Synthesis and physical properties of petroselinic based estolide esters

A new series of petroselinic (Coriandrum sativum L.) based estolide 2-ethylhexyl (2-EH) esters were synthesized, as the capping material varied in length and in degrees of unsaturation, in a perchloric acid catalyzed one-pot process with the esterification process incorporated into an in situ second step to provide the coriander estolide 2-EH ester. The kinematic viscosities ranged from 53 to 75 cSt at 40 °C and 9.1 to 14.6 cSt at 100 °C with a viscosity index (VI) ranging from 151 to 165. The caprylic (C8) capped coriander estolide 2-EH ester had the lowest low-temperature properties (pour point = −33 °C and cloud point = −33 °C), while the coco-coriander estolide 2-EH ester produced an estolide with modest low-temperature properties (pour point = −24 °C and cloud point = −25 °C). The coco-coriander estolide 2-EH ester was explored for the ability to resist oxidative degradation with the use of an biodegradable additive package added in 1.5%, 3.5%, or 7.0% units based on weight. The oxidative stability increased as the amount of stability package increased (rotating pressurized vessel oxidation test (RPVOT) times 65-273 min). Along with expected good biodegradability, these coriander estolide 2-EH esters had acceptable properties that should provide a specialty niche in the U.S. as a biobased lubricant.     

Carotenoid profiling of Hordeum chilense grains: The parental proof for the origin of the high carotenoid content and esterification pattern of tritordeum

The outstanding high carotenoid content of the tritordeum (×Tritordeum Ascherson et Graebner) grains, a promising novel cereal derived from the crossing of durum wheat and the wild barley Hordeum chilense, has previously been assigned as a character derived from the genetic background of its wild parent. The carotenoid profile of H. chilense, especially the lutein esters presented in this study, provide biochemical evidences to confirm this affirmation, being the first time that the individual carotenoid profile of this cereal has been characterized. The total carotenoid content (6.14 ± 0.12 μg/g) and the individual carotenoid composition were very similar to the tritordeum grains, with lutein being the major carotenoid (88%; 5.38 ± 0.11 μg/g) and very low levels of β-carotene. In contrast to tritordeum, H. chilense presented a considerable amount of zeaxanthin (12%; 0.74 ± 0.01 μg/g). Up to 55% of lutein was esterified with palmitic (C16:0) and linoleic (C18:2) acids, presenting a characteristic acylation pattern, in agreement with the tritordeum one, and composed by four monoesters (lutein 3′-O-linoleate, lutein 3-O-linoleate, lutein 3′-O-palmitate and lutein 3-O-palmitate) and four diesters (lutein dilinoleate, lutein 3′-O-linoleate-3-O-palmitate, lutein 3′-O-palmitate-3-O-linoleate, lutein dipalmitate). These data may be useful in the field of carotenoid biofortification of cereals.     

Carotenoid evolution during postharvest storage of durum wheat (Triticum turgidum conv. durum) and tritordeum (×Tritordeum Ascherson et Graebner) grains

The process of in vivo esterification of xanthophylls has proven to be an important part of the post-carotenogenesis metabolism which mediates their accumulation in plants. The biochemical characterization of this process is therefore necessary for obtaining new and improved crop varieties with higher carotenoid contents. This study investigates the impact of postharvest storage conditions on carotenoid composition, with special attention to the esterified pigments (monoesters, diesters and their regioisomers), in durum wheat and tritordeum, a novel cereal with remarkable carotenoid content. For tritordeum grains, the total carotenoid content decreased during the storage period in a clear temperature-dependent manner. On the contrary, carotenoid metabolism in durum wheat was very much dependent on the physiological adaptation of the grains to the imposed conditions. Interestingly, when thermal conditions were more intense (37 °C), a higher carotenoid retention was observed for tritordeum, and was directly related to the de novo esterification of the lutein induced by temperature. The profile of lutein monoester regioisomers was constant during storage, indicating that the regioisomeric selectivity of the XAT enzymes was not altered by temperature. These data can be useful for optimizing the storage conditions of grains favoring a greater contribution of carotenoids from these staple foods.     

10-Undecenoic acid-based polyol esters as potential lubricant base stocks

A new class of polyol esters were prepared by esterification of 10-undecenoic acid (UDA) with three polyols namely trimethylolpropane (TMP), neopentyl glycol (NPG) and pentaerythritol (PE) in 92-96% yields. The esters were characterized by IR, ¹H NMR, HPLC and mass spectral studies. Polyol esters were evaluated for basic lubrication properties and found to be: viscosity at 40 °C, 11.2-36.1 cSt; at 100 °C, 3.2-7.3 cSt; viscosity index (VI), 162-172; pour point +3 to −36 °C; flash point, 254-296 °C. All the three polyol esters synthesized exhibited good thermal stability with TGA onset temperatures above 260 °C. The lubricating properties of the products compared well with polyol esters based on oleic acid.     

Functional characterization of extruded rice noodles with corn bran: Xanthophyll content and rheology

The rheological changes in rice noodles by the substitution of corn bran and the effect of temperature on the xanthophyll content (lutein and zeaxanthin) of the corn bran-rice flour noodles were evaluated. The use of corn bran increased the water holding capacity of rice flour at room temperature while the opposite results were observed after heating. The pasting parameters of rice flour-corn bran mixture were reduced with increasing levels of corn bran and the mixture paste exhibited more dominant liquid-like behavior. The noodles containing corn bran exhibited lower expansion ratio and softer textural properties. The levels of lutein and zeaxanthin in raw corn bran were 336.9 and 123.1 μg/100 g, respectively and were significantly reduced (P < 0.05) by heating. While lutein and zeaxanthin were not detected in the control noodles without corn bran, their levels in corn bran-incorporated noodles ranged from 56.2 to 137.3 μg/100 g and from 37.9 to 61.9 μg/100 g, respectively and were significantly reduced by 37.7–45.4% (P < 0.05) after cooking. Thus, the heat-labile characteristics of two xanthophylls were clearly observed. This study provides useful information on the processing performance and xanthophyll content of corn bran, possibly extending its use in a wider variety of foods.     

Basic properties of grain by-products and their viability in polypropylene composites

The objective was to study the potential of grain by-products (husk) of grains such as wheat (Triticum aestivum L; German name is Weizen) and rice (Oryza sativa) as reinforcements for thermoplastics as an alternative to or in combination with wood fibres. Prior to composites preparation, the chemical components of fibres such as cellulose, hemi-cellulose, lignin, starch, protein and fat were measured and the surface chemistry and functionality of grain by-products were studied using EDX and FT-IR. Structural constituents (cellulose, starch) were found in wheat husk (W) equal 42%, in rice husk 50% and in soft wood 42%, respectively. Thermal degradation characteristics, the bulk density, water absorption and the solubility index were also investigated. Wheat husk (W) and rice husk were found thermally stable at temperatures as low as 178 °C and 208 °C, respectively. The particle morphology and particle size were investigated using microscopy. Water absorption properties of the fibres were studied to evaluate the viability of these fibres as reinforcements. Polypropylene composites were fabricated using a high speed mixer and an ensuing injection moulding process with 40 wt% fibre. The tensile and Charpy impact strength of the resulting composites were investigated. The tensile elongation at break was found to 75% for wheat husk (W) composites and 23% for rice husk composites better than soft wood composites. Rice husk composites showed 13% better Charpy impact strength than soft wood composites. Due to coupling agent, tensile strength of composites found to improve 25% for soft wood, 35% for wheat husk (W) and 45% for rice husk.     

Temperature,Water and Fertilizer Influence the Timing of Key Events During Grain Development in a US Spring Wheat

Controlled environments were used to define the manner in which temperature, water and fertilizer affect the timing of key transition points during grain development and to investigate the effects of combined environmental factors in a US spring wheat (Triticum aestivum (L.)). When plants were subjected to very high temperature regimens (37/17  or 37/28 °C day/night) during grain development, the times to maximum kernel water content, maximum dry weight and harvest maturity were shorter than in plants maintained under a 24/17 °C day/night regimen. Starch accumulated at similar rates, but the onset and cessation of starch accumulation occurred earlier. Apoptosis in endosperm tissue also occurred earlier under high temperatures and coincided with physiological maturity. The addition of drought to the 37/17 °C regimen further shortened the time to maximum water content and dry weight and reduced the duration of starch accumulation, but did not influence the timing of protein accumulation or kernel desiccation. Post-anthesis fertilizer had little effect on time to maximum water content, dry weight, apoptosis, or harvest maturity under any of the temperature regimens and did not influence the timing of starch accumulation. However, both the rate and duration of protein accumulation were reduced when post-anthesis fertilizer was omitted.     

Effect of heating temperature on the particle size distribution in waxy wheat flour

The particle size of waxy (amylose-reduced) wheat (Triticum aestivum L.) starch was determined at isothermal temperatures by laser diffraction analysis. Flour samples were suspended in deionized water at temperatures ranging from 30 to 90 °C for 20–60 min. At 30 °C, all of the flour particles exhibited trimodal size distributions, i.e., the particles in the first, second, and third modes were <10 μm, 10–50 μm, and 51–300 μm, respectively. Control experiments with isolated starch indicated that the first and second modes were associated mainly with starch granules, whereas the third mode may have been related to gluten and gluten adhesion. The particle size distributions of waxy segregant wheat flours were temperature dependent. At 60 °C, there were significant changes in the particle size and distribution of waxy flours, which indicated the swelling of starch granules in response to elevated temperature. As the temperature increased, the peak particle size of waxy segregant wheat flours increased in different ways. The results suggest that variations in the swelling properties of selected waxy genotype flours may be due to the strength of starch–protein interaction and the capacity for starch granule gelatinization.     

Temperature-induced structural and chemical changes in cork from Quercus cerris

The effects of temperature on anatomical and chemical characteristics of Quercus cerris cork were examined. Cork samples were subjected to isothermal air heating between 150 °C and 400 °C and analyzed for mass loss, cellular structure and chemical composition.The thermal decomposition of Q. cerris cork is similar to that of Q. suber cork. Cork is thermally stable below 200 °C and after that degradation depended on temperature and heating time with increasing mass loss, i.e. 3% at 200 °C 10 min and 46% at 350 °C 60 min. With temperature and starting at 200 °C, cells expanded, cell wall thickness was reduced and corrugations were lost.Extractives degraded at lower temperatures, although aliphatic extractives were found to be more stable. Suberin from Q. cerris was more heat resistant than Q. suber suberin, while lignin showed similar resistance.These results provide a basis for studies on the production of Q. cerris bark expanded cork agglomerates for insulation purposes.     

Starch gelatinization distribution and peripheral cell disruption in cooking rice grains monitored by microscopy

Starch gelatinization kinetics governs rice cooking behaviour (cooking time and texture). Starch gelatinization however occurs unevenly in the cooking grain. The aim of this study was to investigate the dynamics of starch gelatinization topography in rice kernels cooked in excess water at two temperatures: 75 °C and 95 °C, for times ranging from 5 to 30 min. Gelatinization front position was assessed over time on 40 μm cross sections using four different tracking methods: directly or after iodine staining using a microscope or a stereomicroscope under normal or polarized light. The four methods gave similar results and the obtained kinetics can be used to model starch gelatinization during grain cooking.     

Use of tomato crop residues into soil for control of bacterial wilt caused by Ralstonia solanacearum

Tomato debris can be used as the soil amendment to reduce agricultural residue accumulation problems and increase soil fertility. However, pathogens present in the debris may form a risk for subsequent crops. In this study, tomato growth substrate was amended with tomato debris artificially inoculated with Ralstonia solanacearum and the effect of heat treatments on the survival of the pathogen was measured. Experiments were carried out in the laboratory and in greenhouses, using peat moss and sand mix in pots as substrates. Pots were enclosed in plastic bags or left open. Then 0, 5, 10 and 15 g of tomato debris were applied to 500 g growing medium, with four replicates per treatment. Treatments at 45 °C lowered tomato wilt indices in tomato cv. Money-Maker and that the pathogen was not eradicated after pot treatments at 25 °C. R. solanacearum remained pathogenic on the assayed growing media after a six-week treatment at 25 °C, but was eradicated after treatments at 45 °C. The lower infectivity of infected debris tomato plants when buried with high doses of organic matter and at temperatures above 45 °C suggests that adverse effects on the soil inoculum would be exerted through increased soil temperatures. This study demonstrates that tomato crop residues, usually considered waste material, could be used as soil amendments to reduce their effect as a source of contamination as they offer additional advantages.     

Fast separation and characterization of water-soluble proteins in wheat grains by reversed-phase ultra performance liquid chromatography (RP-UPLC)

Water-soluble proteins account for about 10% of total grain proteins in wheat (Triticum aestivum L.) and have specific functions in plant growth and development. In this study, a reversed-phase ultra performance liquid chromatography (RP-UPLC) method was trialed and the experimental conditions were optimized for rapidly separating and characterizing water-soluble proteins in wheat grains, and a comparative analysis with traditional RP-HPLC was performed. Under optimized separation conditions, fast, high resolution and reproducible RP-UPLC separation for water-soluble proteins could be obtained by gradually increasing eluting gradient from 21% to 47% in 30 min at 0.6 ml/min and 60 °C. Using this method, separation and characterization of water-soluble protein in wheat grains could be completed in less than 20 min for one sample, and the resolution and efficiency were significantly higher than those obtained with RP-HPLC. In addition, RP-UPLC consumed smaller amounts of samples and reagents as well. The optimized RP-UPLC could be used as an effective and alternative method for rapid separation and characterization of water-soluble proteins in wheat cultivar and germplasm evaluation, genetic and biochemical studies on grain proteins, and environmental influence analysis of water-soluble proteins.     

Control of brown rot of stone fruits by brief heated water immersion treatments

The effectiveness of brief (30 or 60 s) immersion in water at 24, 50, 55, 60, 65, or 70 °C was evaluated for the control of brown rot, caused by Monilinia fructicola, on California-grown peaches, nectarines, and plums. Inoculated fruits were treated and either stored at 20 °C for 5 days or at 0 °C and 95% RH for 30 days followed by 5 days at 20 °C to simulate commercial marketing conditions. Immersion in water at 55 °C for 60 s or at 60 °C for 30 or 60 s significantly reduced both decay incidence and severity among the remaining wounds that developed the disease. Water temperatures of 65 °C or higher were phytotoxic and caused moderate to severe surface injuries. Immersion in water at 60 °C for 60 s was effective for plums and it reduced the incidence of brown rot from more than 80% among control fruit to less than 2%. In nectarines, this treatment reduced decay incidence from 100 to less than 5% on fruit stored at 20 °C and from 73 to 28% on cold-stored fruit. Therefore, brief immersion in heated water can be an effective approach to manage postharvest brown rot of stone fruits, especially for the organic fruit industry.     

Synthesis and physical properties of mono-estolides with varying chain lengths

Saturated mono-estolide methyl esters and enriched saturated mono-estolide 2-EH esters were synthesized from oleic and different saturated fatty acids under three different synthetic routes. Estolide numbers (EN), the average number of fatty acid units added to a base fatty acid, varied with synthetic conditions. The attempts at obtaining saturated mono-estolide 2-EH esters, EN = 1, via distillation proved to be challenging, which lead to estolide samples with EN > 1 and the pour point values followed the same trend as the high EN estolides. The other synthetic routes provided saturated mono-estolide methyl esters with EN = 1. The resulting pour point values showed a linear relationship between the saturated capping chain length and pour point. As the saturated capping chain length increased the pour points also increased (higher temperatures): C-2 capped ?30 °C, C-10 capped ?12 °C, and C-18 capped 3 °C.The saturated mono-estolide methyl ester viscosities also showed an increase in viscosity at 40 and 100 °C as the saturated chain lengths increased. The viscosities for the C-4 saturated mono-estolide methyl ester was 9.5 cSt at 40 °C and 2.6 cSt at 100 °C, while medium chain length derivations (C-10 saturated mono-estolide methyl ester) were 19.7 cSt at 40 °C and 4.2 cSt at 100 °C, and at the longer chain length derivations (C-18 mono-estolide methyl esters) were 27.6 cSt at 40 °C and 10.7 cSt at 100 °C. In general, a new series of saturated oleic mono-estolide methyl esters were synthesized and physical properties were collected. The physical property data indicated that both chain length and EN affect low temperature properties.     

Effect of temperature, time and wheat gluten moisture content on wheat gluten network formation during thermomolding

A plastic-like material can be obtained by thermomolding wheat gluten protein which consists of glutenin and gliadin. We studied the effect of molding temperature (130-170 °C), molding time (5-25 min) and initial wheat gluten moisture content (5.6-18.0%) on the gluten network. Almost no glutenins were extractable after thermomolding irrespective of the molding conditions. At the lowest molding temperature, the extractable gliadin content decreased with increasing molding times and moisture contents. This effect was more pronounced for the α- and γ-gliadins than for the ω-gliadins. Protein extractabilities under reducing conditions revealed that, at this molding temperature, the cross-linking was predominantly based on disulfide bonds. At higher molding temperatures, also non-disulfide bonds contributed to the gluten network. Decreasing cystine contents and increasing free sulfhydryl and dehydroalanine (DHA) contents with increasing molding temperatures and times revealed the occurrence of β-elimination reactions during thermomolding. Under the experimental conditions, the DHA derived cross-link lanthionine (LAN) was detected in all gluten samples thermomolded at 150 and 170 °C. LAN was also formed at 130 °C for gluten samples containing 18.0% moisture. Degradation was observed at 150 °C for samples thermomolded from gluten with 18.0% moisture content or thermomolded at 170 °C for all moisture contents.     

Impact of baking conditions and storage temperature on staling of fully and part-baked Sangak bread

Bread staling involves a combination of physico-chemical phenomena that leads to a reduction of quality. This study aims at evaluating the impact of baking conditions (280 °C, 8 min; 310 °C, 5.5 min; 340 °C, 4 min), baking type (of fully baked (FB) and part-baked (PB)) and storage temperature (−18, 4 and 20 °C) on the staling of Sangak bread. Results showed that lower baking temperature with longer baking time produced drier bread with higher firmness. In FB Sangak breads, amylopectin retrogradation, amount of unfreezable water and firmness (measured by compression test) increased during storage at positive temperatures but hardness (determined by Kramer shear test) decreased significantly during first day of storage. The recrystallized amylopectin traps the free water resulting in crumb hardening. Water is also absorbed by the dry crust resulting in changes of rheological properties in the crust and crumb, and finally in staling. Storage at 4 °C resulted in increasing melting enthalpy of amylopectin crystallite in comparison with storage at 20 °C. Also it was found that firmness of PB breads due to rebaking was significantly lower than FB breads. There were no significant changes in staling parameters of FB and PB stored at −18 °C.     

Effect of high temperature on albumin and globulin accumulation in the endosperm proteome of the developing wheat grain

The accumulation of KCl-soluble/methanol-insoluble albumins and globulins was investigated in the endosperm of developing wheat (Triticum aestivum, L. cv. Butte 86) grain produced under a moderate (24 °C/17 °C, day/night) or a high temperature regimen (37 °C/28 °C) imposed from 10 or 20 days post-anthesis (dpa) until maturity. Proteins were separated by 2-DE and developmental profiles for nearly 200 proteins were analyzed by hierarchical clustering. Comparison of protein profiles across physiologically equivalent stages of grain fill revealed that high temperature shortened, but did not substantially alter, the developmental program. Accumulation of proteins shifted from those active in biosynthesis and metabolism to those with roles in storage and protection against biotic and abiotic stresses. Few proteins responded transiently when plants were transferred to the high temperature regimens, but levels of a number of proteins were altered during late stages of grain development. Specific protein responses depended on whether the high temperature regimens were initiated early or mid development. Some of the heat responsive proteins have been implicated in gas bubble stabilization in bread dough and others are suspected food allergens.     

A quantitative approach to characterize sink–source relationships during grain filling in contrasting wheat genotypes

We present a simple generic framework to quantify source–sink relationships during grain filling, by using a determinate growth function which has a unique property, namely being able of explicitly describing the time for the end of a growth process. This model framework was applied to analyze these relationships in plants of six wheat (Triticum aestivum L.) genotypes grown in pots in climate-controlled greenhouses under two temperature regimes (day/night: 20/15 and 25/20 °C). The function accurately described the sigmoid pattern of grain growth (sink activity), as its modified form did for the reversed sigmoid shape of flag-leaf area (source capacity), during grain filling. The six genotypes differed significantly in grain number as well as in grain yield, ranging from 54 to 81 grains and from 2.67 to 4.52 g DM per culm, respectively, when grown at 20/15 °C. Biomass and grain yield were significantly reduced by a rise of 5 °C. Grain nitrogen contents raised from 2.1 to 2.6% as a consequence of less carbon accumulation resulting in lower grain weights at the high temperature. On average, a rise of 5 °C in temperature reduced the duration of grain growth by 12 days (>30%), and increased the growth rate from 1.32 to 1.67 mg grain⁻¹ d⁻¹ (20%). Genotypic differences in grain-filling duration were also larger than in rate of grain growth. The genetic variation in the flag-leaf area duration (a proxy for the capacity for intercepting radiation and photosynthesis) was positively associated with sink size. Model analysis showed that whether or not the timing for the cessation of grain filling and for the end of post-anthesis source activity was synchronized depended on temperature. The quantitative approach yielded parameters that characterize genotypic differences of post-anthesis source and sink capacity in responding to environmental variables.     

Carotenoids and tocols content in genotypes of colored barley

Carotenoids and tocols of 20 genotypes of colored barley divided into three groups (A, B, C) were investigated. These included 16 F8 recombinant inbred lines obtained from crosses of four parental lines: 2005 FG, K4-31, L94 and Priora. The aim of the present study was to identify, quantify and profile characterize of tocols and carotenoids. Tocols profile is characterized by the prevalence of tocotrienols on tocopherols. The α-tocotrienol was the most represented tocol isomer, contributing about 53.03% of the total content. The highest α-tocotrienol content (33.67 μg g-¹) was found in the blue naked parental genotype 3007 (C-Group). The most abundant carotenoid was lutein on average 86% of total followed by zeaxanthin 10% and by α-carotene 3.40%. The Priora cultivar (C-Group) was the genotype with the highest lutein content (4.10 μg g-¹). The study found great variability in the content of carotenoids and tocols along the lines of each group.