The effect of amylose content from differing botanical sources on the nonlinear viscoelastic properties of semidilute solutions of maize starches*

The effect of the addition of potato or maize on the shear-thickening behavior of semidilute solutions of maize was examined. The experiments were conducted at 25°C using 90/10 weight–weight dimethyl sulfoxide (DMSO)–water as the solvent. The addition of amylose to maize amylopectin reduced and eventually eliminated the observed shear-thickening behavior of maize amylopectin. When potato amylose was combined with maize amylopectin, the shear-thickening phenomenon was observed up to a total amylose content of 10% by weight. For maize amylose, the shear-thickening behavior was eliminated at an amylose content of 5%. Maize amylose is thus more effective in inhibiting the formation of the structure formed after the shear-thickening region than potato amylose. This result indicates that the amylose obtained from potatoes interacts differently, or entangles differently, with maize amylopectin than does the amylose obtained from maize. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2429–2436, 1999     

Starch Derivatives of High Degree of Functionalization, 8. Synthesis and Flocculation Behavior of Cationic Starch Polyelectrolytes

Water soluble starch derivatives with a high degree of substitution (DS) up to 1 containing quaternary ammonium groups were prepared by reacting starch with 3‐chloro‐2‐hydroxypropyltrimethylammonium chloride (QUAB®188) in ethanol/sodium hydroxide/water or preferably with 2,3‐epoxypropyltrimethylammonium chloride (QUAB®151) in aqueous‐alkaline solution. The DS values of the samples can be controlled by adjusting the molar ratio of cationization agent to anhydroglucose unit and is only slightly dependent on the amylose content of the starting starch material. The structure of the cationic starch derivatives was confirmed by means of NMR spectroscopy. Dewatering experiments with the cationic starch derivatives were conducted on a harbor sediment suspension using a laboratory pressure filtration apparatus. The cationic starches were used alone and in combination with a high‐molar‐mass synthetic polyanion. Both dependence on the DS of the sample and influence of the amylose/amylopectin ratios of the initial native starch were observed. The highest dewatering index of 63 was found for the cationic polyelectrolyte based on the amylopectin‐rich waxy maize starch in monoflocculation. In case of dual flocculation using additionally a poly(acrylamide‐co‐acrylate) a dewatering index of even 85 was attained.     

CRISPR/Cas9-Mediated Mutagenesis of the Granule-Bound Starch Synthase Gene in the Potato Variety Yukon Gold to Obtain Amylose-Free Starch in Tubers

Potato (Solanum tuberosum L.) is the third most important food crop after rice and wheat. Its tubers are a rich source of dietary carbohydrates in the form of starch, which has many industrial applications. Starch is composed of two polysaccharides, amylose and amylopectin, and their ratios determine different properties and functionalities. Potato varieties with higher amylopectin have many food processing and industrial applications. Using Agrobacterium-mediated transformation, we delivered Clustered regularly interspaced short palindromic repeats and CRISPR-associated protein 9 (CRISPR/Cas9) reagents to potato (variety Yukon Gold) cells to disrupt the granule-bound starch synthase (gbssI) gene with the aim of eliminating the amylose component of starch. Lugol-Iodine staining of the tubers showed a reduction or complete elimination of amylose in some of the edited events. These results were further confirmed by the perchloric acid and enzymatic methods. One event (T2-7) showed mutations in all four gbss alleles and total elimination of amylose from the tubers. Viscosity profiles of the tuber starch from six different knockout events were determined using a Rapid Visco Analyzer (RVA), and the values reflected the amylopectin/amylose ratio. Follow-up studies will focus on eliminating the CRISPR components from the events and on evaluating the potential of clones with various amylose/amylopectin ratios for food processing and other industrial applications.     

Impact of the starch source on the physicochemical properties and biodegradability of different starch‐based films

Concern about environmental issues has motivated research into the development of biodegradable packaging from renewable sources. Natural polymers such as starch constitute a good alternative for diminishing the use of nonbiodegradable and nonrenewable components in the packaging industry. However, depending on the botanical source, films with different properties are formed. The aim of this study was to evaluate the film‐forming capacity of different starch sources (cassava, corn, potato, and wheat) by casting with starch contents from 2 to 6%. Principal component analysis methodology was used to evaluate the correlation between the formulations and their physicochemical and mechanical properties. It was not possible to produce continuous films based on potato starch, probably because of its very low amylose content (10%). The corn‐, cassava‐, and wheat‐starch‐based films were characterized by their thicknesses (0.06–0.22 mm), moisture contents (19–26%), water solubilities (13.7–26.5%), water‐vapor permeabilities (WVPs; 0.19–0.48 g mm h^?1 m^?2 kPa^?1), wettabilities (35–106°), biodegradabilities in soil, and thermal and mechanical properties (tensile strength = 1.9–6.7 MPa, elongation = 41–166%, and Young's modulus = 8–127 MPa). The wheat starch films presented higher WVPs and lower mechanical properties. The cassava starch films presented lower wettabilities and good mechanical properties; this suggested that their use in packaging for products, such as fruits and vegetables, with higher water activities could be feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46564.     

A method for controlling the surface morphology of centrifugally spun starch‐based fibers

In the present study, we provide a method for controlling the surface morphology of centrifugally spun starch‐based fibers by adjusting the ratio of amylopectin/amylose in starches and combining with a hot blast temperature. The effects of hot blast temperature, amylopectin, and amylose on fiber surface morphologies are investigated. Scanning electron microscopy is used to characterize the morphology of the prepared fibers. The results show that fibers with burr‐shaped nanostructures on the surface can be fabricated by adding amylopectin to starches and are promoted by increasing the hot blast temperature. However, amylose in starches plays the role of smoothing the fiber surfaces. X‐ray diffraction reveals that the fibers are amorphous. Through Fourier transform infrared spectroscopy analysis, it was found that some physicochemical changes occur during centrifugal spinning. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45810.     

Structure and properties of compression-molded thermoplastic starch materials from normal and high-amylose maize starches

The structural and mechanical properties of compression-molded normal and high-amylose maize starches were studied as a function of processing water content and ageing time. Rubbery thermoplastic starches were produced by compression molding of four maize starches with differences in amylose content and amylopectin structure. Glycerol (30% on the basis of dry starch) and water (between 10 and 35% on the basis of total mass) were used as plasticizers. After processing, the amorphous thermoplastic starch materials crystallized during ageing. The semicrystalline materials contained both E-type and V-type, as well as B-type crystallinity. The properties of the thermoplastic starch materials are dependent on water content during processing, starch source, and ageing time. The normal maize starch materials are highly flexible with elongations between 56 and 104%. The elongations of the high-amylose maize starch materials were between 5–35%. The tensile stress and E-modulus of the normal maize starch materials were in the range of 3.9–6.7 and 27–131 MPa, respectively. The tensile stress and E-modulus of the high-amylose maize starch materials increased from approximately 0.5 to 23 and 5 to 700 MPa, respectively, with increasing water content during processing from 10 to 35%. The differences in mechanical properties of the normal and high-amylose materials were explained by differences in the structure of the amylose and amylopectin structure. It was concluded that both lead to differences in the starch network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 631–644, 1997     

Study on the substrate specificity of α-amylases that contribute to soil removal in detergents

The actions of α-amylases in the degradation of amylose and amylopectin were investigated, and the contribution of the enzymatic hydrolysis of high-viscosity gelatinized starch to the removal of food stains that contain starch was characterized. α-Amylases from Bacillus amyloliquefaciens, B. licheniformis, Aspergillus oryzae, and porcine pancreas were used to test the removal of curry stains, which are hard to remove under low-temperature washing conditions and include large amounts of starch. In a detergent, the enzyme from B. amyloliquefaciens was the most effective in removing stains and hydrolyzed amylopectin more efficiently than amylose as a result of the more efficient formation of an enzyme-substrate complex in the former case. It is suggested that the cleaning power of α-amylases is due to their hydrolytic action, with endo-degradation of amylopectin, which results in an efficient reduction in the degree of polymerization. The liquefaction of amylopectin then accelerates the removal of food stains.     

Biodegradable starch particles for controlled release applications: Swelling and leaching mechanisms

Starch-extruded particles have only found infrequent use as delivery systems for active ingredients. We have previously shown that these particles are attractive for releasing hydrophobic compounds in water media. Here, we cover a range of amylose–amylopectin ratios and evaluate the presence of the thyme essential oil (TEO) as active compound to understand the dominant release mechanism in relation to the physicochemical properties of the starch matrices. Starch blends with high amylopectin content (1.8 and 15% amylose) could not be shaped into regular particles. For amylose contents higher than 28%, the equilibrium degree of swelling in water decreased with increasing amylose contents, from nearly 300% for an amylose content of 28–90% at an amylose content of 70%. For both lowest amylose contents, 1.8 and 15%, leaching of solids and disintegration of the particles resulted in a low apparent degree of swelling. The presence of TEO reduces the degree of swelling of the gelatinized starch matrix. This is explained by the formation of thymol–amylose complexes, which is confirmed by Fourier transform infrared spectroscopy analysis and X-ray diffraction.     

Structural changes of injection molded starch during heat treatment in water atmosphere: Simultaneous wide and small‐angle X‐ray scattering study

Native starches with wide varying amylose content were processed by injection molding. The injection‐molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide‐ and small‐angle X‐ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection‐molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form V_h. After wet conditioning, WAXS of the injection‐molded samples shows again the appearance of the crystal forms A or B, and crystallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rapidly decreases until its disappearance at 85–90°C, the invariant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystallinity (form B), presumably stabilized by the presence of the V_h structure (12–15%). Real‐time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystallization of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301–309, 2004     

Jet evolution and fiber formation mechanism of amylopectin rich starches in centrifugal spinning system

This article reports the jet evolution process and fiber formation mechanism of the amylopectin rich starch solution in centrifugal spinning system, and the linear polyvinylpyrrolidone (PVP) is applied to compare with starch solution. The results indicate that jet evolution processes of starch solution include steady state and Rayleigh–Taylor instability over the whole concentration range for the spinnability investigation, which are due to the hyperbranched molecular of amylopectin. As a compression, the linear molecular chain PVP solution expresses a steady state jet under the spinning concentration. The spinnability results show that the obtained starch fibers are always containing the beads due to the Rayleigh–Taylor instability of jet, but can be effectively controlled by solution concentration and amylose/amylopectin. Instead, the PVP fibers show a rapid decreasing of beads till to almost disappear with the increasing of solution concentration, which due to the improvement of chain entanglement increase the steady state portion of jet with the increasing of concentration. The thermal properties of obtained fiber show that fibers obtained from amylose with more thermal stability.     

超声波对木薯淀粉性质及结构的影响

考察了超声波对木薯淀粉理化性质及结构的影响. 结果表明,经超声处理后淀粉表观粘度下降,凝沉增强;经超声处理2 min,淀粉糊透明度提高,抗酶解能力降低;延长超声时间则导致糊透明度下降和抗酶解能力增强. FT-IR和XRD分析结果表明,超声作用未破坏淀粉分子基团,但淀粉结晶结构遭到破坏,结晶度下降. SEM分析显示,淀粉团粒结构减弱,受侵蚀的颗粒数量增多;淀粉-碘复合物分析表明,超声波造成淀粉大量降解,破坏支链结构和淀粉长链,直链淀粉含量增加. DSC分析表明,淀粉经超声处理后糊化焓基本不变,糊化温度升高.     

红薯淀粉烷基多糖苷生产的中试研究

用转糖苷法,以红薯淀粉、乙二醇、长链醇为原料,在2000L反应釜中生产了淀粉烷基多糖苷系列产品。工艺条件为m(红薯淀粉)∶m(乙二醇)∶m(长链醇)=1∶4∶1,残压小于9.3kPa,反应温度100～120℃。平均聚合度DP=1.10%,表面张力31.1～35.5mN/m,w(无机盐)<1.0%,w(固型物)>50%,w(活性物)>80%,w(游离脂肪醇)<1%。分析了刮膜除醇及氧化、还原脱色的生产工艺条件对产物的影响。用红外、气相色谱表征了产品。     

Investigations on esterification reactions of starches in 1‐N‐butyl‐3‐methylimidazolium chloride and resulting substituent distribution

The ionic liquid (IL) 1‐N‐butyl‐3‐methylimidazolium chloride ([C₄mim]⁺Cl^?) was used as solvent for different esterification reactions of the biopolymer starch. Therefore, maize starches with varying content of amylose were used. Different carboxylic acid anhydrides were applied to esterify starch with a degree of substitution (DS) in the range of 0.7–3.0. For example, starch acetates with the mentioned DS are accessible within 30 min at a 105°C‐reaction temperature. The DS distribution of starch acetates synthesized in IL was compared with the common starch acetate synthesis of Mark and Mehltretter. Also, a consideration of starch acetates and cellulose acetates synthesized in [C₄mim]⁺Cl^? is given. The starch esters were characterized by means of Raman spectroscopy for qualitative‐ and nuclear magnetic resonance spectroscopy for quantitative determination of the functionalization pattern. Moreover, the molecular mass distribution was determined after saponification by means of GPC‐MALLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Complexes of starch polysaccharides and poly(ethylene co-acrylic acid): Structure and stability in solution

Chiroptical methods have been used to study the conformation and interactions of amylose and amylopectin with poly(ethylene co-acrylic acid) (EAA) in aqueous solution. These studies, along with X-ray diffraction and solid-state NMR data, show that amylose and EAA, as well as amylopectin and EAA, form helical V-type inclusion complexes when mixed in aqueous suspension. This structure apparently accounts for the partial compatibility observed in films containing starch and EAA. About 2/3 by weight of EAA does not interact with amylose and probably represents the ethylene-rich central core of the EAA micelle. EAA/amylose complexes in 10 mM NaOH were stable to temperatures > 90°C, whereas EAA/amylopectin complexes in the same solvent were largely disrupted at this temperature. Urea, at a concentration of 8 M, further destabilized both EAA/amylopectin and EAA/amylose complexes. Solutions with an alkaline pH (> 9.5) dispersed EAA optimally and allowed maximum complexing with amylose. At pH values > 13, the EAA/amylose complexes were weaker, most likely due to electrostatic repulsion between ionized hydroxyl groups of amylose and carboxyl groups of EAA.     

Solution properties of comb‐like polymers consisting of dimethylsiloxane monomer units

A series of comb‐like polymers consisting of dimethylsiloxane monomer units and differing by side‐chain length have been studied in hexane solution using analytical ultracentrifugation, translational diffusion and viscometry. Analysis of the hydrodynamic parameters and their molar mass dependences based on the Fixman–Stockmayer theory or wormlike spherocylinder model shows that with side chain lengthening, the Kuhn segment length A of the polymers under study increases from the value of A for linear polydimethylsiloxane to values typical for semi‐rigid chain polymers A = 8–10 nm. © 2016 Society of Chemical Industry     

Microhardness and water sorption in injection‐molded starch

The microhardness of injection‐molded potato starch was investigated in relation to the water sorption mechanism. The creep behavior under the indenter and the temperature dependence of the microhardness are reported. The influence of the drying time on microhardness, weight loss and density changes for materials with different injection‐molding temperatures is highlighted. Results reveal the role of the various mechanisms of water evaporation involved. The occurring structural mechanisms are discussed in terms of the gradual transformation of single helices of amylose and amylopectin into a network structure of double helices and the partial destruction of this structure. Experiments on starch samples, heated at 200°C, suggested the occurrence of an extreme densification of the network hindering the water adsorption in a humid atmosphere. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1246–1252, 2002     

Experimental and Theoretical Investigation of Mass Transfer during Leaching of Starch and Protein from Potato

In this article, mass transfer during leaching of starch and protein from potato using water as the solvent was investigated. Leaching experiments were carried out by immersion of slab-shaped potato samples in distilled water at 30°C, 45°C, and 55°C, and amounts of starch and protein loss, and moisture gain by the samples were evaluated at different process duration times. A two-parameter model was proposed for prediction of the kinetics of mass transfer and also estimation of the final equilibrium values of solutes loss and moisture gain by the samples. Effective diffusivities of solutes and moisture were estimated by fitting the experimental data of solute loss and moisture gain to the analytical solution of Fick's second law of diffusion. Moisture, starch, and protein distributions into the potatoes were predicted as a function of time and location into the samples. Mean relative errors (MREs) between the predicted concentrations by the proposed models and experimental data were in the ranges of 0.037–0.104 and 0.063–0.205 for the two-parameter model and the analytical solution, respectively. Estimated equilibrium solute losses were between 0.922 and 1.549 (g/100 g fresh fruit) for protein and between 10.893 and 11.848 (g/100 g fresh fruit) for starch. Also equilibrium water gain (WG) was in the range of 35.842–46.296 (g/100 g fresh fruit). Effective diffusivities were estimated in the range of 1.334–1.817 × 10^?10 m²/s for moisture and 1.070–1.893 × 10^?10 m²/s for solutes.     

Ozone: An Advanced Oxidation Technology for Starch Modification

ABSTRACT

Ozone processing is one of the encouraging non-thermal and bio-friendly techniques in the food processing sector. The applicability of ozone technology in food industry is increasing due to its antimicrobial action and modification of functional properties of the foods. The structural modifications of starches have major applications in the food and bakery industry for producing products with increased shelf life, improved texture, and retention of moisture content. The positive response of ozonation in carboxyl and carbonyl group alters the viscosity of starch molecules. Rheological characteristics like low viscosity even at an increased concentration, desirable binding properties, and film-forming ability have increased its use in the food processing industry. The influence of ozonation in the physicochemical properties is mainly retrogradation and cross-linking of amylose and amylopectin molecules and enzymatic modifications. Ozonation cause change in crystallinity, viscosity, expansion ratio, and gelatinization temperatures. Finally, ozonation induces many possible changes in native starches for the effective utilization in the processing sectors. In this review, starch modifications utilizing ozone and various research achievements and scientific reports focusing on the effect of ozonation in terms of physical, chemical, and thermal properties of native starches and on the possible modifications have been summarized and discussed. In conclusion, ozone is a green technology that can be effectively used as an alternative oxidation technique for starch modification.     

Properties of extruded starch–poly(methyl acrylate) graft copolymers prepared from spherulites formed from amylose–oleic acid inclusion complexes

Mixtures of high‐amylose corn starch and oleic acid were processed by steam jet cooking, and the dispersions were rapidly cooled to yield amylose–oleic acid inclusion complexes as micron‐ and submicron‐sized spherulites and spherulite aggregates. Dispersions of these spherulite particles were then graft polymerized with methyl acrylate, both before and after removal of uncomplexed amylopectin by water washing. For comparison, granular, uncooked high‐amylose corn starch was also graft polymerized in a similar manner. Graft copolymers with similar percentages of grafted and ungrafted poly(methyl acrylate) (PMA) were obtained from these polymerizations. The graft copolymers were then processed by extrusion through a ribbon die, and the tensile properties of the extruded ribbons were determined. Although extruded ribbons with similar tensile strengths were obtained from the three starch–PMA graft copolymers, much higher values for % elongation were obtained from the spherulite‐containing systems. Also, the tensile properties were not significantly affected by removal of soluble, uncomplexed amylopectin by water washing before graft polymerization. These results are consistent with the observation that these PMA‐grafted starch particles did not melt during extrusion, and that continuous plastic ribbons were formed by fusing these particles together in the presence of small amounts of thermoplastic PMA matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40381.