Industrial Oil Products

ABSTRACTS 2019 AOCS ANNUAL MEETING & EXPO May 5–8, 2019

Industrial Oil Products

BIO 1.1/IOP 1: Biopolymers Chairs: Richard Ashby, USDA, ARS, ERRC, USA; and Rongpeng Wang, CVC Thermoset Specialties, USA

Plant Oil Derived Emulsion Copolymers with materials for the synthesis of various Predictable Properties Meghan E. Lamm*, Ping biopolymers. Polyurethanes are an important Li, and Chuanbing Tang, University of South class of polymers because of their wide Carolina, USA industrial applications in consumer and Emulsion polymerization is an important industrial sectors. The main disadvantage of the industrial synthetic method. Unfortunately, it polyurethane foams is their high flammability relies mostly on petroleum-based chemicals. which is due to the predominant presence of Recent research has focused on incorporating carbon and hydrogen in their structure. Highly biomass derived chemicals and intermediates, porous and combustible nature of polyurethane such as plant oil-based monomers. Due to their foams further facilitates the flame spread rate. good hydrophobicity, plant oil monomers can High flammability of polyurethane foams struggle to be incorporated into emulsion restricts some of its valuable applications. In polymers to achieve optimal properties. Herein this work, we have used corn oil as a starting we present an industrially relevant semi-batch material for the synthesis of polyurethane method of emulsion polymerization used to foams. Corn-oil was converted to polyol for prepare copolymers of soybean methacrylate polyurethane foams using “thiol-ene” click (SBMA), using high oleic soybean oil (HOSO), chemistry. Flame-retardant polyurethane foams with various industry co-monomers such as were prepared by addition of different methyl methacrylate, styrene, and butyl concentrations of dimethyl methyl acrylate. All polymerizations displayed good phosphonate in the final foam composition. The control with minimal coagulation and high effect of additive flame retardant on the conversion. Variation in feed ratios (from 0 to physicomechanical and flammability of the 50 wt% of SBMA) offers tunability of thermal polyurethane foams was studied. Additive and mechanical properties in resulting latex flame retardant significantly reduced the materials. The alkene present on the soybean flammability of the polyurethane foams without chains allowed for oxidative crosslinking of affective their physicomechanical properties. latexes films, which resulted in high levels of The foam containing flame retardant showed crosslinking, consistent with SBMA content, and over 30 times reduction in the burning time and significant enhancement in mechanical over 6 times reduction in weight loss during properties. Overall, the promising results horizontal burning test compared to foam indicate good potential for replacement of without the flame retardant. In addition to petrochemical methacrylates in commodity reducing the burning time and weight loss after thermoplastics and acrylic coatings. the addition of the flame retardant, these foams showed a significant reduction in heat Corn Oil for Highly Flame Retardant Rigid release rate and thermal heat release. Our Polyurethane Foams for Industrial Applications research opened a new pathway to utilize Camila Zequine, Sanket Bhoyate, Brooks Neria, vegetable oils for industrial applications, Pawan Kahol, and Ram Gupta*, Pittsburg State particularly in the polyurethane industry. University, USA Vegetable oils are being used as starting Rapid Conversion of Oils into Various

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Monomers and Biopolymers Aman Ullah*, for a range of new products. Here we describe Muhammad Arshad, Reza Ahmadi, and Liejiang the use of bulk polymerization of epoxidized Jin, University of Alberta, Canada soybean oil, linseed oil and triolein to obtain The use of renewable resources in resins useful as encapsulants, potting supplementing and/or replacing traditional compounds, and foams based upon using petrochemical products, through green different cationic initiators. While super acids chemistry, is becoming the focus of research. and Lewis acids were preferable in making The utilization of oils can play a primitive role foams because they enhance reaction rates, towards sustainable development due to their novel catalysts were used to slow down and large scale availability, built-in-functionality, control the polymerization rate and obtain solid biodegradability and no net CO2 production. polymers with unusual properties. Microwaves, being clean, green and environmentally friendly, are emerging as an Synthesis, Properties and Structure Function alternative source for product development. Correlation of Bioplasticizers in PVC. Dharma R. Solvent free conversion of fatty acid methyl Kodali*, and Lucas J. Stolp, University of esters (FAME's) derived from canola oil and Minnesota, USA waste cooking oil under microwave irradiation This presentation provides an overview of demonstrated dramatically enhanced rates. The the synthesis, properties and functional microwave-assisted reactions lead to the most evaluation of bioplasticizers in polyvinylchloride valuable terminal olefins with enhanced yields, (PVC) that are derived from vegetable oils. purities and dramatic shortening of reaction Plasticizers, the largest class of plastic additives, times. Various monomers/chemicals were are non-volatile organic liquids that impart prepared in high yield in very short time. The flexibility and improve the functionality of complete conversions were observed at plastics. The currently used phthalate temperatures as low as 40 ºC within less than plasticizers have EHS concerns. Bioplasticizers five minutes. The products were characterized with various functional groups such as epoxy, by GC-MS, GC-FID and NMR. The monomers acetoxy, methoxy, thiirane, aziridine on the acyl were separated and polymerized into different chain backbone combined with ester group polymers including biopolyesthers, variations of alkyl, mono, di and tri alkoxy or biopolyesters, biopolyamides and solketal of fatty acid esters have been biopolyolefins. The polymers were synthesized and characterized. The characterized in details for their structural, bioplasticizers were derived from regular and thermal, mechanical and viscoelastic properties. high oleic soybean, canola and castor oils, and The ability for complete conversion of oils formulated with PVC and evaluated for their under solvent free conditions and synthesis of functional properties. Epoxysoybean oil fatty different biopolymers is undoubtedly an acid esters served as the key intermediate to attractive concept from both an academic and incorporate most of the functional groups on an industrial point of view. the fatty acid backbone. The ring opening of the epoxy group with acetic acid resulted in cyclic Cationic Polymerization of Epoxidized Oils to tetrahydrofuran derivatives. The high viscosity Cast Resins and Foams Zoran Petrovic*, and and darker color of aziridine and thiirane Dragana Radojcic, Pittsburg State University, derivatives limited their usefulness, whereas USA the other compounds physical and analytical Epoxidized oils are an excellent platform properties such as acid value, color and

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viscosity, were acceptable. The plasticizers having epoxy and acetoxy groups demonstrated Corn Stover and Levulinic Acid: Two Valuable, excellent compatibility in PVC, with high Renewable Substrates for Biosynthesis of efficiency (Shore Hardness), thermal stability Unique Polyhydroxyalkanoate Biopolymers and gelling properties. The structural variations Richard D. Ashby*, Daniel K.Y Solaiman, Gary of molecular weight, polarity, and branching of Strahan, and Alberto Nunez, USDA, ARS, ERRC, the fatty acid esters and their effect on USA functionality is examined and rationalized. The Lignocellulosic materials are abundant and functional properties of number of cheap and as such, are being evaluated as bioplasticizers were comparable to commercial feedstocks for bio-based product synthesis. Our plasticizer, diisononylphthalate (DINP). laboratory used the hydrolysate from corn stover (CSH) as a base fermentation feedstock Synthesis and Characterization of Lipid-based for the synthesis of polyhydroxyalkanoate (PHA) Biopolymers and Bionanocomposites from biopolymers using Burkholderia sacchari DSM Poultry Industry By-product Muhammad 17165 and Azohydromonas lata DSM 1122. B. Safder*, University of Alberta, Canada sacchari utilized all of the available sugars in the Spent hen is a by-product of the poultry hydrolysate while A. lata only used the glucose industry and has potential as a source of lipids. fraction of the hydrolysate to produce poly(3- Lipid-based monomers and corresponding hydroxybutyrate) (PHB). Introduction of polymershave successfully been synthesized by levulinic acid (another inexpensive bio-based using free radical polymerizations. The effect of material produced from both C-5 and C-6 temperature and time on molecular weight of sugars) into the media in a co-feeding strategy polymer was studied and conditions for resulted in block copolymers composed of 3- obtaining high molecular mass biopolymers hydroxybutyrate (3HB) and 3-hydroxyvalerate were optimized. Furthermore, using optimized (3HV; P3HB-3HV) from B. sacchari and conditions, the biopolymers were reinforced terpolyesters composed of 3HB, 3HV, and 4- with different nanoparticles such as nanoclay, hydroxyvalerate (4HV) from A. lata with varying POSS, and monocrystalline cellulose (NCC) using monomer ratios. This presentation will focus on in-situ polymerizations. The monomer, the specific details of polymer production and homopolymer and nano-reinforced polymers characterization protocols involved in the were characterized by different techniques such synthesis of these unique PHA biopolymers. as nuclear magnetic resonance (NMR), attenuated total reflectance fourier transform Microalgae for the Production of Novel infrared spectroscopy (ATR-FTIR), scanning Biopolymer Feedstocks Scott Franklin*1, Zoran electron microscopy (SEM) and transmission Petrovic2, Jian Hong3, Leon Parker1, Lauren electron microscopy (TEM), tensile testing and Slutzky1, Mona Correa4, Nina P. Reyes1, dynamic mechanical analysis (DMA). The Constantine Athanasiadis4, Jon Wittenberg1, thermal properties of the synthesized materials Estelle Schaefer5, and Kevin were evaluated by the thermogravimetric Ward1,1Checkerspot, USA; 2Pittsburg State analysis (TGA) and differential scanning University, USA; 3Kansas Polymer Research calorimetry (DSC). The nanofiller addition into Center, Pittsburg State University, USA; the polymer matrix substantially improved the 4Checkerspot; 5Checkerspot, France thermal and mechanical properties of the The oleochemicals industry represents an composites. enormous market valued at greater than $23B

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U.S. that is responsible for the production of Microalgae, which elaborate fatty acids and myriad products, materials and polymers via triacylglycerols utilizing cellular machinery processing of fats and oils derived from animal homologous to that found in higher plants, have and vegetable sources. Surprisingly, this proven to be highly efficient microbial factories industry relies on just 14 fatty acids to create for the production of biomass, proteins and oils, these chemical building blocks, because these and many species appear to be quite amenable fatty acids are what are readily available at to genetic manipulation as well as to standard commodity scale and price. On the other hand, techniques of microbial strain improvement. plant oilseeds found in nature, most of which Utilizing these tools and combining whole will never be cultivated at industrial scale, genome and transcriptomic sequencing of elaborate an incredible diversity of fatty acid unique oilseeds and host microalgae, novel moieties (> 500 species) unavailable in today’s triglycerides can be produced in these single- oleochemicals industry. The chain lengths, cell factories at exceptionally high purity and degrees of saturation, functionalities and purity titer, exceeding what is present even in the of these fatty acids and their resulting natural oilseed host. Data gleaned from triglycerides offer unique opportunities for the materials (foams, elastomers and cast production of polymer feedstocks, particularly urethanes) produced utilizing the above with regard to polyols for PU applications. approach will be shown.

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IOP 2: Olechemicals and Green Chemistry Chairs: Darrell Sparks, Mississippi State University, USA; and Zheng Guo, Aarhus University, Denmark

Chemistry and Property of pH-responsive functionalities. In addition, the cytotoxicity Amino Acid-based Amphiphiles Weiwei Cheng1, study of selected compounds by Sampson Anankanbil2, Liu Guoqin3, and Zheng sulforhodamine B colorimetric assay proved a Guo*4,1South China University of Technology, non-toxic nature; contributing further evidence China; 2Dept. of Engineering, Aarhus University, to potential multi-purpose applications in food, Denmark; 3School of Food Science and laundry, pharmaceutical, and cosmetic Engineering, South China University of industries. Technology, China; 4Aarhus University, Denmark Two novel series of lysine-based Modifying the Double Bond in Fatty Acids for ampholytic amphiphiles, with alkylsuccinic New Materials: Oleo-chemistry versus Linoleo- anhydrides or fatty O-acylated malic anhydrides chemistry Grigor B. Bantchev*, and Girma of varying chain lengths as hydrophobic Biresaw ,USDA/ARS/NCAUR, USA acylating agents, were synthesized in medium This presentation will be about some to high yield (50.23%‒90.15%) based on a facile, reactions explored in search of novel lipid- catalyst-free, and highly efficient method in based materials, with an emphasis on the water medium. The structures of the differences between the chemistries of oleic synthesized compounds were confirmed by MS, and linoleic fatty acids. Thiol-ene, H- FTIR, and 1H/13C NMR analysis. The phosphonate-ene, and the epoxide-ring synchronous presence of amino and carboxyl opening reactions will be discussed and the groups in the synthetic amphiphiles results in a differences in the products contrasted. Oleate pH-regulatable amphiphilic property, chain has one double bond, and when it reacts, represented by pH-dependent change of critical only two very similar isomers (four isomers, if micellar concentration (CMC), surface tension we account for chirality) are produced. (γ), and stability of oil-in-water emulsion. Linoleate chain has two double bonds, which, Results showed that CMC values decrease, γ upon reaction, yields a larger number of value increase, and emulsion stability increase isomers, with functional groups in close with increasing medium pH, suggesting that the proximity. In some cases, those functional surface activity of synthetic compounds at groups react with each other, leading to a air/water and oil/water interface under neutral variety of linoleate-based structures that are and alkalic conditions was remarkably higher not predictable from studying the reaction of than that under acidic condition. Surprisingly, oleates. Examples of such linoleate-based lauryl O-acylated malic lysine presents excellent structures include: tetrahydrofuran, furan, foaming ability close to detergent sodium tetrahydrothiophene, 1,2-dithiane and others. dodecyl sulphate; and dodecyl succinic lysine affords highly stable o/w nanoemulsion. Membrane-based Oil Washing Nikolai Moreover, lauryl O-acylated malic lysine Kocherginsky*1, Brajendra K. Sharma2, and displays excellent ferrous ion chelating property Kishore Rajagopalan2,1Biomime, USA; 2Illinois as good as lysine and DPPH antioxidative Sustainable Technology Center, USA capacity as effective as commercial food Both edible oils and biodiesel are often ingredient DATEM, indicating its multi-faceted washed with aqueous alkali solutions to reduce

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the fatty acid content – a process called alkali other alcohols. PP of their saturated refining. The resulting soap leads to oil losses homologues were 40-50°C higher. The diesters due to emulsification and typically requires also showed outstanding resistance to heat centrifugation to accomplish a clean phase thinning, with viscosity index VI~200. Methyl separation. A simple method to wash oils branching had only medium effect, while ethyl without mixing with water has been patented or longer branches improved cold fluidity (US 10,065,132 B2, 2018). Oil flows on one side dramatically without significantly compromising of a porous membrane with an aqueous phase VI. Lubricant properties were compared to on the other side. Due to the nature of the those of mineral oil and synthetic membrane, one of the phases is immobilized hydrocarbons, widespread as basestocks. within the pores, vastly increasing the Tribological performance, non-volatility, interfacial area without droplet creation. The additive solvency and other properties were extraction of fatty acids and other polar clearly superior. Oxidative stability was much impurities is then accomplished in a facile better than that of typical fatty esters used for manner. No transmembrane pressure or lubricants. Dioxane and dioxalane esters were additional oil/water separation after washing is also synthesized, but had poorer stability. necessary. It can be used for example for Remarkably good VI, cold fluidity and other removal of free fatty acids from high fatty acid lubricant properties provide excellent feedstocks such as DDG oil, rice bran and opportunities for mono-unsaturated dibasic conversion of virgin to extra virgin olive oil. esters in high performance hydraulic fluids and other lubricants. The project COSMOS has Applicability of Esters from Mono-unsaturated received funding from the European Union’s Linear Dicarboxylic Acids for Lubricants Svajus Horizon 2020 research and innovation J. Asadauskas*1, Asta Griguceviciene2, Linas programme under grant agreement No 645405. Labanauskas2, Jean-Luc Couturier3, and Jean-Luc Dubois3,1FTMC, Lithuania; 2Institute of Investigation of a Heterogeneous Chemical Chemistry, FTMC, Lithuania; 3Arkema, France Process to Convert Sunflower Oil into a Value Good combination of low temperature Added Branched-Chain Oil Helen Ngo Lew*1, fluidity, oxidative stability and tribological Yunzhi Chen2, and Robert A. Moreau1,1USDA, properties makes esters from vegetable oils a ARS, ERRC, USA; 2USDA-Agriculture Research frequent choice as lubricant basestocks, Service, USA hydraulic fluids in particular. Some mono- Vegetable oils (i.e., triglycerides) are unsaturation can be tolerated in lubricant currently used in the industry as bio-lubricants. applications as long as the above properties are Unfortunately, these oils are not stable at high still acceptable. Trans- double bonds often temperatures and are viscous at low result in problematic pour points (PP), temperatures. Modification of triglycerides therefore, lubricant manufacturers strongly (from linear-chain to branched-chain structures) prefer cis-unsaturation. In this study has been found to be one of the most direct predominantly trans- unsaturated linear α-ω- and efficient ways to overcome these C18 diesters were synthesized using various drawbacks. We found that heterogeneous acid branched C5-C20 alcohols. Unexpectedly catalysts such as H+-BETA zeolite and sulfated favorable PP below -50°C were recorded for zirconia solids work well in catalyzing the trans-unsaturated C18 linear dibasic acid, sunflower oil to branched oil products. The esterified with C8 - C12 Guerbet and some solids can be easily prepared, handled, and

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separated from the oily products. These respectively. The dissolved gas analysis result products are usually a complex mixture of (in ppm) of the key gases for MAISO obtained isomers which can be isolated and after epoxidation-esterification are : characterized by various analytical instruments. Such branched-chain oils should exhibit Coating Performance and Rheological improved low temperature fluidity while Characteristics of Novel Soybean Oil-based maintaining good lubricant properties. Emulsions Kangzi Ren1, Tao Fei*1, Tong Wang1, and Keneth Metzger2,1Iowa State University, Feasibility of the novel utilization of modified USA; 2Eurica Group LLC., USA Azadirachta Indica seed oil as transformer Aqueous emulsions of soybean oil based insulating fluid Chinedu Agu*1, Matthew coating materials consist of ethylene glycol and Menkiti1, Albert Agulanna2, and Emeka propylene glycol mono- and di-esters of stearic Udokporo3,1Nnamdi Azikiwe University, Nigeria; acid (EGMD and PGMD, respectively) and 2Project Development Institute, Nigeria; compound emulsions (mixtures of EGMD 3University of Nigeria, Enugu Campus, Nigeria emulsion with four commercial polymer This work focuses on the solvent emulsions) were formulated and tested for extraction and chemical modification of paperboard coating. Paper coated with the Azadirachta Indica seed oil (AISO) into a novel EGMD emulsion alone had low water resistance bio-based transformer insulating fluid. The (5-min Cobb of > 20 gram per square meter) effects of temperature, time and particle size on and grease resistance (100% oil penetration). the AISO yield were studied. Extraction kinetics Paper coated with compound emulsions had and thermodynamics were also investigated. significantly improved water resistance and The AISO batch was sequentially subjected to grease resistance. With EGMD accounting for as transesterification and epoxidation- high as 60% of the emulsion’s solid content, 5- esterification treatments to evaluate product min Cobb value of about 1.0 gsm was achieved. quality after each stage. The vital operational Increased number of coating drawdown characteristics of the modified Azadirachta significantly improved water and grease Indica seed oil (MAISO) were determined. The resistance of the coated papers. With three- AISO yield of 54.14 % was obtained at 55 °C, drawdown and coat weight of 14.93-23.00 gsm, 150 min and 0.5 mm particle size. For the 5-min Cobb value of less than 2 gsm and oil solvent extraction, pseudo-second order, penetration of less than 2% were achieved. hyperbolic, Elovich’s and parabolic diffusion Greater heat exposure during drying resulted in models all described the process kinetics, while better water resistance. Increasing the drying Gibbs free energy, entropy and enthalpy values temperature from 100 to 200 °C for 30 s evaluated at 0.5 mm particle size were – 168.63 reduced the 5-min Cobb value of papers coated kJ/mol, 1.82 kJ/mol, and 428.11 kJ/mol, with PGMD compound emulsions from 34.1 to respectively. MAISO characteristics obtained for 1.1 gsm. The addition of cross-linking agent, epoxidation-esterification were better than that zinc ammonium carbonate (ZAC), in the of transesterification. The final MAISO emulsions improved water repellency but not characteristics after epoxidation-esterification grease resistance. The yield stress of are: -9 °C, 179 °C, 818 Kg/dm3, 1.66 mm2/s, cetyltrimethylammonium bromide (CTAB) 0.25 mgKOH/g, 0.11 mg/Kg and 52.86 KV for based emulsions (1.61-21.32 Pa) were much pour point, flash point, density, viscosity, acid higher than those of Tween 80 based emulsions value, moisture content and dielectric strength, (0.023-0.066 Pa), and they were generally more

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viscous than the compound emulsions. The substantially improved the thermal properties compound emulsions had comparable surface and fire retardancy of the nanocomposites. energy but lower gluability than the commercial While the renewable (waste/recycled cooking emulsions. oil) based biopolymers with good molecular weight have a great potential to replace Synthesis of Lipid Derived Nanocomposites petroleum based products in the future. The and Microwave Assisted Copolymers Aman current studies will contribute greatly in making Ullah, Muhammad Arshad*, Liliang Huang, and fatty acids, derived from renewable materials Mahrzadi N. Shahi,University of Alberta, Canada and waste cooking oil useful for the polymer Fatty acid based monomer and industry. corresponding hybrid polymer nanocomposites have successfully been developed by in situ Waterborne Glycerol Based Thermoplastic polymerization where nanoclay was used a Adhesives for Wood Composites Eric Cochran*, reinforcement material. Different ratios of Chris Williams, Andrew N. Becker, Nacu B. nanofiller was used to prepare hybrid materials Hernandez, and Michael J. Forrester,Iowa State by free radical homopolymerization of 2- University, USA (acryloyloxy)ethyl stearate (AOES) monomer With the rise of biodiesel on a global and copolymerization of AOES with styrene. scale, a large volume of low quality crude Solvent free synthesis of copolymers from fatty glycerol has emerged on the market. Unsuitable acids epoxides, derived from waste cooking oil for many end-use applications without costly and phthalic anhydride was also performed refining, the industry continues to struggle to using (salen)CrIIICl as catalyst and n- valorize this important side-stream. At the same Bu4NCl/DMAP (tetrabutylammonium time, recent EPA rules strictly limit the use of chloride/4-(dimethylamino)pyridine) as co- formaldehyde in the manufacture of wood catalysts for the first time under microwave composite materials, posing challenges to irradiation, where reaction time was reduced manufacturers in terms of identifying cost- from a number of hours to minutes. DMAP was effective substitutes that are compatible with found to be more effective even at lower existing process technologies. Addressing these concentration providing higher molecular problems, we have developed curable water- weight and narrow dispersity values of soluble adhesives from crude glycerol that copolymers as compared to co-catalyst n- provide both cost and performance advantages Bu4NCl. The prepared nanocomposites and over other formaldehyde alternatives such as copolymers were characterized and analyzed by isocyanates. We are currently working with proton nuclear magnetic resonance (1H-NMR) industry partners to produce 3,000 gallons of spectroscopy, transmission electron adhesive for full-scale manufacturing microscopy, XRD, atomic force microscopy, demonstrations. This talk will elucidate the path attenuated total reflectance Fourier transform we followed beginning with the early technical infrared (ATR-FTIR) spectroscopy, gel innovations that gave birth to the base material permeation chromatography, culminating with the development of a thermogravimetric analysis (TGA) and minimum viable product at the cusp of differential scanning calorimetric techniques. successful commercialization. Moreover, flammability tests of nanocomoposites were also performed. Addition of nanofiller into the polymer matrix

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Understanding Improvements to Stiff Asphalt saturated diesters which are commercially Binders Modified with Epoxidized Plant promising phase change materials (PCMs). In Derived Oil Materials through Analytical fact, at least one of these PCM diesters has Chemistry Nacu B. Hernandez1, Chris already been utilized in the food industry for Williams*1, Eric Cochran1, Joseph H. Podolsky2, the regulation of beverage temperatures. As Mohamed Elkashef2, and Austin D. part of efforts to widen the range of accessible Hohmann2,1Iowa State University, USA; 2Iowa temperatures and latent heats of these State University, United States materials, we have studied also the analogous Through recent work at Iowa State dibasic esters. Preliminary results show, University, great potential has been identified however, that not all diesters are created using epoxidized plant oil materials as equally; the dibasic esters of oxalic, malonic and fluxes/rejuvenators in stiff asphalt binders. This succinic acids consistently melt at ~ 10 °C lower work found that improvement in low than the analogous diol-derived diesters of temperature performance was greater than ethylene, trimethylene and tetramethylene improvement in high temperature performance glycols. Furthermore, the dibasic ester series for Solvent De-Asphalting (SDA) and Residuum possess consistently lower energy storage Oil Super critical Extraction (ROSE) unit bottoms densities (~ 200-240 J/g) compared to the diol- when using epoxidized plant oils as compared derived diesters (230-260 J/g). We propose that to results from modified Vacuum Distillation the differences in the thermal performances lie (VD) tower bottoms. Additional research work in their packing behaviours. In this work, we will has been done on recycled asphalt pavement report on the phase trajectories of these demonstrating the performance and economic materials using X-ray diffraction, Differential opportunity for using the epoxidized plant oils Scanning Calorimetry and Polar Light facilitating the increased amount of RAP that Microscopy experiments. While crystal can be used in asphalt paving mixtures. structure elucidation has traditionally not Analytical chemistry was done using Fourier played a significant role in the characterization Transformed Infrared with Attenuated total of phase change materials, we expect that such reflection (FTIR-ATR) and Ion Mobility Mass insights will lead to a better understanding of Spectrometry equipment on the asphalt binders the observed thermal properties. This studied. information, in turn, can be used to make informed chemical modifications that improve Engineering Green Phase Change Materials: the performance lipid derived phase change Dibasic or Diol Esters? Latchmi Raghunanan*1, materials for the chemical enterprise. Laziz Bouzidi2, and Suresh Narine2,1Trent Centre for Biomaterials Research, Departments of New Insights for the Advancement of Bio- Physics & Astronomy and Chemistry, Trent based Diamides as Phase Change Materials University, Canada; 2Trent University, Canada Kosheela D. Poopalam*1, Latchmi Raghunanan2, Increasing sustainability in the chemical Laziz Bouzidi1, Yeong SK3, and Suresh enterprise continues to be a significant Narine1,1Trent University, Canada; 2Trent Centre motivator for the use of renewable resources to for Biomaterials Research, Departments of prepare functional materials that perform Physics & Astronomy and Chemistry, Trent similar to or better than commercially existing University, Canada; 3Malaysian Palm Oil Board, petro-chemical materials. Already, our group Malaysia has presented several series of diol-derived The thermal transition properties and the

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crystal structure of a series of linear aliphatic 18). The uniqueness of 18-2-18 was further diamide phase change materials (PCMs) were highlighted via a singularity observed in the investigated. The diamides were prepared from transition temperatures versus n curve. The stearic acid (C18) and diamines of varying thermal data were corroborated by the XRD. carbon number (18-n-18, n=2, 4, 6, 8 and 10) via The diamides with n≥4 crystallized in single a simple amidation reaction. The 1H NMR, DSC high-stability β-phases, whereas the 18-2-18 and XRD results were predictably correlated, diamide crystallized in a lesser stable β-phase and their differences was explained primarily in co-existing with a β'-phase. Experiments terms of intermolecular hydrogen bonding conducted at very different cooling rates (20 - ability. These data revealed a peculiar 0.1 °C/min) indicated that the thermal behaviour of 18-2-18 attributed to its unique transition behaviour and crystal structure were conformational arrangement influenced by solely dependent on thermodynamics. Overall, limited degrees of freedom and strong steric the diamides are shown to have energy storage hindrance within the ethylene diamine and thermal transition temperatures amongst segment. Notably, although all the diamides the highest currently accessible by organic presented sharp and narrow thermal phase PCMs. The results also show that one can transitions without significant supercooling, custom engineer the thermal and structural those with n≥4 showed a similar thermal properties of diamide PCMs by fine-tuning the storage density of ~220 J/g (160 J/g for 18-2- hydrogen bonding and aliphatic chains.

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ANA 3.1 / EAT 3.1 / IOP 3.1: Analysis of Food Applications of Low Saturated Fats/Oils; and PUFA, and Fat-Soluble Vitamins with Emphasis on Nutrition Labeling Chairs: Jillonne Kevala, Food and Drug Administration, USA; and Serpil Metin, Cargill R&D, USA

Modernizing the Nutrition Facts and manufacturers in implementing changes in the Supplement Facts Labels Jillonne H. Kevala*, NFL and SFL. The presentation will provide an Food and Drug Administration, USA overview of the key changes. Objective: To modernize the Nutrition Facts and Supplement Facts labels (NFL and SFL) Low Saturate High Oleic Canola Oil in Health to reflect current scientific information on and Nutrition Xiaolan Luo*1, Nisa Tharayil1, and nutrition and enhance its presentation to Diliara Iassonova2,1Cargill, USA; 2Cargill Inc., consumers. Methods: Review and analysis of USA information from sources including the U.S. Nutrition research has been focused on Department of Health and Human Services’ and specific food ingredients beneficial to nutrition the U.S. Department of Agriculture’s, “Dietary and health as diet has been linked to various Guidelines for Americans 2015–2020”; the diseases such as diabetes, obesity and Report of the Dietary Guidelines Advisory cardiovascular disease. Fats and oils are one of Committee on the Dietary Guidelines for the most important components of diet as one- Americans (February 2015); The Institute of fourth of total daily dietary energy is supplied Medicine, which reviewed several reports on by these fatty acids. Recently, Cargill scientists individual nutrients, from 1997 to 2011; have developed a low saturate high oleic canola consensus statements from the National oil with a high level of mono-unsaturated and Institutes of Health; and a Surgeon General moderate level of polyunsaturated fatty acids. report on Bone Health and Osteoporosis The new canola oil has the lowest saturated fat (October, 2004). FDA also relied on data from content on the market and can offer a 40% the National Health and Nutrition Examination reduction in saturated fat from conventional Survey (2003-2008). Results: FDA’s review and canola oil. Oxidative stability and performance analysis of the large body of information in food applications of the new canola oil was described above showed that a significant evaluated by analytical tests such as rancimat number of different elements in the NFL and and schaal oven tests as well as sensory test in SFL, established in January 1993, were out of comparison with other specialty and date with respect to current nutrition science. commodity oils. The new canola oil Other elements of the label needed updating to demonstrated superior flavor and high present nutrition information in a manner more oxidative stability. Its OSI slightly decreased clear and useful to consumers. Conclusions: FDA from 18.6 to 18 even after storage for over 3 made numerous amendments to the years at 55F. Food fried in low saturate canola requirements for mandatory and voluntary oil showed favorable flavor, texture and high declarations of specific nutrients and overall liking score while containing significantly amendments addressing different aspects of reduced saturated fat content. The impact of label formatting and issues related to serving natural antioxidants on oxidative stability of low sizes. The final rules published in May of 2016. saturate canola oil was also investigated. With FDA is drafting numerous guidance documents, high oxidative and application performance, low in different stages of development, to aid saturate high oleic canola oil offers a healthier

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choice through reduced saturated fat per Rheology and Baking Stability of Water in Oil serving in labelling of a wide range of foods. Emulsion Designed as Low saturated Bakery Shortening Fernanda Davoli*1, Serpil Metin2, Validation of a HPLC Method for Analysis of and Paul Smith3,1Cargill, USA; 2Cargill R&D, USA; Provitamin A Carotenoids (β-carotene, α- 3Cargill Global Foods Research, Belgium carotene and β-cryptoxanthin) Sneh Bhandari*, There is a strong drive for low SAFA and Ming Gao, Merieux NutriSciences, USA shortenings, but development is challenging The 2016 Nutrition labeling regulation by because of the difficulty in reproducing the US FDA (FR 33741) replaced the International “plasticity” of traditional systems with unit (IU) for label declaration of vitamin A to reductions in SAFA. In this study, a two-step mcg Retinol Activity Equivalents (RAE). β- approach was taken. First water in oil emulsions carotene, and α-carotene, and β-cryptoxanthin were produced and their rheology was have different RAE values. There is a need for manipulated by emulsifier composition an accurate and precise method for analysis of (including combinations), in order to find the α-carotene, β-carotene and β-cryptoxanthin in behavior most resembling a traditional foods for labeling of correct amount of total shortening. Then, the water phase was vitamin A, the current study is an attempt to structured as a stable hydrocolloid gel to allow validate such a method. The carotenoids were better water management during baking. extracted using a hot sponification followed by Emulsion systems (water in oil emulsion) the solvent extraction. The extract was analyzed containing 35% saturated fat were prepared by a reverse-phase HPLC on a C30 column. The using a variety of different emulsifiers and method did provide a good chromatograppy crystallized with careful processing control in a and response of the carotenoids. The NIST SRM pilot scale SSHE and characterized by rheology 2383 a baby food and BCR 485 vegetable and water droplet size. Fat systems with good powder reference material were analyzed by rheological behavior were selected, then used the method and the results of β-carotene, α- to further prepare emulsions with alginate to carotene and β-cryptoxanthin as well as trans- structure the water phase. Application tests β-carotene were with in the range specified by were then performed with cookies. Control and the respective reference materials for the manipulation of rheological properties were corresponding carotenoids. The method achieved, showing that the mechanical precision in different food matrices in terms of properties of the emulsion could be % RSD values for β-carotene, α-carotene and β- manipulated through the choice of emulsifier. cryptoxanthine were in the range 1.9-5.4%, 3.1- Emulsions where the water phase was an 15.1% and 1.6-7.9% respectively. Spike recovery alginate gel presented the best application in different matrices of carotenoids was found performance in terms of cookie dimensions, to be in the range of of 86- 106%. LOD and LOQ suggesting better water control during baking. of the method in terms of mcg/100g was in the This research aims to build the foundational range 1.1-2.2 and 2.1-3.6, respectively.The knowledge to lead to the development of a low method was found to be accurate and precise saturated fat system that deliver the expected for the analysis of carotenoids in different food plasticity of a bakery shortening (responsible for matrices. The method can be used for proper dough formation) as well as an emulsion carotenoid analysis for nutrition labeling of which maintains the final cookie dimensions by vitamin A. managing water loss during the baking process.

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Quantification of Furan Fatty Acids by LC- MS/MS and their Identification in New Zealand Physicochemical Properties, Chemical Marine Oils Matthew R. Miller*1, Donato Composition and Risk Assessment of Polycyclic Romanazzi2, Hajime Uchida3, Johnathon Aromatic Hydrocarbons of Commercial Puddick2, Yutaka Itabashi3, Masashi Hosokawa4, Fragrant Rapeseed Oils Youfeng Zhang*, School Toshiyuki Suzuki 3, and Michael of Food Science and Technology, Jiangnan Boundy2,1Cawthron, New Zealand; 2Cawthron University, People’s Republic of China Institute, New Zealand; 3National Research Fragrant rapeseed oil is a type of hot- Institute of Fisheries Science, Japan; 4Hokkaido pressed oil in China. In this work, University, Japan physicochemical properties, chemical Furan fatty acids (F-acids) are heterocyclic composition, presence and risk assessment of fatty acids with a furan moiety in the acyl chain. (PAHs) polycyclic aromatic hydrocarbons in 38 They are generally found as minor components representative Chinese fragrant rapeseed oil in the lipid fraction of marine organisms, plants samples were evaluated for the first time. The and mammals. F-acids are potent antioxidants acid value (0.64-2.68 mg KOH/g), peroxide value and radical scavengers and are thought to (1.58-4.86 mmol/kg) and color value (R=2.6-5.8 contribute to the health benefits of fish-rich Y=35) were all within codex limits. Thirty-two diets. The role and benefits of dietary F acids samples whose erucic acid concentrations are yet to be fully understood, however they exceeded 2%. A well negative linear correlation show promising potential as therapeutic marine between oleic acid and erucic acid was shown drugs for the treatment of inflammatory- (R2=0.876), which suggested to be a potential disorders. Objectives To develop a rapid marker for prediction of adulteration. quantitative liquid chromatography tandem Benzo[a]pyrene and PAH4 (chrysene, mass spectrometry (LC-MS/MS) method for un- benz[a]anthracene, benzo[b]fluroranthene, and equivocal identification and quantitation of F- benzo[a]pyrene) were nd-6.93 and nd-30.79 acids in marine oils Methods For the past two μg/kg, respectively. Monte Carlo simulation was years, the Cawthron Institute (NZ) has been applied to deal with the uncertainties in the engaged in an international research dietary exposure and risk estimation. The collaboration with the Hokkaido University median dietary exposure of BaPeq contents (Japan) and the National Research Institute of from total PAH4 were found to be 0.0826, Fisheries Science (NRIFS) of Japan to develop 0.0530, 0.3082 and 0.0724 ng·kg-1·d-1 for novel methods to identify and quantify F-acids. children, adolescents, adults and seniors of We have developed LC-MS/MS methods that in male, respectively, whereas that for the above positive ESI mode, F-acids gave a prominent [M groups of female were 0.0777, 0.0504, 0.3014 + H] ion, by which individual F-acids could be and 0.0659 ng·kg-1·d-1. Results from health risk detected and identified to a level of 5 ng/mL. estimation indicated high potential carcinogenic Results Our LC-MS/MS method provides risk. Fragrant rapeseed oil is still a product selective detection of F-acids in marine oils subject to contamination by PAHs. Limits for without the need of lengthy sample processing. PAH4 of fragrant rapeseed oil should be Through our research we have also identified a included in Chinese regulation to improve the new source of F-acids, a unique New Zealand safety. marine oil with surprisingly high levels of these minor fatty acids, offering new research opportunities in this field.

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The Role of Fat in Determining the Structural desirable textural properties of baking products, and Textural Properties of Semi-sweet Biscuit particularly biscuit. Hasmadi Mamat*,Universiti Malaysia Sabah, Malaysia Effect of Tempering Parameters on the Fat plays a unique role in many food Plasticity and Hardness of Puff Pastry products due to its hygroscopic nature. In the Margarine Miroslav Buchmet*, DuPont area of baked goods, biscuits belong to a group Nutrition Bioscience, Denmark of products that contains considerable fat and Puff pastry margarine is one of the most the overall quality is largely determined by the challenging products for the margarine type of fat used. In this study, the effect of fat industry. There are many demands to good puff type on dough rheology properties and quality pastry margarine; it must be stable, plastic and of semi-sweet biscuit (rich tea type) was non- greasy. Plasticity of margarine is investigated using varies techniques. Four types determined by fat base and processing. Usually, of fat, namely palm oil, palm olein, palm mid- fat base consists of palm oil and/or its fractions fraction and butter, which varied in composition and some liquid oil. Such blends give good and solid fat content, were used to produce plasticity and workability. But to achieve that, it semi-sweet biscuits. The role of fat and type of is necessary to temper margarine at proper fat were analysed in terms of the texture, temperature right after production and before appearance and the starch behaviour of the distribution. Results of this study have proven final baked biscuit. Rheological properties of the that tempering conditions have a great dough were also compared. Texture profile influence on the margarine quality. Freshly analysis results showed that the type of oil produced samples of full-fat puff pastry significantly influenced dough rheological margarine were tempered for one week at properties. Hardness measurement showed temperatures of 10, 20, 30°C, and followed by that biscuit produced with higher solid fat oil evaluation after one week’s and two months’ had higher breaking force, but this was not storage at 20°C. Samples were evaluated by perceived when tested with a human panel. hand for plasticity and workability. Hardness of Gelatinization and pasting results showed that margarine was measured by means of texture fat type also influenced thermal profiles of analyzer. The samples demonstrated different starch granules in biscuits with most of the plasticity and hardness. Hardest and most granules retaining their crystallinity. Microscopy plastic were samples tempered at 10°C, observations showed that biscuit produced with followed by samples at 20°C. Samples tempered palm mid-fraction had an open internal at 30°C were brittle. Observed behavior can be microstructure and heterogeneous air cells as explained by the polymorphic nature of fat. compared to the other samples. As conclusion, Data can be used as a guideline during fat is an important ingredient in baking margarine production and troubleshooting. products and it plays many roles in providing

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BIO 3.1/IOP 3/PRO 3.1: Biofuels Chairs: Frank Dumeignil, Lille University, France; Xiaofei P. Ye, University of Tennessee, USA; and Megan Hums, USDA, ARS, ERRC, USA

Synthesis of Thiophene and Thiolane Associates, LLC, USA; 2Institute of Chemistry, Derivatives Found in Biodiesel Produced from University of Graz, Austria Brown Grease Lipids. Shehu Isah*, Delaware The unexpected in-situ formation of State University-USDA, USA heterophases from residual impurities in Brown grease lipids (BGL), the primary biodiesel fuels has deleterious consequences component of dewatered grease trap waste stemming from limited solubility. To get beyond (GTW) and sewage scum grease (SSG) is a simple expressions of “like dissolves like” potential low-value feedstock for biodiesel requires an understanding of compositional production. Market limitations of these factors which promote or discourage entry of feedstocks for use in biodiesel production an impurity into the molecular network of the include high sulfur (S) content. A combination liquid fuel. As such, the liquid composition acts of analytical techniques including GC-FID, GC- to modulate dissolution and precipitation PFPD, and GC-MS have been previously used to processes. Diesel fuels are comprised of elucidate the identity of thiophene derivatives hundreds to thousands of distinct chemical (C4H4S-X), thiolane derivatives (C4H8S-X) and compounds when mixed together in other S-bearing compounds in BGL-derived commercial blends of diesel #2(ULSD)diesel biodiesel. These compounds do not exist in the #1(ULS kerosene), renewable diesel (RD) and MS library; therefore, a small degree of biodiesel FAME. Together with FAME these uncertainly surrounds their identification. These compounds create an environment with a molecules cannot be isolated from biodiesel defined polarity- a predisposition to modulate because their concentrations are too low. solubility that is determined by concentrations Therefore, this project was designed to of main and minor hydrocarbon components at synthesize the S-bearing compounds believed levels greater than about 0.1%. Despite the to be found in BGL-derived biodiesel in complexity in the molecular composition of quantities sufficient to characterize them by biodiesel fuels, various international definitions analytical methods such as NMR. We have and restrictions greatly narrow the range of developed strategies to synthesize thiophene possible compositions. However, low and thiolane and preliminary results indicate concentrations of impurities have intrinsic they can be produced in yields sufficient to solubilities complicated by specific assist in their characterization in biodiesel. The interactions*. We present here a study of identification of S-bearing compounds in BGL- possible relationships between the saturation derived biodiesel is necessary to devise points (SP) of GLY and SMG, fuel composition, effective desulfurization protocols needed to and classical markers of solvent polarity, using reduce the concentration of S-bearing existing theories to assist in explaining impurities in biodiesel to < 15 ppm, as specified experimentally determined SPs and by ASTM. interactions. The results help establish an improved understanding of the compositional Modulating the Solubility of Saturated factors defining solubility, the barriers imposed Monoglycerides (SMG) and Glycerol (GLY) in by current fuel definitions, and the magnitude Blended Biodiesel Fuels Richard W. Heiden*1, of compositional changes needed to reduce the and Martin Mittelbach2,1R.W. Heiden unwanted effects of impurities.

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*Heiden,Schober, Mittelbach,(2017)JAOCS 94:285-299.

Co-production of acrylic acid in a typical The Use of Controlled Flow Cavitation to biodiesel plant: a techno-economic assessment Improve the Performance of Degumming, Xiaofei P. Ye*, University of Tennessee, USA Refining and Biodiesel Operations Darren J. Producing value-added chemicals from Litle*, Arisdyne Systems, Inc., USA glycerol is imperative for a sustainable future of An overview of the application of biodiesel. Despite efforts worldwide, the controlled flow cavitation and compression- commercial production of acrylic acid from decompression jet atomization phenomenon glycerol faces challenges, both technologically for the intensification of chemical processing and economically. Based on our patented applications is presented. For vegetable oil acid technology using carbon dioxide as reaction degumming and/or neutralization reactions, the medium in a two-step process to catalytically reasons for enhanced performance of the convert glycerol to acrylic acid, we established refining operation, reduced environmental computer simulation models to analyze the impact, observed reduction in necessary acid energy efficiency and economics of the process. and/or caustic addition as well as decrease in oil The analysis was conducted in conjunction with loss, potential savings in steam consumption published data of a typical intermediate-sized and decrease in maintenance opex is discussed biodiesel facility, aiming at the possibility of and industrial scale examples given. The producing acrylic acid on site. Sensitivity efficient removal of residual soaps, phosphorus, analysis in response to the market value of ffa and metals while minimizing and in some glycerol, the source and cost of carbon dioxide cases even eliminating the need for water recycling, and the changes in process kinetics washing or silica addition is also described. will also be presented. Finally, the power of controlled flow cavitation to reduce catalyst consumption, increase throughput, and reduce monoglyceride content in finished biodiesel is also described.

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IOP 4 / PRO 4.1: Biorefinery Technology and Catalysis Chairs: Helen Ngo Lew, USDA, ARS, ERRC, USA; and Kris Knudson, Crown Iron Works Co., USA

An Efficient Catalytic Approach to the efficient access to specific cosmetic oils. It paves Synthesis of Wax Esters from Fatty Acid Methyl the way for further larger implementation of Esters Duc Hanh Nguyen1, Guillaume Raffa1, this catalytic approach, which affords wax Yohan Morin1, Simon Desset1, Frédéric Capet1, esters from readily available bioresources, with Véronique Nardello-Rataj1, Franck Dumeignil*2, applicative properties comparable to those of and Régis Gauvin1,1UCCS, France; 2Université de benchmark products. Lille, France Objective: Wax esters are commodity Towards the Biolubricants Endgame: Building materials used as cosmetics, lubricating agents, Superior Lubricants, One Structural Feature at plasticizers or surface coatings. They are a Time Latchmi Raghunanan*1, Laziz Bouzidi2, obtained either from specific bioresources, with and Suresh Narine2,1Trent Centre for limited availability, or from non-trivial synthetic Biomaterials Research, Departments of Physics processes. In order to circumvent these issues, & Astronomy and Chemistry, Trent University, we propose to develop an efficient access to Canada; 2Trent University, Canada these compounds using catalytic upgrading of Structure‐property relationships are fatty acid methyl esters (FAME). Methods used: increasingly valued for the identification of To achieve this, we reasoned that catalytic specifically engineered materials with dehydrogenative conversion of alcohol into properties optimized for targeted application(s). esters and its reverse reaction, ester To date, a significant amount of research effort hydrogenation, can be performed using the has been exerted globally towards the same cataytic system, by adjusting operational preparation of bio-derived lubricants with conditions. Thus, we targeted the one-pot, two- continually improved performance properties, step conversion of fatty acid methyl esters into including a large body of work from our own wax esters using a molecular ruthenium-based group, the Trent Center for Biomaterials catalyst. The first step was performed under Research. However, while numerous reviews hydrogen pressure, affording fatty alcohols, can be found in the recent literature on the which were then converted into wax esters by synthesis and performance of bio-derived H2 extrusion. Results: In the absence of solvent lubricants, those content which review and of base additive, and after optimization, specifically the recent advances in their excellent conversion and selectivity were predictive cold flow properties (i.e., reached, from both methyl oleate and from a crystallization/melting, viscosity and flow commercial FAME mixture. Specific studies behaviours) are still noticeably absent from the were devoted to feed purification, which literature. Such studies are important not only proved to be the key to achieve full conversion for applications including lubricants and of FAME substrates. Physicochemical biodiesel production which are obviously investigations revealed that resulting influenced by fluidity at low temperatures, but compounds display properties similar to also for applications whose properties are in benchmark commercial products such as jojoba whole or in part dependent upon thermal oil, of lesser availability compared to the herein processing and/or flow. The latter includes considered bioresources. Conclusions: This materials such as phase change materials for study validates the interest of this simple and energy storage, and waxes for cosmetic

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formulations and as food modifiers. In this renewable jet fuel the feed stock needs to contribution, the structure-property undergo various types of chemical reactions, relationships of linear and branched esters like hydrodeoxygenation (HDO), hydrodewaxing prepared from lipid‐based oleochemicals are (HDW), hydrocracking (HDC) and reviewed from a fundamental perspective. We hydrodearomatization (HDA). Detailed will show that ester materials with tunable-on- knowledge and control of these reaction demand cold flow properties can be custom mechanisms is key to design a process, that will engineered based on the judicious design of the produce a high yield of renewable jet fuel molecular architecture from a toolbox of sorts meeting the ASTM D 7566 specification. The comprising of all possible structural elements. properties of different fats and oils have been analyzed, and the impact of those properties, Renewable Diesel from Waste Lipids: like fatty acid distribution, contaminants ect. on Challenges and Conversion Impacts David the design and setup of the conversion process, Schwalje*1, Larissa Perotta2, and Michael will be discussed. Especially, the carbon chain Zhao3,1Axens NA, USA; 2Axens, France; 3Axens, length plays a huge role in determining the final USA jet yield, since alkanes with a carbon number of Renewable diesel production via the 18 of higher cannot be included in the jet fuel hydrogenolysis, saturation, and isomerization of product, and therefore has to be converted into lipid feedstocks is a proven technology solution, molecules with lower carbon number, which with multiple worldwide projects either in result in a jet yield loss. Another important step operation, construction, or engineering. Recent in the process is the isomerization of linear debates related to land usage and multi- alkanes into branched alkanes, a step that is key industry demand for traditional vegetable oils to produce a jet fuel meeting the low freezing coupled with regulatory incentives has resulted point requirement. Case studies covering the in renewable diesel plants increasing the whole process from fats and oils to renewable percentage of feedstocks derived from animal jet fuel will be presented. fats and wastes such as tall and used cooking oil. This presentation will focus on the catalytic Effect of Thermal Treatment on Feeding Value and processing impacts of those feedstocks of Expeller Soybean Meal in Hexane-free including: • Tall oil rosin acid conversion and Soybean Processing Michal Kaválek*1, and impacts • The effects of organic nitrogen on Vladimír Plachý2,1Farmet a.s., Czech Republic; hydroisomerization activity and the value of 2czech, Czech Republic reliable feedstock pretreatment • Used cooking Extrusion-expeller processing (EP1) of oils: contaminants and process impacts • Co- soybeans is used mainly in local processing and processing alternative feedstocks with it is suitable for annual capacities up to 400,000 petroleum diesel and catalytic challenges tonnes. The EP1 process is based on separation associated with alternative feedstocks The of oil from seed in a screw press, therefore no topics will be addressed utilizing pilot test chemicals like hexane are used. EP1 products results, case studies, and commercial feedback. are expeller meal and vegetable crude oil. Expeller meal has about 6-8% of residual oil. Challenges in converting various fats and oils Before oil pressing in a screw press, the oilseed into a high yield of renewable jet fuel Asbjørn is usually conditioned and extruded. Extrusion S. Andersson*,Haldor Topsoe A/S, Denmark process is accompanied by flash steam release – In order to convert fats and oils into a mixture of steam and air under atmospheric

– 18 – ABSTRACTS 2019 AOCS ANNUAL MEETING & EXPO May 6–9, 2018 pressure. About 65 kilograms of flash steam per allow existing installations to reduce steam tonne of soybeans is released. Therefore there consumption, with low capex and minimal is a great potential for recuperation of energy shutdown time for installation. These modules and it can be transferred to soybeans in can be installed on top of existing bean multistep preheating conditioner before conditioners, allowing use of waste heat to soybeans reach the extruder. During the study increase capacity, improve overall conditioning the amount of recuperated energy and or replace leaking tube sections. The modular influence of thermal exposition on feeding design makes installation faster and less values has been evaluate (PDI, urease activity, expensive. The modules can also be used for protein fraction according to CNCPS and protein new conditioning application using a digestibility in chicken balance trials). combination of waste heat and steam sources. Experiences have shown that it is possible to The long life of the plates in this abrasive recuperate 20 kWh per tonne from this flash environment reduces maintenance costs steam. Recuperation of heated air from the oil associated with frequent replacement of tube press can save additional 10 kWh per tonne. sections and required downtime. The external Energy savings of recuperation amount to about flexible hoses connected to manifolds allow for 25%. Optimization of thermal exposure during easy isolation. Any plate can be blocked off the EP1 is the key to achieve the best feeding without opening the modules. Also each value at lower operating costs. Different module has an access door that can be used to thermal exposition of soybeans causes changes replace any plate with minimal disruption of in the protein solubility and digestibility, production. therefore an optimized feed for ruminants and monogastric animals can be produced. A New Material for Reducing Glycidyl Esters in Edible Oil Chelsea L. Grimes*, and Cristian Maximizing Heat Recovery in Soybean Libanati,W.R. Grace, USA Processing Mohamed Abid*,Solex Thermal Glycidyl esters (GE) in edible oil are known Science Inc., Canada carcinogenic and mutagenic process Soybean processing plants are always contaminants that have recently been evaluating options to maximize operating subjected to European legislation. In order to margins. Conditioning of Soybeans is an energy reduce glycidol concentrations in one pass RBD intensive process and is critical in achieving oil to proposed regulatory limits, we have target efficiency in oil extraction plants. The studied a material at different temperatures, availability of waste heat sources vary with contact time, dosages, and initial GE plant layout, steam sources and meal cooling concentrations without adversely affecting oil technology used. However the choice of a heat quality. Our presentation will outline properties transfer technology to efficiently recover this of this novel material as well as catalytic low grade energy is critical to finding an performance in multiple oil matrices. We will efficient and economical solution. Plate Heat also present a kinetic analysis of this reaction to exchangers provide high density of heat incorporate this material into existing oil transfer area within a compact design that refining technologies and ultimately remove the allows for an efficient utilization of the necessity for secondary refinement. recovered energy. The plate channels maintain high velocities which is essential to higher rates A Comparison of Conventional Short Path of heat transfer. The Bean Heater Modules Distillation to a Proprietary Short Path Stripper

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in Reducing Glycidyl Fatty Acid Esters ( GEs) FAMEs, monoglycerides, tocopherols, and and 3-MCPD Esters in Refined Edible Oils Marc similar products, owing to its ability to operate Koukoulas*,Artisan Industries Inc. , USA at extremely low pressures. This presentation Short Path Distillation has been identified compares the viability of applying “Short Path as a potential technology for significantly Distillation” in eliminating these heat-induced reducing the concentration of GEs and MCPDs, contaminants to a “Proprietary Short Path identified as potential carcinogens, in refined Stripper”. An overview of the features of the edible oils. The technology, also commonly Short Path Stripper and Short Path Distillation is referred to as “Short Path Evaporation” has presented for this “Stripping-only” application. been predominantly used in the distillation of high boiling, heat sensitive materials, such as

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IOP-P: Industrial Oil Products Poster Session Chair: Jerry King, Critical Fluid Symposia, USA

1. Copolymers from Photochemical Thiol- Eastern red cedar (ERC) is an abundant ene Polycondensation of Fatty Dienes with resource in the U.S. and has been investigated Alkyl Dithiols. Bryan R. Moser*, USDA for the extraction of cedarwood oil (CWO) and Agricultural Research Service, USDA CWO bioactivity, particularly its use to protect Photochemical thiol-ene polycondensation wood against termites and decay fungi. of unsaturated monomers based on renewable Methanol extraction of ERC sawdust gives a 9-decenoic acid with various alkyl dithiols burgundy oil (BO). This BO contains CWO and a readily afforded copolymers in high yield. burgundy solid (BS). Evidence indicates the BS Monomers were prepared by acid-catalyzed itself has inhibitory bioactivity. This study condensation of 9-decenoic acid with diols such investigated the wood preservation properties as ethylene glycol, 1,2-propylene glycol, 1,3- of BS alone, in combination with CWO and in propanediol, 1,4-butanediol, neopentyl glycol, conjunction with an amylose inclusion complex 1,4-cyclohexanedimethanol, 9-decenol, and 2- (AIC) against termites, brown-rot decay fungi allyloxyethanol to give fatty dienoic esters. and white-rot decay fungi. Wood was treated These dienes were then polymerized with 1,2- by vacuum impregnation and tested for ethanedithiol, 1,3-propanedithiol and 1,4- resistance to termites and four species of decay butanedithiol in the presence of catalytic 2,2- fungi. The AIC made wood less palatable and dimethoxy-2-phenylacetophenone as more toxic to termites but did not inhibit the photoinitiator to afford a family twelve novel brown-rot fungi or the white-rot T. versicolor linear copolymers. Physical properties such as but did inhibit the white-rot I. lacteus. The CWO molecular weight, polydispersity index, degree led to both lower termite mass loss and higher of polymerization, glass transition temperature, termite mortality and had an inhibitory effect melting point, crystallization onset on the white-rot decay fungi. However, it took a temperature, and thermal stability were combination of AIC and CWO to have an measured. Number average molecular weights inhibitory effect on the brown-rot fungi. The BS ranged from 11 – 45 kDa, melting points were had a minor inhibitory effect on termites but 25 oC or greater, crystallization onset did not inhibit the brown-rot fungi or the white- temperatures ranged from -15 to 55 oC, glass rot I. lacteus. It did, however, inhibit the white- transitions varied from -26 to 17 oC, and rot T. versicolor. Wood blocks vacuum thermal stabilities were greater than 330 oC impregnated with the combination of the AIC, (temperature corresponding to 10% mass loss CWO and BS resulted in the highest termite by DSC). Determination of mechanical mortality, and the lowest percentage wood properties such as tensile strength and Young’s mass losses for the termites and all four wood modulus are planned for future studies. In decay fungi species studied. summary, thiol-ene chemistry is a useful tool for rapid production of renewable polymers 3. Synthesis of Thiophene and Thiolane utilizing mild, solventless reaction conditions. Derivatives Found in Biodiesel Produced from Brown Grease Lipids. Shehu Isah*, Delaware 2. Effect of Burgundy Solid Extracted from State University-USDA, USA Eastern Red Cedar on Subterranean Termites Moved to talk in BIO 3.1/IOP 3/PRO 3.1: and Wood-Decay Fungi. Fred J. Eller*, USDA, Biofuels ARS, NCAUR, USA

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4. Proximate Composition, Fatty Acid ratio of reactants, the hydroxyl numbers (OH#) Profile, Mineral and Tocopherol Contents of of polyols varied from 120-330 mg KOH/g, Two Industrial Hempseed Varieties in useful for foams, adhesives, sealants and Response to Sowing Dates and Pesticide coatings. Polyols were used to formulate strong Treatment. Peiyi Shen*1, Zili Gao1, Hui Li1, and and elastic polyurethane sealants and adhesives Bingcan Chen2, 1Dept. of Plant Sciences/North with glass transitions above room temperature, Dakota State University; 2North Dakota State tensile strengths above 10 MPa and elongations University, USA above 100%. With the 2018 Farm bill, industrial hemp will be treated as an emerging crop which is 6. Lipid-Based Sulfones as Next-Generation anticipated to encourage rapid growth in the Organic Phase Change Materials. Navindra burgeoning U.S. hemp industry. Industrial Soodoo*1, Latchmi Raghunanan2, Laziz Bouzidi1, hempseed contains all the essential amino acids and Suresh Narine1, 1Trent University, Canada; and fatty acids necessary to maintain healthy 2Trent Centre for Biomaterials Research, human life, and could be a new good source of Departments of Physics & Astronomy and nutrients for both humans and livestock. Chemistry, Trent University, Canada However, the nutritional quality of industrial Three n-alkyl sulfones (n-SO2-n) hempseed, including the levels of protein and synthesized from vegetable oil derivatives and oil, is influenced by numerous factors, such as representative of an n-SO2-n series (n = 10, 12 seed varieties, sowing date, and pesticide & 18) were investigated and contrasted with treatment, etc. In order to obtain a specific the current lipid-based PCMs found in the quality of industrial hempseeds suitable for literature. The resulting sulfones displayed growth in the United States, we investigated excellent thermal characteristics suitable for the impact of sowing dates and pesticide phase change material (PCM) applications. The treatments on the proximate composition, fatty series were synthesized in high yield and purity acid profile, mineral and tocopherol contents of via the solvent-free oxidation reaction of the two industrial hempseeds varieties (Katani and lipid-based n-alkyl sulfides using hydrogen Delores) grown at the NDSU Langdon Research peroxide and acetic acid catalyst. Their Extension Center (LREC), Langdon, ND. The molecular structures were confirmed by Fourier results showed that there was an important Transform Infrared Spectroscopy, Proton range of variation for almost all seed Nuclear Magnetic Resonance, and Mass composition, and the cultivars × sowing date × Spectrometry. Their thermal transition and pesticide treatments interaction effect was thermal stability properties were studied under significant for chemical compositions. an inert environment using Differential Scanning Calorimetry and Thermogravimetric 5. Cost-effective Polyurethane Sealants and Analysis, respectively. Crystal structures were Adhesives from Soybean Polyols. Jian Hong*1, elucidated by Powder X-Ray Diffraction. The Dragana Radojcic2, Mathew Long1, and Zoran sulfones possessed melting points from 89-109 Petrovic2, 1Kansas Polymer Research Center, °C and energy storage densities of 196-266 J/g, Pittsburg State University, USA; 2Pittsburg State and underwent evaporation with an onset University, USA which increased with molecular mass. Further, Cost-effective soybean oil-based polyols were 10-SO2-10 crystallized in the energetic γ- developed by an economical process based on polymorphic form, whereas 12-SO2-12 and 18- one-pot two stages reaction. By adjusting the SO2-18 crystallized in the thermodynamically

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more stable β′ + β and β-polymorphs, and amines, and without use of hazardous respectively. Overall, the sulfones possessed isocyanates. Due to some structural specifics, higher melting points and enthalpies, and along with easy variation of their chemical better thermal stability than analogous structure and characteristics, soybean oil based monofunctional lipid-based counterparts. The NIPUs can be a material of choice for fabrication superior performance of the sulfones is by SLA of many products, particularly for attributed to the strong intermolecular healthcare industry and for variety of consumer interactions associated with the highly polar products. We created a range of novel soybean sulfonyl group within the fatty chains. The new oil based NIPU resins; the effect of their knowledge generated on the thermal behavior structure on characteristics of SLA printed parts and crystal structure of these sulfones revealed was studied. The experimental results showed that they have desirable tunable-on-demand that these resins can be used as virgin or properties to be used as PCMs for thermal blended with commonly used petrochemicals, energy storage. and, as such, they can be used for preparation of variable products. 7. Soy Oil-Based Non-Isocyanate Polyurethane Resins for Stereolithography. 8. Renewable Polyols for Polyurethane from Ivan Javni*1, Olivera Bilic2, Vivek Sharma1, Soybean Oil. Maha L. Shrestha*1, Petar Camille Holman3, and Xianmei Wan1, 1Pittsburg Dvornic2, and Mathew Long1, 1Kansas Polymer State University, USA; 2Kansas Polymer Research Center, Pittsburg State University, Research Center/PSU, USA; 3Pittsburg State USA; 2Pittsburg State University, USA University - KPRC, USA The main objective of the research is to Stereolithography (SLA) is a three-dimensional synthesize renewable, bio-based polyols from printing method. It is based on soybean oil and utilize them in preparation of photopolymerization of liquid reactive rigid polyurethane foams and casts. Thiol-ene precursor by focused ultraviolet laser beam “Click” Chemistry was employed for synthesis of controlled by specific software. Parts made by functionalized polyols from soybean oil derived SLA have good surface finish, excellent polymercaptans. The reaction can be initiated dimensional accuracy and good mechanical with UV light in presence of 2-hydroxy 2- properties. Stereolithography can be used to methylpropiophenone as a photoinitiator or via create prototypes, models and fabricate a thermal pathway utilizing radical initiator, 2,2’- variety of products. The rapid expansion of Azobis(2-methylpropionitrile). The stereolithography caused strong demand for polyurethanes prepared from these polyols novel resins, which are dominantly produced possesses good thermal and mechanical from petrochemicals. Due to the depleting of properties, which are comparable to the natural resources and the negative effect of commercially available polyurethanes. carbon dioxide on the environment, there is a tendency for replacement of petrochemicals 9 Isocyanate-Free Polyurethane Coatings with bio-based renewable materials. Natural from Soybean Oil. Olivera Bilic*1, Ivan Javni2, oils are one of those that have great potential Tim Dawsey3, Xianmei Wan2, and Camille for synthesis of variety of resins for Holman1, 1Kansas Polymer Research stereolithography. Among them are non- Center/Pittsburg State University, USA; isocyanate polyurethanes (NIPUs), which are 2Pittsburg State University, USA synthesized from soy oil based cyclic carbonates

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Polyurethanes, due to their excellent 10. Feruloylated Vegetable Oils Protect physical and mechanical properties, find uses in Vitamins C and E from UV Degradation. David a wide range of applications, such as adhesives, L. Compton*1, Kervin O. Evans1, and John R. packaging, insulation, bedding, upholstery, Goodell2, 1USDA, ARS, NCAUR, USA; 2iActive footwear, vehicle parts, coatings, etc. Naturals, USA Recognized as being among the most versatile Vitamins C and E and their derivatives are used families of polymers, polyurethanes are as antioxidants in topical formulation in commonly prepared by the reaction of cosmetics and personal care products. Vitamin isocyanates with polyols. However, an E (100 μM) was rendered a poor antioxidant in increasingly strict regulatory environment, the 2,2-diphenyl-1-picrylhydrazyl (DDPH*, 200 within which the industry must operate, is μM) assays in acetonitrile, scavenging < 50 % of driving strong demand for safer, and renewable, DPPH* within 30 min, after exposure to (UV) for components in polyurethane production. 4 h. Vitamin C solutions (100 μM) were Growing pressure to reduce the use of the rendered moderate antioxidants, scavenging > highly toxic and hazardous isocyanate starting 50 % of DPPH* within 30 min, after exposure to materials is in addition to ongoing concerns UV radiation for 4 h. Feruloyl soy glycerides around depletion of petrochemical resources (FSG) are UV absorbers synthesized from the and the negative effects of carbon dioxide on biocatalytic conversion of soybean oil and the environment. A promising alternative for ferulic acid ethyl ester that have a total UV the preparation of isocyanate-free absorbance and photostability comparable to polyurethanes, with renewable content, the commercial UV absorber, octinoxate (ONX). involves the reaction of cyclic carbonates FSG (100 – 1000 μM) was added to acetonitrile (carbonated soybean oil - CSBO) with solutions of the vitamins and their derivatives multifunctional amines. Using this approach we to determine if FSG could photoprotect the have developed methods for the production of vitamins and their derivatives, allowing them to isocyanate-free soy-based polyurethane retain their antioxidant efficacy after 4 h of UV coatings. The two-step preparation, reported irradiation. The addition of FSG, 500 and 1000 here, involved synthesis of a soy polyamine μM, allowed Vitamin E and most of the non-isocyanate (NIPU) followed by reaction to antioxidant derivatives to retain rapid produce a soy polyamide-polyester NIPU resin antioxidant activity after 4 h UV exposure. with pendant double bonds. The resin was used Vitamin C retained rapid antioxidant capacity for thiol-ene photopolymerization. The goal of with 100 μM FSG after 4 h of UV exposure. FSG this work is a cost-competitive route to high performed slightly better than the commercial modulus, and high abrasion resistant, coatings UV absorber, ONX, in protecting the vitamins’ from safe and renewable feedstocks. and their derivatives’ antioxidant activities from Mechanical and thermal properties are UV degradation. FSG also possessed intrinsic reported here on our work to date, along with antioxidant capacity that ONX did not, which plans for continued improvement to the may have contributed to its better performance process. Promising results indicate that soy- when mixed with the vitamin’s and their based coatings have comparable, or better, derivatives in the DPPH* assays. properties than representative commercial coatings. 11. Development of New Coconut Oil-based Biting Fly Repellents. Jim A. Kenar*1, Steven C.

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Cermak1, and Junwei J. Zhu2, 1USDA-ARS- P.D. Wanasundara2, 1University of NCAUR-FFR, USA; 2USDA-ARS-Lincoln, USA Saskatchewan, Canada; 2Agriculture and Agri- Many blood-sucking insects such as are capable Food Canada, Canada of transmitting human and animal pathogens Application of green technology is becoming a worldwide and can be serious pests of humans foremost tool in any industries to mitigate and animals. For example, stable flies harmful results created by environmentally- (Stomoxys calcitran) alone can cause over $2 unfriendly processes and solvents. A new billion annually in losses to the U.S. cattle designer solvent, natural deep eutectic solvents industry. Repellents are an important tool for (NaDES) is a potential green, bio-based ionic reducing the impact of biting insects on humans liquids composed of two or more compounds and animals and plant- and botanical-based that are generally plant based primary derivatives have been used against insects in metabolites. NaDES can provide desired agricultural and urban settings for at least two extractability for a range of compounds by millennia. However, most of plant-based employing the most suitable solvent repellents are short-lived in their effectiveness, composition. This study focused on extraction primarily due to their high volatility. We of phenolic compounds from canola seed and recently discovered that inexpensive coconut meal using NaDES as a replacement for organic oil-based fatty acids are an excellent insect solvents. Eight different NaDES systems were repellent and active against a broad array of prepared by mixing choline chloride (hydrogen blood-feeding insects. The C8 to C12 medium- bond acceptor) with different hydrogen bond chain fatty acids represent >65% of total fatty donor compounds that are found in plant acids present in coconut oil and were shown to cellular environment. Those solvent be the predominant repellent compounds. combinations were choline chloride:citric acid Laboratory bioassays showed these compounds (1:1, 2:1, 3:1), choline chloride:glucose (1:1, to repel biting flies for two weeks after 2:1), choline chloride:sucrose (4:1), choline application with stronger repellency and longer chloride:maltose (4:1), and choline residual activity than that of DEET (N,N-Diethyl- chloride:raffinose (11:2) with 20% (w/w) water meta-toluamide) the most effective and long- content in each. Defatted samples of canola lasting repellent currently available seed coat, endosperm, ground whole seed, and commercially. The coconut fatty acids were also commercial canola meal [expeller pressed (EP) formulated into an aqueous starch formulation and desolventized and toasted (DT)] were that showed up to 96 h protection (which to our extracted at 1:30 (solid:solvent, by weight) ratio knowledge is the longest lasting repellent at 50oC for 1 hr. Direct UV absorbance spectrum reported to date) against biting flies for cattle of each extract was taken at 200 – 340 nm and treated with this formulation. These promising compared with sinapic acid standards. The results suggest these compounds may be easily different NaDES showed a wide range of adopted for livestock animal producers as well difference in the extractability of sinapic acid as other public health applications for and derivatives for different canola substrates. preventative repellent protection. This presentation will discuss the potential of utilizing NaDES on different canola substrates 12. Application of Green Technology using using 1H- and 13C-NMR as the tool of Natural Deep Eutectic Solvents (NaDES) for confirmation of compound identity. Recovering Canola Seed Phenolics. Sumudu N. Warnakulasuriya*1, Takuji Tanaka1, and Janitha

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13. Extraction, Purification and 14. Novel Catalyst for Cationic Characterization of Wax from Sorghum as an Homopolymerization of Epoxidized Methyl Alternative Natural Wax. Junsi Yang*, Loren Oleate. Dragana Radojcic* and Zoran Petrovic, Isom, Felipe Sperotto, Curtis Weller, and Ozan Pittsburg State University, USA N. Ciftci, University of Nebraska-Lincoln, USA Epoxidized natural oils are very valuable There is a growing demand for alternative monomers in various polymerization reactions. natural wax sources due to dwindling wax Various cationic catalysts were used to supply, increasing wax applications and prices. polymerize epoxidized oils such as superacids Global wax demand will grow 1.5% annually till and Lewis acids. Here, we report polymerization 2019, whereas wax supply growth will be only of epoxidized methyl oleate as a model 0.4%. Sorghum is a promising alternative compound in the presence of the new catalyst natural wax source. However, there is no (BCF), affording lower reaction rate at very low specific processing method to obtain high concentration and higher degree of quality sorghum wax that meets natural wax polymerization. The effect of different catalysts industry specifications. Therefore, the objective on the polymerization process was investigated. of this study was to develop an improved processing method to obtain a high quality wax 15. Filled Epoxy Resins from Natural Oils. from sorghum. Sorghum whole kernel, bran, Dragana Radojcic*, Pittsburg State University, and DDGS were extracted with hexane and USA supercritical carbon dioxide (SC-CO2) and then Thermosetting cast resins with different purified by a simple ethanol washing process. SiO2 filler content were prepared from Wax yield from whole kernel was 0.11 wt.% epoxidized soybean oil (ESO) and epoxidized from hexane extraction, whereas it was 0.8 algal oil (EAO) in order to study matrix-filler wt.% from SC-CO2 extraction at 40 MPa/70 ºC. interaction. Ring opening polymerization and Temperature and pressure of SC-CO2 extraction copolymerization was catalyzed by fluoroboric positively affected wax yield. Following ethanol acid. Effect of filler on thermal and mechanical washing, wax recovery from whole kernel, bran properties was investigated. Matrix cross-link and DDGS extracts was 81, 32.3 and 27.5%, density was a direct function of epoxy oxygen respectively, and the melting point improved to content in epoxidized oils, being higher for ESO 80, 79, and 78 °C from 77.5, 56.8, and 56.3 °C, polymer samples. Effect of filler on properties respectively. Moreover, the ethanol washing was stronger in composites prepared with process improved the hardness (needle lower functional EAO. penetration method) from 40 to 2, which is comparable to Carnauba waxes. Ethanol 16. Impact of Delivery System Type on washing also decreased acid and iodine Curcumin Bioaccessibility: Comparison of numbers (USP 401) from 20 to 3.3, and from Curcumin-loaded Lipid Nanoparticles with 59.4 to 23.6, respectively. Sorghum wax is Commercial Curcumin Supplements. D. Julian J. promising natural wax which may reduce U.S. McClements, Bingjing Zheng*, Xiaoyun Zhang, dependence on non-renewable petroleum- and Shengpeng Pen, University of derived waxes or natural wax imports. Our Massachusetts Amherst, USA process minimizes processing steps and The bioavailability of curcumin depends on generates superior quality sorghum wax. the physical form that it is delivered. In this study, nanoemulsion-based delivery systems fabricated using pH-driven method was

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compared with three commercially available curcumin supplements. The pH-driven method involved dissolving curcumin in an alkaline solution (pH 12.5) and then adding this solution to an acidified nanoemulsion (pH 6.0). The three commercial curcumin products were capsules or tablets purchased from an online supplier: Nature Made, Full Spectrum, and CurcuWin. The different curcumin formulations were then subjected to a simulated gastrointestinal tract (GIT) model consisting of the mouth, stomach, and small intestine phases. A comparison of the prepared nanoemulsions and commercial products indicated that the curcumin concentration in the mixed micelles decreased in the following order: CurcuWin ≈ nanoemulsion >> Full spectrum > Nature Made. This study provides valuable information about the impact of the delivery form on the bioavailability of curcumin. It suggests that encapsulating curcumin within small lipid particles may be advantageous for improving its absorption from the GIT.

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