Field Performance of High Oleic Soybeans with Mutant FAD2-1A and FAD2-1B Genes in Tennessee

Soybean [Glycine max (L.) Merr.] oil with high oleic acid (>75%) has increased oxidative stability and health benefits that are valuable for food, fuel, and industrial products. It has been determined that two naturally occurring mutations in genes FAD2-1A and FAD2-1B can combine to produce high oleic soybeans. The objective of this study was to test the effect of these mutant alleles on seed yield and oil and protein concentration. Molecular markers assisted in the creation of a population of 48 BC₃F_2:4 lines (93.75% expected genome commonality). Each line was classified into one of four genotypic groups where both FAD2-1A and FAD2-1B genes were either homozygous wild type or mutant, respectively. Twelve lines for each genotypic group were evaluated in three replications at six locations across Tennessee. There was no seed yield difference between the high oleic genotypic group and the other groups (P < 0.05). On the other hand, there were differences in fatty acid profiles and oil and protein concentrations. In combination, the mutant FAD2-1A and FAD2-1B alleles produced a mean of 803.1 g kg⁻¹ oleic acid. This is, on average, approximately 500 g kg⁻¹ more oleic acid compared to soybean lines with only one mutant FAD2-1 allele. The high oleic double mutant group had more total oil (228.0 g kg⁻¹) and protein (401.0 g kg⁻¹) compared to all other genotypic groups (P < 0.05). Overall, this specific combination of mutant FAD2-1A and FAD2-1B alleles appears to generate conventional high oleic soybeans without a yield drag.     

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.     

Alkyl Tail Segments Mobility as a Marker for Omega-3 Polyunsaturated Fatty Acid-Rich Linseed Oil Oxidative Aging

Omega-3 polyunsaturated fatty acid (PUFA)-rich linseed oil (LSO) is an important component in biological systems, foods, and many other industrial products. In recent years, LSO has attracted increased attention in the field of functional foods, which has highlighted its facile susceptibility to aging by autoxidation. Common colorimetric and a long list of spectral methodologies have been used to follow after and predict LSO shelf life's quality, especially in regards to aging by autoxidation. These standard methodologies are nevertheless limited, because of the complexity of the LSO's chemical and physical changes. The goal of the present study is to develop a sensorial ¹H LF-NMR energy relaxation time application based on monitoring primary chemical and structural changes occurring with time and temperature during oxidative thermal stress for better and rapid evaluation of LSO's aging process. Using ¹H low-field NMR, the different T₂ times of energy relaxations due to spin–spin coupling, and proton motion/mobility of LSO molecular segments were monitored. As previously reported, we characterized the chemical and structural changes in all phases of the autoxidation aging process. Starting from the initiation phase (abstraction of hydrogen radical, fatty acid chain rearrangement, and oxygen uptake yielding hydroperoxides products), through to the propagation phase (chain reactions resulting in tail cleavage to form alkoxy radicals, and alpha, beta-unsaturated aldehydes formation), and a termination phase (cross linking and production of polymerization end products). The ¹H LF NMR transverse relaxation approach, monitors both the covalent bond's strong forces (100–400 kJ mol⁻¹) in LSO oxidative aging decomposition, as well as secondary relatively weak interactive forces by hydrogen bonds (~70 kJ mol⁻¹), and electrostatic bonds (0–50 kJ mol⁻¹) contributing to secondary crosslinking interactions leading to a LSO viscous gel of polymerized products in the termination phase. In the present paper, we show that LSO tail segments mobility in terms of T₂ multi-exponential energy relaxation time decays, generated by data reconstruction of ¹H transverse relaxation components are providing a clear, sharp, and informative understanding of LSO sample's autoxidation aging processes. To support T₂ time domain data analysis, we used data from high-field band-selective ¹H NMR pulse excitation for quantification of hydroperoxides and aldehydes of the same LSO samples treated under the same thermal conditions (25, 40, 60, 80, 100, 120 °C) with pumped air for 168 hours. Peroxide value, viscosity, and self-diffusion analyses, as well as fatty acids profile and by-products determined by GC–MS on the same samples were carried out, and correlated with the LSO tail T₂ energy relaxation time results. From these results, it is postulated that selective determination of LSO tail T₂ time domain can be used as a rapid evaluation marker for following omega-3 PUFA-rich oils oxidative aging process within industrial and commercial products.     

Graphite powder coated polyurethane sponge hollow tube as a high-efficiency and cost-effective oil-removal materials for continuous oil collection from water surface

In this study, the cost-effective graphite powder (GPd)-coated polyurethane (PGPd-PU) sponge hollow tube (PGPd-PUHT) was prepared for high-efficient continuous oil removal, the hydrophobicity-superoleophilicity PGPd-PU sponge was fabricated through a simple dip-coating method, which dipping PU sponge into GPd dispersion and drying, then coating polydimethylsiloxane (PDMS) on sponge skeleton, as-prepared sponge could selectively absorb a variety of oils up to 34 times of its own weight for dimethyl sulfoxide (DMSO). The PGPd-PUHT was prepared via wrapping PGPd-PU sponge on porous tubular support. The obtained PGPd-PUHT could continuously collect various types of oils from water surface with flux as high as 1.52 kL/m²h, and excellent separation efficiency (up to 97.7%) for toluene, as well as remarkable reusability. Moreover, a continuous floating oil collection device based on PGPd-PUHT was designed which showed excellent floating oil collection ability. In addition, our strategy possesses the advantages of low cost, simple preparation, highly efficient, and easily scale-up, showing a great potential for dealing with practical oil spill remediation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48921.     

Influence of the chemical structure of additives poly(ethylene-co-vinyl acetate)-based on the pour point of crude oils

One of the methods to prevent wax precipitation, during petroleum production, transport, and refining, is the use of polymer additives that can reduce the oil pour point. However, no single additive work for all types of crude oil and this relation is not yet well known. In this study, a family of polymers based on poly(ethylene-co-vinyl acetate), containing hydroxyl groups and long pendant hydrocarbon chains (from C6 to C18), were synthesized and characterized by H¹ nuclear magnetic resonance and solubility test. Four crude oil samples containing different amounts and size distribution of the wax were used. The additive's action is favored by higher contents of iso + cycloalkanes and lower contents of n-paraffins with larger chain sizes. The presence of the CH₃COO group in the copolymers promoted the lowering of the pour point, supported by a low OH concentration and the presence of a long pendant hydrocarbon chain: the best results were obtained with C10 and C12 chain lengths. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48969.     

Highly efficient supported AlCl3-based cationic catalysts to produce polyα-olefin oil base stocks

The main aim of this research is to decrease the amount of AlCl₃ content that is very corrosive and hazardous in the catalytic system, required for the α-olefin oligomerization without substantial change of final oil features. This was successfully achieved by supporting AlCl₃ on different carriers. More precisely, a series of supported bimetallic catalysts was synthesized by immobilization of AlCl₃ and TiCl₄ onto Al₂O₃, SiO₂, and mixed supports, that is, Al₂O₃/FeCl₃ and SiO₂/FeCl₃. It was found that silica and alumina-based catalysts had higher catalytic activities compared to support free AlCl₃; however, this enhancement for silica-based supports was more significant. According to gel permeation chromatography (GPC) results, the use of single supports, that is, Al₂O₃ and SiO₂, increased oligomer's molecular weight, while the application of mixed supports resulted in the decrease of molecular weight of the oligomers. Viscosity characteristics of the synthesized oligomers have also been studied at two different temperatures of 40 and 100°C (KV⁴⁰ and KV¹⁰⁰). The viscosity index (VI) values, derived from KV⁴⁰ and KV¹⁰⁰, of the prepared oligomers were in the range of 126–145. The molecular weight and termination mechanisms of the oligomers were studied by ¹H-NMR spectroscopy. The obtained results disclosed that the employed reaction conditions led to the production of oligomer chains with various structures including vinylidene (Vd), and di and three-substituted vinylene (2Vn, 3Vn) structures.     

Facile synthesis of a castor oil-based hyperbranched acrylate oligomer and its application in UV-curable coatings

Fabrication and performance of the castor oil (CO)-based hyperbranched acrylate (C20AA) UV-curable coatings are highlighted in this work. Herein, C20AA was obtained through a facile reaction of a castor oil-based hyperbranched polyol (C20) with acrylic acid. FT-IR and ¹H NMR spectra confirmed the synthesis of the target C20AA. Subsequently, the as-prepared C20AA was employed for crosslinking a commercialized linear polyurethane acrylate (PUA) UV-curable oligomer. Specifically, by varying the content of C20AA over the range of 0, 20, 40, and 60 wt%, a series of UV-curable coatings were prepared and coded as C20AA-0, C20AA-20, C20AA-40, and C20AA-60, respectively, which were further cured under UV irradiation. The effect of C20AA loadings on the UV-curing efficiency and final polymer performance were investigated. Consequently, the tensile strength, Shore D hardness, pencil hardness, gel content, water resistance, and glass-transition temperature of the UV-cured coatings were greatly improved upon the addition of C20AA. Impressively, with the incorporation of 40 wt% C20AA, the resultant UV-cured coating exhibited highest double bond conversion, superior chemical resistance, and good flexibility. Additionally, all of the coatings showed outstanding transparency and good surface microstructures.     

Effects of phenylenediamines and alkoxysilanes on gas transport properties of polyimide - silica hybrid membranes

Gas transport properties of polyimides (PIs) and their silica hybrids were investigated. The PIs synthesized with several methyl-substituted phenylenediamines were hybridized with silica via a sol–gel process with different alkoxysilanes. The prepared hybrid membranes showed controlled gas permselectivity, depending on the selected phenylenediamines and alkoxysilanes. It was worth noting that the hybrids prepared with tetraethoxysilane possessed improved CO₂ permselectivity with increasing silica content, which tended to exceed the upper-bound trade-off line. This fact suggested the additional formation of free volume holes especially favorable for the CO₂/CH₄ separation around the polymer/silica interfacial area.     

Investigation of OSN properties of PDMS membrane for the retention of dilute solutes with potential industrial applications

Few commercially available membranes can be used for organic solvent nanofiltration (OSN). Applying OSN in chemical industries is nevertheless of high interest to cut with energy consumption linked to solvent recycling and soluble catalysts recovery. A commercial membrane, PERVAP4060, was used to investigate the retention of dilute solutes in toluene feeds and to mimic metathesis medium. The studied solutes were R-BINAP a neutral polyaromatic molecule used in metathesis chemistry, tetraoctylammonium bromide (ToABr), a charged molecule used as a homogeneous catalyst and n-hexadecane. Retention of polar ToABr (95%) was higher than that of neutral R-BINAP (80%). The transfer mechanism, either pore flow or solution-diffusion, was discussed. All the results obtained suggested that the transport is governed by the solution-diffusion mechanism. The measured retentions could be explained in terms of solubility affinities and diffusion coefficients. The stability and performances of PERVAP4060 were well established, showing the strong potential for industrial applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48359.     

β-环糊精协同乙烯基咪唑离子液体脱除溶剂油中的萘

采用1-乙烯基-3-正丁基溴代咪唑离子液体（[VBIM]Br）为脱除剂,在β-环糊精协同作用下萃取溶剂油中的萘。本实验考察了不同单因素条件在[VBIM]Br离子液体与β-环糊精共同作用下对溶剂油中脱萘率的影响,同时通过响应面法优化脱除工艺条件。实验结果表明：[VBIM]Br离子液体与β-环糊精共同作用下对萘的萃取率比单独利用[VBIM]Br离子液体提高了15%以上,萃取率达到90%以上。离子液体简单回收后,重复使用5次过后,脱除率仍在80%以上。实验通过红外分析和紫外光谱分析了[VBIM]Br离子液体协同β-环糊精脱萘的机理,与[VBIM]Br离子液体协同作用下,β-环糊精对萘存在包合作用,实现了对溶剂油中萘的脱除。