterization of Energetic Materials: 1‐Methyl‐5‐Nitramino‐1H‐Tetrazole

Pressure–volume relations and optical Raman and Infrared spectra of polycrystalline 1MNT have been obtained under quasi‐hydrostatic conditions up to 16 and 40 GPa, respectively, by using diamond anvil cell, synchrotron‐based angle‐resolved X‐ray diffraction, and microspectroscopy. The X‐ray measurements show that the pressure–volume relations remain smooth up to 16 GPa at room temperature, while vibrational measurements show no evidence of a phase transition to near 40 GPa. Anomalous increases of several vibrational intensities and bandwidths suggest that subtle molecular distortions and structural modifications occur in the crystal as pressure increases. Decompression experiments indicate the structural modifications are reversible.     

Experimental studies and population balance equation models for breakage prediction of emulsion drop size distributions

A population balance equation (PBE) model for pure drop breakage processes was developed from homogenization experiments and used to investigate model extensibility over a range of emulsion formulation and homogenizer operating variables. Adjustable parameters in the mechanistic breakage functions were estimated from measured drop volume distributions by constrained nonlinear least-squares optimization. Satisfactory prediction of measured bimodal distributions was achieved by the incorporation of two different breakage functions that accounted for large drop breakage due to turbulent shear and for small drop breakage due to collisions between drops and turbulent eddies. Model extensibility to different emulsion compositions and homogenizer pressures was investigated by comparing model predictions generated with the base case parameters to drop volume distributions measured under different conditions. The PBE model satisfactorily accounted for changes in the dispersed phase volume fraction and the interfacial tension with the base case parameters. By contrast, significantly improved predictions for the continuous phase viscosity or multiple formulation variables were obtained through re-estimation of the model parameters using multiple data sets in which the associated variables were systematically varied. The model was not able to satisfactorily predict drop volume distributions resulting from homogenizer pressure changes, perhaps due to the assumption of a constant pressure throughout the homogenizer. We conclude that PBE models of drop breakage can be used to reasonably predict the effects of emulsion formulation variables on drop volume distributions and have the potential for guiding experimental efforts aimed at the design of novel emulsified products.     

Low‐Temperature Chemical Synthesis of High‐Purity Diacylglycerols (DAG) from Monoacylglycerols (MAG)

A chemical method was developed for low‐temperature synthesis of DAG from MAG followed by an easy purification procedure in order to obtain high‐purity DAG. Solvent‐assisted and solvent‐free reaction conditions were used, combined with different catalysts (sodium methoxide, p‐toluenesulfonic acid, methanesulfonic acid, and sulfuric acid). All reactions were performed at 35 and 70 °C. By increasing both acidity and polarity of the catalyst the equilibrium shifts towards the formation of DAG. When using sulfuric acid in solvent‐assisted condition at 70 °C, 88 % conversion was obtained after 20 min of reaction (77 % w/w DAG in the reaction mixture after evaporation of the solvent). After purifying by means of column chromatography, 96 % pure DAG were obtained. The overall yield of DAG was 81 %.     

Preparation and Performance Evaluation of Fatty Amine Polyoxyethylene Ether Diethyl Disulfonate for Enhanced Oil Recovery in High‐Temperature and High‐Salinity Reservoirs

To enhance oil recovery in high‐temperature and high‐salinity reservoirs, a novel fatty amine polyoxyethylene ether diethyl disulfonate (FPDD) surfactant with excellent interfacial properties was synthesized. The interfacial tension (IFT) and contact angle at high temperature and high salinity were systematically investigated using an interface tension meter and a contact angle meter. According to the experimental results, the IFT between crude oil and high‐salinity brine water could reach an ultra‐low value of 10^?3 mN m^?1 without the aid of extra alkali at 90°C after aging. The FPDD surfactant has strong wettability alternation ability that shifts wettability from oil‐wet to water‐wet. The FPDD surfactant with a high concentration also has good emulsion ability under high‐temperature and high‐salinity conditions. Through this research work, we expect to fill the lack of surfactants for high‐temperature and high‐salinity reservoirs and broaden its great potential application area in enhanced oil recovery.     

High‐Throughput Screening Technology for Automotive Applications

The development of advanced emission control systems to meet the strict regulations requires efficient and flexible material screening capabilities. Here, a high throughput test unit is described. Two case studies demonstrate the rapid screening of relevant parameter spaces and material functionalities which can be used in product development. One involves steady‐state testing of hydrocarbon oxidation in Diesel aftertreatment systems, while the other shows the evaluation of oxygen storage capacity in the optimization of three‐way catalysts for gasoline engines.     

Chemical Characterization of a High‐Oleic Soybean Oil

High‐oleic low‐linolenic acid soybean oil (HOLLSB, Plenish^®) is an emerging new oil with projections of rapid expansion in the USA. HOLLSB has important technological advantages, which are expected to drive a gradual replacement of commodity oils used in food applications such as soybean oil. A key technological advantage of HOLLSB is its relatively high oxidation stability. This oxidation stability is the result of a favorable fatty acid composition, high (76%) oleic acid, low linoleic (6.7%), and alpha‐linolenic (1.6%) acids, and high concentration of tocopherols (936 ppm) after refining, enriched with the gamma‐homolog (586 ppm). A detailed analysis of the fatty acid composition of this HOLLSB by gas chromatography–mass spectrometry allowed the identification and structural determination of 9‐cis‐heptadecenoic acid (or 17:1n‐8). To our knowledge, this is the first time 9‐cis‐heptadecenoic acid has been unequivocally reported in soybean oil. This unusual fatty acid component has the potential to be used as a single authenticity marker for the quantitative assessment of soybean oil. The Rancimat induction period (IP) of Plenish^® (16.1 hours) was higher than those of other commercially available high‐oleic oils, such as canola (13.4 hours), and Vistive^® Gold (10 hours), a different variety of soybean oil. Plenish^® showed the same IP as high‐oleic sunflower oil. Plenish^® shows a modest increase in oxidation stability with the external addition or relatively high concentrations of tocopherols. The characteristic high oxidative stability of Plenish^® may be further enhanced with the use of nontocopherol antioxidants.     

Quantitative Determination of Natural Glycolipids from Oil Seed by Automated High‐Performance Thin‐Layer Chromatography (HPTLC)

The role of glycolipids in vegetable oil refining and production of bio‐based fuels has not been disclosed so far. Such investigations required a reliable and reproducible quantitative determination of these compounds. Fundamental data were therefore established on the quantitative determination of glycolipids in vegetable oil gums by means of high‐performance thin‐layer chromatography (HPTLC). Concentrating on five abundant natural glycolipid classes found in these oils, identification of a suitable separation method for the employed glycolipid mixture and those parameters relevant for successful detection were considered in detail. The special importance of sample volume when employing quantitative HPTLC was discussed. Acetone/chloroform/water 6:3:0.4 (v/v/v) was identified as a convenient mobile phase for the investigated issue. A derivatization reagent comprising methanol, copper(II)sulfate pentahydrate, sulfuric acid 98 %, and phosphoric acid 85 % was identified. Subsequent heating at 135 °C for 10 min finished the derivatization and enabled detection at λ = 370 nm. Calibration curves ranging from 1500 to 31.25 ng/mL, regarding both peak area and peak height, were determined. The good correlation of parameters enabled the application of the method to real oil gum samples from sunflower and soybean oil. This revealed that digalactosyldiglycerides in combination with either sterylglucosides or acylated sterylglucosides represented the major glycolipid classes in these oils.     

Performance of New Biodegradable Di‐Sulfonate Surfactants as Hydrotropes in High‐Temperature and Salinity Environments

Propyl alkyl ether sulfonate (PAES) surfactants, recently developed by The Dow Chemical Company, show excellent electrolyte, hard water and caustic solubility, with attractive ECOTOX profile and biodegradability. Due to their unique structure and properties, they are good candidates for use as hydrotropes in formulations containing nonionic surfactants. The goal of these studies was to evaluate hydrotropic efficiency of PAES materials via cloud point analysis. The effects of PAES alkyl tail length, concentration, and mono‐ and di‐sulfonate components on the cloud point of TERGITOL? 15‐S‐9 in solutions of varying electrolyte strength were investigated. In the presence of high electrolyte levels, PAES 12C had the highest hydrotropic efficiency of all materials tested, including commonly used commercial hydrotropes. Di‐sulfonate components of the PAES materials were found to be more efficient hydrotropes than mono‐sulfonate in high electrolyte environments for all tail lengths tested. The di/mono ratio and tail length were found to be critical parameters.     

Salt‐Free Aqueous Extraction of a Cell‐Bound Biosurfactant: a Kinetic Study

A cell‐bound biosurfactant produced by Lactobacillus pentosus was obtained under eco‐friendly conditions and used directly as an emulsifying agent in order to stabilize fluorene/water emulsions. The biosurfactant was extracted from L. pentosus cells with an aqueous phosphate buffer solution in the absence of NaCl. This is important because most the cell‐bound biosurfactants are extracted in the presence of NaCl, which is considered highly phytotoxic. A pseudo‐second order kinetic model best described the batch extraction of the biosurfactant from cells. As expected, the initial extraction rate of the biosurfactant increased with the temperature. Calculation of the activation energy with the Arrhenius equation yielded a positive value, indicating that the process is endothermic. The aqueous solution containing the biosurfactant was able to stabilize fluorene/water emulsions, with relative emulsion values of 62.2 % after 7 days of emulsion formation.     

Activity‐Fed Translation (AFT) Assay: A New High‐Throughput Screening Strategy for Enzymes in Droplets

There is an increasing demand for the development of sensitive enzymatic assays compatible with droplet‐based microfluidics. Here we describe an original strategy, activity‐fed translation (AFT), based on the coupling of enzymatic activity to in vitro translation of a fluorescent protein. We show that methionine release upon the hydrolysis of phenylacetylmethionine by penicillin acylase enabled in vitro expression of green fluorescent protein. An autocatalytic setup where both proteins are expressed makes the assay highly sensitive, as fluorescence was detected in droplets containing single PAC genes. Adding a PCR step in the droplets prior to the assay increased the sensitivity further. The strategy is potentially applicable for any activity that can be coupled to the production of an amino acid, and as the microdroplet volume is small the use of costly reagents such as in vitro expression mixtures is not limiting for high‐throughput screening projects.     

High‐Pressure 31P{1H} NMR Studies of RhH(CO)(TPPTS)3 in the Presence of Methylated Cyclodextrins: New Light on Rhodium‐Catalyzed Hydroformylation Reaction Assisted by Cyclodextrins

The effect of methylated cyclodextrins on the RhH(CO)(TPPTS)₃ complex in hydroformylation conditions [50 atm of CO/H₂ (1/1) and 80 °C] has been investigated by high‐pressure ³¹P{¹H} NMR spectroscopy. In the presence of methylated β‐cyclodextrin, the equilibria between the rhodium species lie in favor of phosphine low‐coordinated rhodium species. The formation of a stable inclusion complex between this cyclodextrin and the trisulfonated triphenylphosphine ligand (TPPTS) was found to be the key to understanding the displacement of the equilibria. Indeed, the methylated α‐cyclodextrin which does not interact with the TPPTS and the methylated γ‐cyclodextrin which can weakly bind to the TPPTS have no and a very low effect on the equilibria, respectively. These results explain for the first time why a decrease in the normal to branched aldehydes ratio is always observed when cyclodextrins are used as mass‐transfer agents in aqueous biphasic hydroformylation processes.