Insights into the Supramolecular Structure and Degradation Mechanisms of Starch from Different Botanical Sources as Affected by Extrusion-based 3D Printing.

Extrusion-based 3D printing has emerged as the most versatile additive manufacturing technique for the printing of practically any material. However, 3D printing of functional materials often activates thermo-mechanical degradation, which affects the 3D shape quality. Herein, we describe the structural changes of eight different starch sources (normal or waxy) as a consequence of the temperature of an extrusion-based 3D printing system through in-depth characterization of their molecular and structural changes. The combination of size-exclusion chromatography, small-angle X-ray scattering, X-ray diffraction, dynamic viscoelasticity measurements, and in vitro digestion has offered an extensive picture of the structural and biological transformations of starch varieties. Depending on the 3D printing conditions, either gelatinization was attained ("moderate" condition) or single-amylose helix formation was induced ("extreme" condition). The stiff amylopectin crystallites in starch granules were more susceptible to thermo-mechanical degradation compared to flexible amorphous amylose. The crystalline morphology of the starch varieties varied from B-type crystallinity for the starch 3D printing at the "moderate" condition to a mixture of C- and V-type crystallinity regarding the "extreme" condition. The "extreme" condition reduced the viscoelasticity of 3D-printed starches but increased the starch digestibility rate/extent. In contrast, the "moderate" condition increased the viscoelastic moduli, decreasing the starch digestion rate/extent. This was more considerable mainly regarding the waxy starch varieties. Finally, normal starch varieties presented a well-defined shape fidelity, being able to form a stable structure, whereas waxy starches exhibited a non-well-defined structure and were not able to maintain their integrity after printing. The results of this research allow us to monitor the degradability of a variety of starch cultivars to create starch-based 3D structures, in which the local structure can be controlled based on the 3D printing parameters.

Potential interactions between starch and fruit pomace may impact the expansion ratio of direct expanded extrudates.

Due to their dense characteristics, direct-expanded products fortified with insoluble fiber are generally not well accepted. Understanding the interactions between starch and fiber could help to effectively choose and modify ingredients to produce products containing high amounts of fiber. Therefore, this study aims to explain the interplay between two starches (native and waxy corn) and two pomace types (blueberry and cranberry). Blends up to 100% of pomace were extruded using a co-rotating twin-screw extruder. Raw material and milled extrudates were analyzed for their pasting and hydration properties. Fourier-transform infrared (FTIR) and solid-state nuclear magnetic resonance (NMR) spectroscopy were conducted to observe molecular changes. The expansion ratio (ER) significantly decreased as pomace was added and ranged from 3.85 for pure waxy corn starch to approximately 1 for blends that contained 80% pomace. Distinctions between the blends were observed. Particularly, at 20% of pomace inclusion, native corn starch with cranberry pomace showed a significantly higher ER. Different behaviors were also detected during the physicochemical analyses. A nonlinear trend between pomace level and water solubility as well as absorption was observed for native corn starch blends, suggesting that molecular interactions between the biopolymers occur. FTIR and NMR results give no evidence for new covalent bonds; hence, the most likely interactions occurring are hydrogen bonds. In addition to the dilution effect of pomace addition, the enhancement or weakening of such interactions between starch molecules by pomace compounds may reduce the ER.

Proteomics characterization nitrogen fertilizer promotes the starch synthesis and metabolism and amino acid biosynthesis in common buckwheat.

Nitrogen (N) affects common buckwheat quality by affecting starch and amino acids (AAs) content, but its molecular mechanism is still unclear. We selected two common buckwheat varieties with high and low starch content, and designed two treatments with 180 and 0 kg N/ha. Application of high-N led to significant increases in starch, amylose and amylopectin content. Of 1337 differentially expressed proteins (DEPs) induced by high-N conditions. 472DEPs were significantly upregulated and 176DEPs downregulated for Xinong9976. 239DEPs were significantly upregulated and 126DEPs downregulated for Beizaosheng. The six alpha-glucan phosphorylases, three alpha-amylases, one granule-bound starch synthase 1 and one sucrose synthase exhibited higher expression at the 180 kg N/ha than at the 0 kg N/ha. In addition, high-N application promoted arginine, leucine, isoleucine and valine biosynthesis. This study revealed the effect of N on the starch and AA content of common buckwheat and its mechanism. The crucial proteins identified may develop the quality of common buckwheat.

Deciphering molecular interaction and digestibility in retrogradation of amylopectin gel networks.

The impact of the internal part of aewx amylopectin on the gel network and digestibility during retrogradation was investigated using wx amylopectin as a reference. After ß-amylolysis for 60 min (aewx-60), greater shifts in both λmax value and absorbance of iodine binding profiles were observed, accompanied by an increment of short chains (DP 3-5) with reducing the external long chains (DP 17.2). For the amylopectin gels aged 7 days at 4 °C, aewx had greater intermolecular aggregation of double helices to form junction zones, resulting in remarkably higher G', which was significantly greater than that of wx amylopectin or aewx-60. Moreover, aewx amylopectin had a greater RS accompanied by a reduction in RDS after retrogradation. The gel network models of retrograded amylopectins were built to interpret more molecular interactions for aewx than those of wx. The results revealed that aewx amylopectin with a higher proportion of longer external chains prompted the flexibility to align and interact for the formation of double helices and enzyme-resistant structures.

Effect of wheat bran dietary fiber on structural properties of wheat starch after synergistic fermentation of Lactobacillus plantarum and Saccharomyces cerevisiae.

This study investigated the changes in the structure of wheat starch after synergistic fermentation of Lactobacillus plantarum and Saccharomyces cerevisiae at different wheat bran dietary fiber (WBDF) levels. The results showed that WBDF was slightly resistant to the decrease in acidity within the fermentation system. The amylose content decreased from 32.12% to 19.92% (P < 0.05), amylose/amylopectin ratio decreased from 0.47 to 0.25 (P < 0.05), and relative crystallinity decreased from 12.17% to 9.40% (P < 0.05) in the samples containing WBDF compared with the control. Scanning electron microscopy showed more eroded starch as the WBDF level increased. Fourier-transform infrared spectroscopy revealed a decrease in the starch-hydrogen binding absorbance in the 3600-3000 cm-1 wavemumber; and the 1047/1022 and 995/1022 cm-1 data indicated an increase in the degree of order and degree of double helix of the samples containing WBDF. The results of the study might help understand the interaction between dietary fibers and starch during fermentation and guide the production of fermented high-fiber flour products.

Comparative study on physicochemical properties of starch films prepared from five sweet potato (Ipomoea batatas) cultivars.

Five different sweet potato (Ipomoea batatas) cultivars (Daeyumi, Gogeonmi, Sincheonmi [SCM], Singeonmi, and Sinyulmi [SYM]) were used to extract sweet potato starch (SPS) for developing starch-based films. After the chemical composition and amylose contents of all SPSs were evaluated, the morphological, moisture, mechanical, and barrier properties of the SPS-based films were investigated. As one of the film characteristics, the X-ray diffractograms revealed that the SCM-based film with the highest amylose content (26.34%) had the highest relative crystallinity (24.31%). The SCM-based film also showed higher tensile strength (3.05-fold) and elastic modulus (2.38-fold) than the SYM-based film with the lowest amylose content (21.84%). The water vapor and oxygen permeabilities of the SPS-based films were negatively correlated with the amylose content. Thus, the SCM-based film was less permeable for water vapor (3.16-fold) and oxygen (1.81-fold) than the SYM-based film. These results demonstrated that the sweet potato cultivar, especially the amylose content, plays a significant role in determining the physicochemical properties of the SPS-based films.

Characteristics of starch from rice seeds modified by T-DNA insertion of ascorbate peroxidase 2.

Starch is the main storage carbohydrate in rice seed. The amylose and amylopectin content differ among varieties. A transgenic rice line was obtained by T-DNA insertion of ascorbate peroxidase 2 (apx2), resulting in decrease of thousand kernel weight. In this study, starches were isolated from apx2 and wild type seeds. Morphology, physical and chemical properties of starch granules were analyzed. The seed micro-surface in apx2 showed distinct textures, compared with that of wild type. The morphology of starch granules in apx2 exhibited irregular shapes, while the wild type starch granules presented regular polyhedral shapes. Additionally, the length and width of starch granules in apx2 were significantly decreased, compared with that of wild type. Further analysis found that apx2 starch showed low crystallinity and high amylose with the methods of X-ray diffraction pattern, iodine binding and blue value analysis, fourier transform infrared (FT-IR) spectrum and thermogravimetric investigation. This study broadened our knowledge of relationship between antioxidant enzyme and rice seed starch formation.

Correlation of taste values with chemical compositions and Rapid Visco Analyser profiles of 36 indica rice (Oryza sativa L.) varieties.

Yield, taste quality, and cultivar utilisation improvements are important research topics in indica rice breeding. Herein, we compared the relative effectiveness and relationship of three taste evaluation methods, namely, chemical composition, Rapid Visco Analyser (RVA), and taste analyser. We assessed associations among these methods using 36 indica varieties commonly grown in Yunnan, Sichuan, and Guizhou, China. Temperature and sunlight duration during grain filling influenced rice cooking quality. Varieties with high taste quality had low amylose and protein contents; high peak viscosities and breakdowns; and low hold viscosities, setbacks, and final viscosities. Protein and combined protein and amylose explained 38.6% and 62.1% of the variation in taste value, respectively. The RVA profile was affected by protein, amylose, and amylopectin contents and explained 60.5% of the taste-value variation. This study lays the foundation for taste evaluation of high-quality rice varieties early in the breeding process, which can improve cultivation and marketing potential.

A simplified method of determining the internal structure of amylopectin from barley starch without amylopectin isolation.

To determine the internal structure of barley starch without amylopectin isolation, whole starch was hydrolyzed using ß-amylase to remove the linear amylose and obtain ß-limit dextrins (ß-LDs). The ß-LDs were treated with extensive α-amylase to prepare α-limit dextrins (α-LDs), and the α-LDs were further hydrolyzed with ß-amylase into building blocks. The chain-length distribution of ß-LD and building block composition were analyzed by size-exclusion chromatography and anion-exchange chromatography. The internal structure of the barley whole starches had similar pattern to barley amylopectins analyzed by conventional methods. The starch of barley amo1-mutated varieties contained more short internal B-chains and less long internal B-chains than that of other varieties. The starch from amo1-mutated varieties had more large building blocks than that from waxy varieties. The simplified method presented in this study can effectively characterize starch internal structure that relates to physicochemical properties of starch, although some details of amylopectin structure are not assessable.

The influence of chemical composition diversity in the cooking quality of Andean bean genotypes.

Andean beans (Phaseolus vulgaris) chemical compositions and cooking characteristics contribute to a healthy diet. The objective of this study was to evaluate the influence of chemical composition on the cooking quality of 14 Andean beans genotypes with different seed coat colors. More specifically, water retention (WR), cooking time (CT), and solids released in the broth, were analysed. WR values ranged from 128.4% to 160.7% and CT ranged from 13.7 (BRS Embaixador) to 21.7 min (KID44). Andean beans showed variability in chemical composition, mainly starch content (39.43 g 100 g-1, BRS Realce to 51.92 g 100 g-1, LP15-04) and polymer composition. The profile of starch and interactions among minerals and chemical compounds influenced the cooking profiles than do the individual compounds. Andean beans traits of cooking, mainly CT, were influenced by their chemical composition; however they can be incorporated into diets without drastic changes in preparation methods.

Morphological and physicochemical characterization of starches from underground stems of Trimezia juncifolia collected in different phenological stages.

In this study, starches from underground stems of Trimezia juncifolia were evaluated during dry season (DSS), wet season (WSS) and sprouting (SS). Results evidenced that drought stress did not interfere with the yield, amylose content and degree of polymerization (DP) of amylopectin. However, the extraction yield in SS was 58% lower, being observed and increase of 7.5% in the content of amylose, and 13.5% in DP values for SS amylopectin, with a predominance of A-chains. The amount of total sugar, the starch granules size as well as solubility and swelling properties varied as function of the phenological status. Also, starch granules changed from A-type polymorph in DSS and SS to a CA-type in WSS. Nevertheless, it was observed a crystallinity reduction from 56% in DSS to 37.1% in SS. In addition, thermograms evidenced the presence of amylose-lipid complexes, with endothermic transition temperatures being affected by drought stress and sprouting. Finally, results demonstrate that underground stems from T. juncifolia have adaptative strategies involving changes in the morphological and physicochemical properties of the starch granules.

Influence of the addition of different ingredients on the bioaccessibility of glucose released from rice during dynamic in vitro gastrointestinal digestion.

Rice represents a primary source of carbohydrates in human nutrition. Upon its consumption, the released sugars are mostly absorbed, categorising rice as a high glycemic index food. Addition of ingredients is common practice when cooking rice, which may affect rice digestibility and influence nutrients absorption in the gastrointestinal (GI) tract, enabling a controlled glucose release. In this sense, rice formulations were submitted to a dynamic in vitro GI model, constituted by reactors that simulates peristalsis coupled to filtration membranes, to evaluate carbohydrates hydrolysis and bioaccessibility. Addition of quinoa and wholegrains reduced carbohydrates hydrolysis (i.e. 38.5 ± 5.08% and 57.98 ± 1.91%, respectively) and glucose bioaccessibility (i.e. 25.92 ± 5.70% and 42.56 ± 1.39%, respectively) when compared with brown rice (i.e. 63.86 ± 2.96% hydrolysed and 44.33 ± 1.88% absorbed). Addition of vegetables significantly decreased sample chewiness and resulted in superior hydrolysis (71.75 ± 7.44%) and glucose absorption (51.61 ± 6.25%).

Colorimetric assay for the determination of molecular weight distribution and branching characteristics of starch hydrolysates.

Here, we present a gold nanoparticle-based colorimetric assay for the determination of molecular weight distribution and branching characteristics of enzymatically hydrolyzed starch. The steric stabilization effect of starch hydrolysate on the colloidal stability of AuNPs was found to be proportional to the ratio of high molecular weight amylopectins, which was clearly reflected by the intensity of the characteristic surface plasmonic resonance (SPR) absorbance peak of the AuNPs. The fractional change of high molecular weight amylopectin over the course of enzymatic hydrolysis reaction could be measured based on the intensity of SPR peak, in which the results correlated well with those obtained by conventional gel permeation chromatography. With the proper calibration of a specific set of enzyme and starch type, this method would provide a fairly simple and fast means of analyzing the molecular weight distribution of starch hydrolysate on site as well as the amylose content in native starch.

Changes in structural, physicochemical, and digestive properties of normal and waxy wheat starch during repeated and continuous annealing.

Effects of repeated annealing treatments (8 cycles, 12 h each) or continuous annealing treatments (12-96 h) at 50 °C on structural, physicochemical, and digestive properties of normal and waxy wheat starches were investigated. Wheat starches retained the original crystalline structure of A-type after annealing. Annealing treatments increased crystallinity, short chain of amylopectin, viscosity, and gelatinization temperatures of starch. However, molecular weight, long chain of amylopectin, solubility, and swelling power of starch decreased after annealing. Additionally, annealing reduced the in vitro digestibility of wheat starches. The changes in properties of starch varied depending on starch type, normal or waxy, and annealing methods, repeated or continuous. The repeated annealing was found to be more effective in modification of normal wheat starch properties. However, continuous annealing efficiently modified properties of the waxy wheat starch. The obtained results may help in choosing appropriate applications of annealed wheat starches in the food industry.

The relationship between the expression pattern of starch biosynthesis enzymes and molecular structure of high amylose maize starch.

Two high amylose (HAM) inbred lines with apparent amylose contents of 55 % and 62 %, respectively, were selected to explore the relationship between molecular structure and gene expression of starch-synthase involved enzymes. GPC analysis of debranched starches showed that the HAM starches (HAMSs) had shorter amylose chains and longer amylopectin chains than normal maize starch (NMS). FACE analysis showed that these HAMSs had a higher content of amylopectin chains of DP > 21. Quantitative Real-Time PCR analysis showed that the HAM lines had specifically low expression of the starch branching enzyme IIb (SBEIIb), and the starch synthase IIIa (SSIIIa) homologue, and high expression of the isoamylase 2 (ISA2), potentially suppressing the generation of amylopectin molecules through deficient branching and excessive debranching process, thereby increasing the relative amylose content. A high expression of GBSS1 was potentially associated with increased short amylose chain lengths in HAMSs.

Structural basis for the low digestibility of starches recrystallized from side chains of amylopectin modified by amylosucrase to different chain lengths.

The structures and physicochemical properties of modified starch recrystallized from amylosucrase-modified amylopectin side chains were investigated during in vitro digestion. The digestion of the modified starches followed the first-order kinetics and revealed the existence of rapid and slow digestion phases. The B-type crystalline structure of the modified starches remained unchanged, but the degree of crystallinity remarkably increased during the initial 20-min digestion, followed by insignificant changes after 120-min digestion. Enzymatic digestion for 20 min increased the thermal stability of the starches, but a slight decrease in the gelatinization temperatures was observed after 120-min digestion. Starch digesta showed irregular shapes, and no obvious damage was observed. These observations suggest that the digestion of the modified starches started from the loosely packed outer shell consisting mainly of amorphous materials, followed by even digestion of the interior amorphous and crystalline regions of the starch particles to result in slow digestion properties.

Structural, pasting and thermal properties of common buckwheat (Fagopyrum esculentum Moench) starches affected by molecular structure.

Common buckwheat starch (CBS) has extensive using value in the human diet. In this study, the molecular structure and physicochemical properties of CBS isolated from five cultivars collected from three regions of China were studied. Variations in molecular structure, crystalline structure, complexity, water solubility (WS), swelling power (SP), pasting properties, and thermal characteristics were recorded among the starches. The CBS had both similarities and differences in its properties by comparison with maize starch (MS) and potato starch (PS). The average molecular weight (MW) and amylopectin average chain length (ACL) of CBS ranged from 3.86 × 107 g/mol to 4.68 × 107 g/mol and from 21.29% to 22.68%, respectively. CBS and MS were divided into one subgroup and showed typical A diffraction patterns, while PS was divided into two subgroups and exhibited a typical B polymorphic pattern. The WS and SP of all the starches significantly increased with increasing temperature and had great variation at 70 °C and 90 °C. Pearson's correlation analysis showed that the molecular structure of starches greatly affected the physicochemical properties. This study revealed that the physicochemical properties of CBS could be affected by the molecular structures.

Bambusa vulgaris starch: Characterization and technological properties.

The starch industry has grown quickly, and starch production has expanded around the world because it is a very versatile ingredient, despite limits in some foodstuffs. So, this study aimed to analyze morphology, physic and chemical characteristics of the starch extracted from three different parts (bottom, middle and top) of the young bamboo culm of B. vulgaris (SB, SM, and ST, respectively). The obtained data were evaluated by analysis of variance and Scott-Knot test (p < 0.05), and no significant difference was observed between SB, SM and ST samples. The starches presented yellowish coloration (L* > 88, a* > -0.2, and b* > 9), and SEM images showed compound granules with polyhedral shapes and average diameter of 6.55 µm; apparent amylose content of 37.45%, wherein SB and SM showed characteristics of resistant starch type 2, whereas ST was more similar to normal starch. Amylopectin presented high proportion of chains with DP 13-24 and lower proportion of long chains, corroborating with A-type crystalline pattern. The absence of a shoulder in the branch chain length distribution, suggest a perfect crystalline structure, similar to starches from D. asper and B. tuldoides. DSC shows gelatinization temperatures higher than 80 °C, lower transition temperatures and the percentage of retrogradation above 44%. The results are promising to obtain slow digesting starches, although it is necessary to evaluate the starch from other bamboo species, which may have different characteristics.

Structure and properties of soft rice starch.

Pasting and rheological properties of starch from soft rice and two traditional rice varieties were analyzed. Soft rice starch was found to have a low pasting temperature of 67.2 °C, with a high system viscosity, including peak and trough viscosity. The storage modulus and loss modulus of soft rice starch were high and showed good viscoelasticity. The amylose content of soft rice starch was found to be 11.3%, classifying it was low amylose content type. Compared with japonica rice starch, soft rice starch had lower solubility but higher swelling power, gel consistency, and water binding capacity. The medium particle size and volume mean particle size of soft rice starch were the highest. The average molecular weight of soft rice starch was 5.4 × 107. The molecular density and proportion of short amylopectin side chains, with a range of 6-12, were the highest among all varieties tested. These findings provide a theoretical basis for the processing of soft rice starch and breeding of high-quality rice.

Flour functional properties of purple maize (Zea mays L.) from Argentina. Influence of environmental growing conditions.

The objective was to characterize thermal and viscosity properties of flour of purple maize from Argentina, and to evaluate the environmental effects on composition and flour properties. Half-sib families were selected from original germplasm and reproduced during 2014 and 2015. Chemical composition, thermal and pasting properties of whole grain flour were determined. Non-purple genotypes were used as controls. Composition of purple maize did not show significant differences with controls, but amylose content was significantly lower. High variability in pasting and thermal properties of flour was observed between genotypes. Anthocyanin content positively correlated with breakdown (r = 0.37, P < 0.05), indicating that anthocyanins increased starch granules fragility during cooking. The higher gelatinization enthalpy of purple genotypes was coincident with the lower amylose content in relation to non-purple. The amylopectin retrogradation enthalpy negatively correlated with polyphenols (r = -0.35, P < 0.05) and anthocyanins (r = -0.40, P < 0.05), probably due to interactions formed after starch gelatinization. Flour functionality parameters showed higher effect of genotype and lower effects of environment and genotype × environment interaction. The variability found among genotypes indicates different flour behavior that would facilitate the identification of progenies with particular properties for production of functional maize based-foods.