The location of octenyl succinate groups within octenyl succinic anhydride (OSA)-modified waxy maize (WM) starch granules was studied in order to better understand the relationship between the structure and physical properties of OSA starches. OSA starches of D.S. 0.03-0.11 were prepared by reaction between starch, OSA and NaOH in aqueous suspension; the native granular structure of starch was retained after reaction. Backscattered electron imaging of osmium-stained, sectioned OSA starch granules showed a uniform distribution of OSA groups over the cross-section of the granules. Anion-exchange chromatography of OSA starches solubilized in water showed that most of the amylopectin molecules contain some negative charge, suggesting that most of the starch granule is accessible to and reacts with OSA. However, after partial debranching with pullulanase, more of the resulting chains were neutral than would be expected on statistical grounds, suggesting heterogeneity in OSA substitution at the branch level. X-ray photoelectron spectroscopy suggested that the concentration of OSA groups on the immediate surface of the OSA starch granules was about 3-4 times that of the bulk.
To be able to tailor and optimize the physical properties of oleogels for various food applications, more information is needed to understand how different gelators interact. Therefore, the objectives of this study were to evaluate the interactions between binary mixtures of beeswax (BW), candelilla wax (CLW), and sunflower wax (SFW) in pure form as well as in 5% wax oleogels made with soybean oil, in terms of their crystallization and melting properties, crystal morphology, solid fat content, and gel firmness. CLW:BW mixtures had eutectic melting properties, and oleogels from these mixtures with 40:60 to 90:10 CLW:BW were firmer compared to oleogels made with one wax. The main components in SFW and BW appeared to cocrystallize or crystallize at the same temperature, but nonlinear changes in melting point and solid fat content profile of oleogels prepared with the mixed waxes indicated that SFW dominated oleogel formation. In addition, oleogels prepared with mixtures of SFW and BW had lower firmness compared to oleogels prepared with one wax, indicating an incompatibility between the two waxes. The main wax components in SFW and CLW never cocrystallized, and low levels of CLW appeared to prevent SFW from forming a crystalline platelet network. This resulted in low firmness of oleogels made from mixtures of 90:10 to 60:40 SFW:CLW compared to oleogels prepared with one wax. However, the firmest oleogels of all mixtures were made from 10:90 SFW:CLW. Changes in gel firmness and melting properties with mixed wax oleogels were likely to be due to changes observed in the crystal size and morphology. In addition, the firmest gels were shown to result from mixtures that were predicted to have >40% hydrocarbon content, and a high hydrocarbon to wax ester ratio, but minor components such as free fatty acids and fatty alcohols may have also influenced firmness.
Tissue distribution and activity of enzymes involved in sucrose and hexose metabolism were examined in kernels of two inbreds of maize (Zea mays L.) at progressive stages of development. Levels of sugars and starch were also quantitated throughout development. Enzyme activities studied were: ATP-linked fructokinase, UTP-linked fructokinase, ATP-linked glucokinase, sucrose synthase, UDP-Glc pyrophosphorylase, UDP-Glc dehydrogenase, PPi-linked phosphofructokinase, ATP-linked phosphofructokinase, NAD-dependent sorbitol dehydrogenase, NADP-dependent 6-Pgluconate dehydrogenase, NADP-dependent Glc-6-P dehydrogenase, aldolase, phosphoglucoisomerase, and phosphoglucomutase. Distribution of invertase activity was examined histochemically. Hexokinase and ATPlinked phosphofructokinase activities were the lowest among these enzymes and it is likely that these enzymes may regulate the utilization of sucrose in developing maize kernels. Most of the hexokinase activity was found in the endosperm, but the embryo had high activity on a dry weight basis. The endosperm, which stores primarily starch, contained high PPilinked phosphofructokinase and low ATP-linked phosphofructokinase activities, whereas the embryo, which stores primarily lipids, had much higher ATP-linked phosphofructokinase activity than did the endosperm. It is suggested that PPi required by UDP-Glc pyrophosphorylase and PPilinked phosphofructokinase in the endosperm may be supplied by starch synthesis. Sorbitol dehydrogenase activity was largely restricted to the endosperm, whereas 6-P-gluconate and Glc-6-P dehydrogenase activities were highest in the base and pericarp. A possible metabolic pathway by which sucrose is converted into starch is proposed.
Invertase (β‐fructofuranoside fructohydrolase, EC 3.2.1.26) activity in developing maize (Zea mays L. inbred W64A) was separated into soluble and particulate forms. The particulate form was solubilized by treatment with 1 M NaCl or with other salts. However, CaCl2 inhibited invertase activity, and neither detergents nor 0.5 M methyl mannoside were effective in solubilizing the invertase activity. The soluble and particulate invertases were both glycoproteins, both had pH optima of 5.0 and Km values for sucrose of 2.83 and 1.84 mM, respectively. The apparent molecular weight of salt‐solubilized invertase was 40 kDa. Gel filtration of the soluble invertase showed multiple peaks with apparent molecular weights ranging from 750 kDa to over 9 000 kDa. Histochemical staining of cell wall preparations for invertase activity suggested that the particulate invertase is associated with the cell wall. Also, nearly all the invertase activity was localized in the basal endosperm and pedicel tissues, which are sites of sugar transport. No invertase activity was found in the upper endosperm, the embryo or in the placento‐chalazal tissue. In contrast, sucrose synthase (EC 2.4.1.13) activity was found primarily in the embryo and the upper endosperm, which are areas of active biosynthesis of storage compounds.
Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent-extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03-0.05 mg per cm 2 of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water-wet PE surfaces, air-dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch-coated film surfaces showed that starch was deposited as particles less than 1 m in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface-deposited starch in all experiments contained 90 -100% amylose; and exhibited the same V h X-ray diffraction pattern, indicative of helical inclusion complex formation.
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