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Three zeolites were treated with magnesium nitrate hexahydrate (Mg(NO3)2⋅6H2O) salt to generate active magnesium oxide (MgO)–zeolite catalysts for the isomerization of oleic acid to give the iso-oleic acid (precursor of isostearic acid). Isostearic acid is a crucial component used in the formulation of bio-lubricants including cosmetic and personal care products. The treatment step is intended to poison (or neutralize) the external acid sites of the zeolites, thus inhibiting the formation of by-products (i.e., dimer fatty acids). The acid sites, crystallinity, thermal property, morphology and elemental composition of the zeolites before and after treatments were investigated by scanning electron microscopy, fourier-transform spectroscopy, thermogravimetric analysis, and x-ray powder diffraction. In addition, the effect of a calcination step after treatment was examined to determine if this step was necessary to obtain an active and stable catalyst. As expected, the higher the concentration of MgO on the zeolites, the less dimer was detected in the isomerization products, while the conversion of oleic acid and selectivity of iso-oleic acid remained at a relatively high level. This is promising because the MgO has deprotonated the external acids of the zeolites to generate a high purity isostearic acid that is potentially suitable for personal care products.

Current evidence indicates that foods with added plant sterols or stanols can lower serum levels of low-density lipoprotein cholesterol. This review summarizes the recent findings and deliberations of 31 experts in the field who participated in a scientific meeting in Winnipeg, Canada, on the health effects of plant sterols and stanols. Participants discussed issues including, but not limited to, the health benefits of plant sterols and stanols beyond cholesterol lowering, the role of plant sterols and stanols as adjuncts to diet and drugs, and the challenges involved in measuring plant sterols and stanols in biological samples. Variations in interindividual responses to plant sterols and stanols, as well as the personalization of lipid-lowering therapies, were addressed. Finally, the clinical aspects and treatment of sitosterolemia were reviewed. Although plant sterols and stanols continue to offer an efficacious and convenient dietary approach to cholesterol management, long-term clinical trials investigating the endpoints of cardiovascular disease are still lacking. International Plant Sterol and Stanol Association (IPSSA); National Center for Complementary and Integrative Health (NCCIH); National Center for Advancing Translational Sciences [IR13AT009270-01]

Sorghum has potential as a domestic source of wax for applications in the food and nonfood industries. The waxes extracted from sorghum have similar physical properties to those of Carnauba wax, a common imported commercial wax. This work focused on the extraction, fractionation, and characterization of waxes from sorghum kernels. Extraction was performed by varying the extraction conditions including temperature and solvents (hexane, ethanol, and methanol). A fractionation technique was developed to separate and quantify waxes from nonwaxes. The fractions were then characterized using a reverse-phase high-performance liquid chromatography method developed in our laboratory that utilizes an evaporative lightscattering detector for quantification. The results showed that the average amount of wax extracted from the surface of intact sorghum kernels was about 0.3 wt% using hexane at temperatures between 25 and 120C and 1000 psi. The yield of wax via hexane extraction increased with temperature and ranged from about 0.06 to 0.39 wt%. Extraction with alcohols resulted in higher yields of extracts, but after fractionation to remove nonwax components, the yield of waxes was reduced by 31% for ethanol and 47% for methanol compared to hexane.

Commercial waxes are difficult to analyze due to their limited solubility in most organic solvents. Recently, our laboratory published a new reverse phase HPLC-MS method using a C30 column, a gradient of methanol and chloroform, an evaporative light-scattering detector (ELSD), and atmospheric pressure chemical ionization mass spectrometry (APCI-MS) to analyze jojoba wax (jojoba oil), carnauba wax, and sorghum wax. In the current study, the published HPLC method was modified by reducing the solvent gradient program to 60 minutes and this new method was evaluated for its usefulness for the analysis of five other commercial waxes (beeswax, rice bran, sunflower, candelilla and paraffin waxes). The ELSD appeared to detect all types of wax components, whereas the APCI-MS was most useful for the identification of wax esters and was unable to detect hydrocarbons, such as those in candelilla wax and paraffin wax. Previous HPLC methods for waxes and most GC methods for waxes only separate wax esters with size up to 54 carbons (C54) but this method was able to separate those with size up to 60 carbon wax esters. This report presents the first HPLC chromatograms for rice bran, sunflower, candelilla, and paraffin waxes. The main contribution of this work is the evidence that a C30 reverse phase HPLC system provides acceptable chromatographic separation of major components in commercial waxes.

The acylglycerols (AG) in sorghum bran and distiller’s dried grains and solubles (DDGS) from sorghum postfermentation have been converted to fatty-acid methyl esters (FAME) using an in situ transesterification method. The reactions were conducted at 25 or 40 C by incubating 8 g of feedstock, containing 1.3–2.4 mmol AG, in a solution of 2.4 or 4.8 mmol of NaOMe dissolved in 6.4 or 12.8 mL MeOH. The experimental results confirmed that reducing the moisture to approximately 2% (w/w) within the feedstock was necessary for the reaction to proceed. All of the reactions were monitored using high-performance liquid chromatography and all performed better at 40 C than at 25 C. The most successful reactions used a AG:NaOMe:MeOH molar ratio of 1.0:2.0:131.7. Those reactions used 4.8 mmol NaOMe dissolved in 12.8 mL MeOH producing up to 98.3% FAME when sorghum bran was used as the feedstock. When DDGS from sorghum were used as the feedstock, the yield averaged 32.2% under the previously established optimal conditions.

There is tremendous demand for the development of new bio-based materials with bioactive properties to replace antimicrobials or antibiotics that are no longer effective against microorganisms. For this current research, a new group of phenolic branched-chain fatty acids (n-PBC-FA), hybrid molecules of natural monophenols (i.e., thymol, carvacrol and creosote) and mixed fatty acid (i.e., derived from soybean and safflower oils), are efficiently produced through a process known as arylation. The reactions for producing these compounds involve a combination of the modified H+‐Ferrierite zeolite catalyst and water co-catalyst which give 72.4%, 77.2%, and 48.8% yields for thymol-safflower branched-chain fatty acids (BCFA), creosote-safflower BCFA and carvacrol-BCFA, respectively. The ratios (2.2–17 wt/wt) of water co-catalyst to zeolite catalyst were found to have a significant influence on the arylation reaction as the water co-catalyst depressed the isomerization reaction and favored the arylation reaction. This modified H+-ferrierite zeolite can be regenerated by calcining at 500 °C in air for 2 h, and the activity of the catalyst can be maintained at a relatively stable level without significant deactivation even after 7 reused cycles. The n-PBC-FA products are thoroughly characterized by gas chromatography and high performance liquid chromatography with high-resolution mass spectrometry. Most importantly, these products can be purified up to 97 wt% by the wiped-film molecular distillation device.

Phytosterols (plant sterols) occur in the cells of all plants. They are important structural components that stabilize the biological membranes of plants. Sterols can occur in the "free" unbound form or they can be covalently bound via an ester or glycosidic bond. Since our previous 2002 review on phytosterols and phytosterol conjugates, phytosterol glucosides have been found to be important structural components in the lipid rafts of the plasma membrane of plant cells, where they are thought to be essential to the function of plasma membrane enzymes and perhaps other proteins. Phytosterols also serve as precursors in the synthesis of important bioactive compounds such as steroidal saponins, steroidal glycoalkaloids, phytoecdysteroids, and brassinosteroids. Methods for the analysis of phytosterols range from traditional gas chromatography of free phytosterols to modern sophisticated forms of mass spectrometry which have been used for the new field of sterol lipidomics, sometimes called "sterolomics." Phytosterol-enriched functional foods first appeared about twenty years ago and many clinical studies have confirmed the low density lipoprotein (LDL) cholesterol-lowering properties of various types of phytosterols. In recent years additional clinical studies and more than ten important meta-analyses have provided insights to better understand the cholesterol-lowering and other biological effects of plant sterols.

In the preceding manuscript [ Moreau et al. 2018 , 10.1021/acs.jmedchem.7b01691 ] we described a successful fragment-based lead discovery (FBLD) strategy for discovery of bacterial phosphopantetheine adenylyltransferase inhibitors (PPAT, CoaD). Following several rounds of optimization two promising lead compounds were identified: triazolopyrimidinone 3 and 4-azabenzimidazole 4. Here we disclose our efforts to further optimize these two leads for on-target potency and Gram-negative cellular activity. Enabled by a robust X-ray crystallography system, our structure-based inhibitor design approach delivered compounds with biochemical potencies 4-5 orders of magnitude greater than their respective fragment starting points. Additional optimization was guided by observations on bacterial permeability and physicochemical properties, which ultimately led to the identification of PPAT inhibitors with cellular activity against wild-type E. coli.

The discovery and development of new antibiotics capable of curing infections due to multidrug-resistant and pandrug-resistant Gram-negative bacteria are a major challenge with fundamental importance to our global healthcare system. Part of our broad program at Novartis to address this urgent, unmet need includes the search for new agents that inhibit novel bacterial targets. Here we report the discovery and hit-to-lead optimization of new inhibitors of phosphopantetheine adenylyltransferase (PPAT) from Gram-negative bacteria. Utilizing a fragment-based screening approach, we discovered a number of unique scaffolds capable of interacting with the pantetheine site of E. coli PPAT and inhibiting enzymatic activity, including triazolopyrimidinone 6. Structure-based optimization resulted in the identification of two lead compounds as selective, small molecule inhibitors of bacterial PPAT: triazolopyrimidinone 53 and azabenzimidazole 54 efficiently inhibited E. coli and P. aeruginosa PPAT and displayed modest cellular potency against the efflux-deficient E. coli Δ tolC mutant strain.

The design and synthesis of macrocyclic inhibitors of human rhinovirus 3C protease is described. A macrocyclic linkage of the P1 and P3 residues, and the subsequent structure-based optimization of the macrocycle conformation and size led to the identification of a potent biochemical inhibitor 10 with sub-micromolar antiviral activity.

Biodiesel production in the U.S. from vegetable oils has increased substantially during the past decade. However, its further increase is limited by the low amounts of oil produced per hectare from temperate oilseed crops. Recently novel transgenic sugarcane has been developed to accumulate both sugars and lipids in stems, making it a promising dual-purpose feedstock to produce both ethanol and biodiesel. In this study, two lines of the transgenic lipid producing sugarcane (lipid-cane) and the non-transformed sugarcane were characterized and processed. The total lipid concentrations were 0.7%, 0.9% and 1.3% for the non-transformed sugarcane and lipid-cane lines19B and 25 C, respectively. Lipid composition analysis showed that about 31–33% of the total lipids were triacylglycerols, main feedstock for biodiesel production, for the lipid-cane samples, while this value was only 5% for the non-transformed sugarcane. By processing the sugarcane stems with a juicer, about 90% of the sugars and 60% of the lipids were extracted with juice. The extracted sugars in juice were fermented to ethanol and the lipids were later recovered from the fermented juice using organic solvents. The recovered lipids from the fermented juice were 0.3, 0.5 and 0.8 g/100 g dry stem for the non-transformed sugarcane and lipid-cane lines 19B and 25 C, respectively. This study proved the concept of the lipid and sugar coproduction from the novel lipid-cane, which have a potential to make a large-scale replacement of fossil derived fuel without unrealistic demands on land area.

Sorghum is a genus of plant in the grass family, which is used for both grain and forage production throughout the world. In the United States, sorghum grain is predominantly used as livestock feed, and in ethanol production. In recent years however, sorghum grain has been investigated for other industrial applications, including gluten free food sources for the US food market, and waxes. The United States is the world's largest producer of grain sorghum, which is grown in the arid regions of the southern Great Plains, Arizona and California.Carnauba wax is used in a variety of products; including cosmetics, industrial polishes, food products, and paper products. The United States has no domestic source of carnauba wax, and imports 100% of its carnauba wax supply. Sorghum wax has demonstrated similar physical properties to carnauba wax, and could potentially be a viable substitute for carnauba wax.In this paper we present the first successful reversed phase HPLC method, via a C30 column, for the analysis and characterization of waxes, without the need for specialized columns or sample derivation. Sorghum wax is composed of a heterogeneous mixture of compounds, dominated by C28 and C30 saturated and unsaturated species, while carnauba is more homogeneous in nature, and composed primarily of C56-C60 saturated wax esters.

The aim of this study was to determine if the compositional difference between grain sorghum and corn impact ethanol yields and coproduct value when grain sorghum is incorporated into existing corn ethanol facilities. Fermentation properties of corn and grain sorghum were compared utilizing two fermentation systems (conventional thermal starch liquefaction and native starch hydrolysis). Fermentation results indicated that protease addition influenced the fermentation rate and yield for grain sorghum, improving yields by 1-2% over non-protease treated fermentations. Distillers Dried Grains with Solubles produced from sorghum had a statistically significant higher yields and significantly higher protein content relative to corn. Lipid analysis of the Distillers Dried Grains with Solubles showed statistically significant differences between corn and sorghum in triacylglycerol, diacylglycerol and free fatty acid levels.

In this updated analysis of patients with relapsed/refractory multiple myeloma (RRMM) from the RandomizEd, OpeN Label, Phase 3 Study of Carfilzomib Plus DExamethAsone Vs Bortezomib Plus DexamethasOne in Patients With Relapsed Multiple Myeloma (ENDEAVOR) trial, clinically meaningful overall survival improvements continue to be observed with carfilzomib 56 mg/m(2) and dexamethasone (Kd56; n = 464) versus bortezomib and dexamethasone (n = 465), including in key patient subgroups. With longer-term data, the favorable benefit-risk profile of Kd56 continues to support its use as a standard-of-care in RRMM. Introduction: The phase III RandomizEd, OpeN Label, Phase 3 Study of Carfilzomib Plus DExamethAsone Vs Bortezomib Plus DexamethasOne in Patients With Relapsed Multiple Myeloma (ENDEAVOR) trial showed significantly improved progression-free survival and overall survival (OS) with carfilzomib (56 mg/m(2)) and dexamethasone (Kd56) versus bortezomib and Kd56 (Vd) in patients with relapsed or refractory multiple myeloma (RRMM). We report updated OS and safety data after 6 months of additional follow-up. Patients and Methods: Patients with RRMM (1-3 previous lines of therapy) were randomized 1:1 to Kd56 or Vd. Median OS was estimated using the KaplaneMeier method; OS was compared between treatment groups using Cox proportional hazards models. Results: As of July 19, 2017, median follow-up was 44.3 months for Kd56 and 43.7 months for Vd. Median OS was 47.8 months (Kd56) versus 38.8 months (Vd; hazard ratio, 0.76; 95% confidence interval, 0.633-0.915). OS was longer with Kd56 versus Vd within age and cytogenetic subgroups, and according to number of previous lines of therapy, previous bortezomib exposure, previous lenalidomide exposure, and lenalidomide-refractory status. Exposure-adjusted incidences per 100 patient-years of adverse events (AEs) were 1352.07 for Kd56 and 1754.86 for Vd; for Grade >= 3 AEs, these values were 162.31 and 175.90. Conclusion: With median follow-up of approximately 44 months, clinically meaningful improvements in OS were observed with Kd56 versus Vd, including in all subgroups examined. The Kd56 safety profile was consistent with previous analyses.

Alkylresorcinols are long-chain phenolic compounds that have been reported to be localized in the outer layers of the kernels of wheat, rye, barley, and other grains. A sensitive HPLC method with fluorescence detection was recently reported for the quantitative analysis of alkylresorcinols in cereal grains and products. Using this new HPLC method we report for the first time that wheat germ oil contains moderate levels of alkylresorcinols, approximately 800–1,500 µg per gram of oil. We also found that commercial wheat germ oil and some experimental samples of wheat germ oil and barley germ oil also contained three unknown peaks. Upon further evaluation of these peaks it was found that the peaks appeared to be tocopherols (one peak of α-tocopherol, one peak of δ-tocopherol, and a peak with the combination of β- and γ-tocopherol), even though the excitation and emission wavelengths for alkylresorcinols (excitation 274 nm and emission 300 nm) are different than those for tocols (excitation 294 nm and emissio...

Carotenoids are potentially valuable components in grain sorghum and there is a need to better understand their concentration, composition, and value. Thirteen modern commercial grain sorghum hybrids and five sorghum lines were extracted and analyzed and the levels of oil and carotenoids were compared. The same samples were also evaluated for lipolytic enzyme activity. The oil content in all eighteen samples ranged from 3.21 to 4.29 wt%. Lutein and zeaxanthin were the predominant carotenoids and the levels of total carotenoids ranged from 3.82 to 19.5 ppm in the oil, which was much lower than the levels of total carotenoids in two yellow corn samples (70.8 and 103 ppm). Lipolytic enzyme activity was estimated by storing milled kernel samples for 2 weeks at 25 °C and measuring the levels of total free fatty acids. After 2 weeks, the levels of free fatty acids in the oil of the eighteen sorghum samples ranged from 11.49 and 52.17 wt%, compared to 10.29 and 17.54 wt% in oil from the two corn samples. This new data will be useful for persons using grain sorghum for food, biofuels and other industrial applications. Examples of sorghum genotypes with high and low levels of carotenoids and high and low levels of lipolytic enzymes were both identified.

Dimer acids are a class of important intermediates that are widely used in many practical applications including polyamides, lubricants, paints, and coatings. They are typically produced through the polymerization (dimerization) of tall oil fatty acids (TOFA) using clays as catalysts. Although this technology is well developed and efficient, the drawback is that the clay catalysts cannot be recycled, generating considerable amounts of hazardous waste. In addition, these products consist of a complex mixture of dimer acids, trimer acids, and polymeric acids. This complexity has limited the ability to thoroughly evaluate their chemical structures. This study reports an advanced recycle zeolite catalysis process using plant-based soybean oil fatty acid (SOFA) which can selectively control the structure formation of the dimer acids and result in yields that are just as efficient as the TOFA technology. The detailed chemical structures of products were thoroughly verified by Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), gas chromatography–mass spectroscopy (GC–MS), and liquid chromatography-mass spectrometry (LC–MS). The reuse process was demonstrated by conducting ten recycle experiments and maintaining high yields, which shows great potential in replacing clay to produce dimer acids. These valuable insights into the structures of the dimer acid products and catalyst reuse results will improve the value and production of dimer acids to meet new industrial uses.

Epoxy resins are one class of important reactive pre-polymers used in the coating industry. To manufacture epoxy resins with antimicrobial properties, active quaternary ammonium groups are often introduced into the polymeric backbones following resin polymerization reactions for structure modification. However, these complicated approaches associated with these types of reactions make the commercialization of the antimicrobial epoxy polymers uneconomical, impractical and inconvenient. Besides, quaternary ammonium groups are undesirable because the hydrophilicity of the groups makes the resins less water-resistant. In order to simplify the development of antimicrobial epoxy polymers, we prepared an amide by reacting novel bio-based phenolic-branched fatty acids with ethylenediamine. The resulting amide was cured into a commercial epoxy resin -- diglycidyl ether of bisphenol A (DGEBA), which was solution-cast into epoxy polymer films. The antimicrobial activities of the resulting epoxy polymer films were investigated. The crude phenolic branched fatty acid amides (PBC-FAAs) as curing agents were separated and characterized by thin-layer chromatography, proton nuclear magnetic resonance (1H-NMR), gas chromatography-mass spectrometry (GC MS), liquid chromatography-mass spectrometry (LC/MS) and Fourier-transform infrared spectroscopy (FT-IR). The thermal and mechanical properties of the polymer films were also investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Cured epoxy films prepared from purified PBC-FAA exhibited antimicrobial activity against Listeria innocua. However, the crude, unpurified PBC-FAA-cured epoxy film showed much more promising antimicrobial activity against both Listeria innocua (Gram positive) and Escherichia coli (Gram negative).

Drug-resistant Gram-negative bacteria are of increasing concern worldwide. Novel antibiotics are needed, but their development is complicated by the requirement to simultaneously optimize molecules for target affinity and cellular potency, which can result in divergent structure-activity relationships (SARs). These challenges were exemplified during our attempts to optimize inhibitors of the bacterial enzyme CoaD originally identified through a biochemical screen. To facilitate lead optimization, we developed mass spectroscopy assays based on the hypothesis that levels of CoA metabolites would reflect the cellular enzymatic activity of CoaD. Using these methods, we were able to monitor the effects of cellular enzyme inhibition at compound concentrations up to 100-fold below the minimum inhibitory concentration (MIC), a common metric of growth inhibition. Furthermore, we generated a panel of efflux pump mutants to dissect the susceptibility of a representative CoaD inhibitor to efflux. These approaches allowed for a nuanced understanding of the permeability and efflux liabilities of the series and helped guide optimization efforts to achieve measurable MICs against wild-type E. coli.

All fruits, vegetables, grains and other plant materials contain small amounts of plant sterols, which are essential for the function of the biological membranes in living cells. The average human consumption of plant sterols has been estimated to be about 150–350 mg/day and trace amounts of stanols (which are defined as saturated sterols such as sitostanol), but this number varies regionally and is higher for vegetarians. When consumed in the diet, plant sterols reduce the levels of serum cholesterol. In 1995 the first functional food product, Benecol spread (enriched in plant stanol fatty acid esters), was developed by Raisio and marketed, first in Finland and then globally. Since then many other functional food products have been developed and are now available globally. In addition to stanol esters, other functional food products contain plant sterol esters and/or free (unesterified) plant sterols and stanols. In essentially all of the current functional foods that are enriched in sterols and stanols, the feedstock from which the sterols and stanols are obtained is either tall oil (a byproduct/ coproduct of the pulping of pine wood) or vegetable oil deodorizer distillate (a byproduct/coproduct of the refining of vegetable oils).

An aqueous enzymatic method was developed to extract oil from wheat germ. Wheat germ pretreatment, effect of various industrial enzymes, pH, wheat germ to water ratio, reaction time and effect of various methods of demulsification, were investigated. Pretreatment at 180 °C in a conventional oven for 4 min reduced the moisture 12.8–2.2 % and significantly increased the oil yield. Adding a combination of protease (Fermgen) and cellulase (Spezyme CP) resulted in a 72 % yield of emulsified oil from wheat germ (both commercial and laboratory milled wheat germ). Using the same oil extraction conditions optimized for wheat germ, yields of 51 and 39 % emulsified oil were obtained from barley germ (laboratory milled), and rice bran, respectively. Three physical demulsification methods (heating, freeze-thawing, and pH adjustment) and enzymatic methods (Protex 6L, Protex 7L, Alcalase, Fermgen, Lysomax and G-zyme 999) were compared. After demulsification with Protex 6L, free oil yields of 63.8 and 59.5 % were obtained with commercial wheat germ and with laboratory milled wheat germ, respectively. Using the same demulsification conditions optimized for wheat germ, yields of 45.7 % emulsified oil and 35 % free oil were obtained for barley germ and rice bran, respectively.

There is significant research interest in developing new industrial materials from vegetable oils and animal fats. Such biobased materials can be more environmentally friendly because they tend to have good biodegradability and are derived from renewable resources. This paper describes a catalytic approach for the addition of phenol to the olefinic site of oleic acid using the H-ferrierite zeolite. A number of experimental parameters were examined, including different reaction components and their ratios, and reaction conditions. Under optimized conditions, phenol-branched-chain fatty acid isomers were obtained in up to 70% yield. The materials were characterized using various analytical techniques, including GC, GC–MS, and HPLC–MS.

The global interest in reducing the use of petroleum resources to mitigate climate change has created a need for the continuing demand for environmentally friendly systems from renewable resources to produce clean and sustainable technology. One promising approach involves the development of catalysts and process improvements to increase the efficiency of the chemical modification reactions. In this study, sunflower oil was used in the skeletal isomerization reaction to introduce methyl branching at the alkyl fatty acid chain of the oil (methyl-branched-chain triglycerides (MBC-TG)) in the presence of a modified H+-BETA zeolite catalyst. Such modification of the oil is proposed to improve its low temperature fluidity, by preventing precipitation at low temperatures. The modified catalyst was easy to handle and separate from the reaction products. The products were thoroughly characterized by common analytical instruments. To evaluate the practicality of this environmentally friendly process, a techno-economic model was constructed to estimate the production cost.

A process was developed to produce a germ-enriched fraction from hull-less barley using a Fitzpatrick comminuting mill (FitzMilling) followed by sieving. Hulled and hull-less barleys contain 1.5–2.5% oil and, like wheat kernels, which contain wheat germ oil, much of the oil in barley kernels is in the germ fraction. A process that combined FitzMilling and sieving produced a germ-enriched fraction with an oil content of ≈15% and a yield of ≈1.1%. For comparison, this is higher than the levels of oil in most samples of commercial wheat germ. Experimental conditions were also described to produce a germ-enriched fraction with a higher yield (2.16%), but it would have lower oil content (10.24%). Germination and compositional analysis studies suggested that FitzMilling hull-less barley for 2 min or longer reduced germination rates to 1% or less, which was interpreted to mean that almost the entire viable germ was removed. In contrast, FitzMilling conventional hulled barley for 4 min had no effect on g...

In this study, the effect of the 80% ethanolic extract of corn bran (EECB) on inhibition of nitric oxide (NO) production and inducible nitric oxide synthase (iNOS) expression in lipopolysaccharide (LPS)-stimulated Raw 264.7 cells was investigated. The EECB inhibited LPS-induced NO production and iNOS expression in a dose-dependent manner. Four hydroxycinnamic acid derivatives (HADs), including two free cinnamic acids, p -coumaric acid (CA) and ferulic acid (FA), and their conjugate phenolic amides, p -dicoumaroyl-putrescine (DCP) and diferuloylputrescine (DFP), were found to be present in the EECB by LC–MS analysis, and DFP (378.66 μg/g) was the predominant phenolic compound, followed by DCP (7.83 μg/g) > CA (5.58 μg/g) > FA (1.84 μg/g). The four HADs significantly inhibited NO production and iNOS expression in a dose-dependent manner. Among the four HADs tested, DFP showed the most potent inhibition on NO production and iNOS mRNA and protein expression, followed by DCP > FA ⩾ CA. DFP also exhibited the strongest inhibition on LPS-induced iNOS and NF-κB luciferase activity, which was followed by DCP ⩾ FA (CA) > CA (FA). Thus, these results suggest that phenolic amides in the corn bran may be a potential source of natural anti-inflammatory agents.

Widespread epidemics of Stenocarpella ear rot (formerly Diplodia ear rot) have occurred throughout the central U.S. Corn Belt in recent years, but the influence of S. maydis infected grain on corn ethanol production is unknown. In this study, S. maydis infected ears of variety Heritage 4646 were hand-harvested in 2010 from a production field in central Illinois and segregated into one of five levels of ear rot severity based upon visual symptoms. The concentration of ergosterol, a sterol produced by fungi but not plants, was observed to increase with the severity of ear rot (127–306.5 μg/g), and none was detected in the control corn. Corn test weight declined with progression of the disease and was 42.6% lower for the most severely rotted grain from ears infected early in their development. Accompanying changes in composition were also apparent. Crude fat and oil contents decreased (from 4.7 to 1.5%) and fiber increased (from 6.6 to 9.6%), but starch content remained largely invariant. Oil compos...

Corn fiber gum (CFG) is a hemicellulose (arabinoxylan)-enriched fraction obtained by the extraction of corn bran/fiber using a mild alkaline hydrogen peroxide process. The unique polysaccharide, CFG, with its low solution viscosity has been proposed as a stabilizer for oil-in-water emulsions. We have verified that in some model systems, CFG can out-perform the “gold standard” emulsifier, gum arabic. Our results have also shown that “pure” CFG fractions often contain considerable amounts of associated lipids, phenolic acids and proteins which contribute to its emulsifying properties. The extraction of CFG with alkaline hydrogen peroxide was investigated using different combinations of alkali concentration and time to identify the optimum extraction condition to retain its functional groups (protein, lipids and phenolic acids). The pure CFG prepared by this process was hydrolyzed with 1.5 N methanolic KOH at 70 °C for 1 h to release hydroxycinnamic acids (p-coumaric and ferulic) and lipids. The total lipid was extracted with chloroform/methanol, evaporated and quantified. The released phenolic acids were identified and quantified using HPLC with detection by both UV and evaporative light-scattering detection (ELSD). The protein content was determined by an AACC approved combustion method. The total lipids, phenolic acids and protein content in CFGs isolated with lower alkali concentration for a shorter time was comparatively higher than CFGs isolated with higher alkali concentration for a longer time. The presence of these phenolic acids, lipids and protein in CFG may contribute to its excellent emulsifying properties and may combine to give improved chemical, physical, and even nutritional properties. Understanding these critical structural elements required for optimal emulsification properties will allow future commercial producers of CFG to provide consistent quality and functionality in their products.

In previous aqueous enzymatic oil extraction (AEOE) experiments we reported a best free oil yield of 49% of the hexane extracted yield of dry fractionated corn germ. In the current experiments, a dispersion of 10% cooked, dry-fractionated germ in water was treated with α-amylase, glucoamylase and a cellulase complex. Free oil was collected by centrifuging a foam fraction of the dispersion. Several dispersion treatments were tried to evaluate their release of free oil and effect on the production of foam. The foam contained up to 8% free oil (dispersed from germ containing 26% oil) and fines oil (not centrifugally separable), protein and germ particles. Treatment with α-amylase and glucoamylase prior to treatment with the commercial cellulase used in previous AEOE studies increased the free oil yields about 25–61% of the hexane-extractable yield. A preliminary cost analysis indicates that oil separation with the amylase enhanced AEOE appears to be preferable to AEOE alone and profitable if crude corn oil cost exceeds $1.1/kg ($0.50/lb).

Maize prolamin (zein), together with starch, hydroxypropyl methylcellulose, sugar, salt, yeast and water can form wheat-like cohesive, extensible, viscoelastic dough when mixed above room temperature (e.g. 40 � C). This dough is capable of holding gas. However, it is excessively extensible, and when used for hearth-type rolls, it tends to become flat. Bench-scale defatting of zein with chloroform at room temperature significantly (P

During the dry grind ethanol process, ground corn is fermented and the major co-product is a feed called distillers dried grains with solubles (DDGS). This study investigated the changes that occur in the composition of corn oil that can be extracted from various process fractions during the dry grind ethanol process. In the first part of this study, samples of distillers dried grains, thin stillage, condensed distillers solubles (also known as syrup), and DDGS were obtained from 7 dry grind ethanol plants. The levels of deleterious free fatty acids were high (>7%) and those of valuable total phytosterols were also high in all fractions (>2%). In the second part of this study, changes in the content and composition of the fatty acids, phytosterols, tocopherols and tocotrienols were quantitatively analyzed in crude oil samples extracted from nine dry grind process fractions from three commercial ethanol plants. Fatty acid and phytosterol composition remained nearly constant in all nine fractions, although some significant variations in phytosterol composition existed among the fractions. Examination of the tocopherols and tocotrienols revealed that γ-tocopherol was the most abundant tocol in ground corn but an unknown tocol became the predominant tocol after fermentation and persisted in the remaining processing fractions and in the final DDGS product. Overall, the remaining majority of tocols remained relatively unchanged.

Oat (Avena sativa L.) kernels appear to contain much higher polar lipid concentrations than other plant tissues. We have extracted, identified, and quantified polar lipids from 18 oat genotypes grown in replicated plots in three environments to determine genotypic or environmental variation in these lipids. Validation experiments indicated a solid phase silica gel extraction step elution provided excellent and clean separation of extracted lipids into neutral lipid, glycolipid, and phospholipid fractions. Analysis of phospholipids by HPLC (normal phase, diol column) indicated phosphatidylethanolamine, phosphatidylcholine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, and lyso- forms but very little genotypic or environmental variation. Di, tri and tetragalactosyl-diacylglycerols were quantified in the glycolipids, along with their mono-, di-, and triacyl estolides. Most of these exhibited significant genotypic variation. Molecular species analysis of the glycolipids in the Morton...

The many recent dry-grind plants that convert corn to ethanol are potential sources of substantial amounts of corn oil. This report describes an aqueous enzymatic extraction method to separate oil from dry-fractionated corn germ. The method is an extension of a method previously developed for wet-mill germ. Oil dispersed in lipid bodies throughout the germ was converted to oil droplets suspended in an aqueous solution and then to drops of oil large enough to be separated from the solution as a continuous, buoyant phase (free oil). A microwave oven was used to cook the germ to its highest temperature, just short of burning. Thereafter the germ was extracted using the method developed for wet-mill germ: mix the heated germ with water and cook it under pressure, followed by colloid milling and enzymatic digestion of the milled germ particles overnight. A foam fraction was removed from the digested dispersion by bubbling nitrogen through a short column connected to a mixing tank. The foam fraction was then centrifuged to separate free oil. An estimate of aqueous enzymatic extraction plant costs to extract 24 million kg of dry-fractionated germ per year [40 million gal/year ethanol], showed that income from the unrefined oil streams and a stream sending the rest of the germ to the fermentation process was roughly equal to the estimated operating cost, with an investment of $2.6 million. Recycle of the enzyme may reduce the estimated enzyme cost of $750,000/year.

Isostearic acids (ISA) are important bio‐based ingredients for many commercial products such as lubricants, detergents, and cosmetics. This study is targeted to compare the efficacy of various phosphine derivatives in neutralizing the external acidic surface of zeolite which is responsible for the unwanted oligomerization during zeolite based skeletal isomerization reaction producing dimer as byproducts. Sixteen phosphine derivatives were individually evaluated with heat activated ammonium (NH₄⁺) cationic ferrierite zeolite to produce iso‐oleic acid from oleic acid which was converted to ISA through the hydrogenation process. In comparison, eight newly tested phosphine additives were found more effective than the previously reported phosphines (TPP, TPTP) to increase the product yield of iso‐oleic acid, ultimately ISA, either by suppressing the byproducts or accelerating the reaction rate as a whole. The performance depends on the electron donating capacity of central phosphorus atom of phosphine derivative attracting proton from the external surface of zeolite. This phenomenon is resulted from the combination of electronic effects and structural hindrances posed by the different substituents attached to the phosphine derivatives. The effectiveness of sixteen Lewis base phosphine additives were tested in neutralizing the external acidic surface of zeolite. The neutral outer surface of zeolite is ideal for suppressing dimer formation and thus producing the iso‐oleic acid (precursor of isostearic acid) in high yield through Lewis base‐zeolite combination skeletal isomerization reaction.

A study was conducted to examine the chemical composition of corn oil obtained after fermentation of corn to make fuel ethanol via centrifugation and compare its composition to that of corn germ oil (commercial corn oil) and experimental corn oils. The levels of free fatty acids in the post fermentation corn oil were high (11-16%), as previously reported. The levels of free phytosterols and hydroxycinnamate steryl esters (similar to oryzanol in rice bran oil) were higher than those of corn germ oil and were comparable to those of ethanol-extracted corn kernel oil. The levels of tocopherols were lower in post-fermentation oil than in either corn germ oil or ethanol extracted corn kernel oil. The levels of lutein and zeaxanthin in post-fermentation were much higher than those in corn germ oil and were comparable to those in ethanol-extracted corn kernel oil. Overall, exposure to all upstream processes of a fuel ethanol plant, including high-temperature liquefaction, saccharification and fermentation appeared to have the most notable effect on tocopherols, but it had little effect on the levels of free phytosterols, hydroxycinnamate steryl esters, lutein and zeaxanthin. It may be desirable to recover these valuable functional lipids prior to using the post-fermentation corn oil for industrial applications such as making biodiesel if a cost-effective recovery process can be developed.

Fluidized-bed fast pyrolysis was carried out on three different barley biomass coproduct streams, straw, hulls, and distiller’s dried grains with solubles (DDGS), from Saccharomyces cerevisiae fermentation of barley grain. Each of these byproducts of fuel ethanol production from barley grain is a possible source of feedstock for advanced biofuels production via fast pyrolysis. Bio-oil recovery was in the range of 42−50 wt % of the biomass, but optimized yields could be as much as 70 wt % for each feedstock when the mass balance is mathematically adjusted to account for all unrecovered products using optimization modeling. Biochar yields were 16−21% from the barley feedstocks. Bio-oil produced from straw and hulls had an energy content of 24−25 MJ/kg on a dry basis, while bio-oil produced from DDGS had a dry basis energy content >30 MJ/kg. The bio-oils were further characterized for composition and stability. None of the bio-oils were found to be shelf-stable, as established by an increase in average molec...