Effects of Four Highland Barley Proteins on the Pasting Properties and Short-Term Retrogradation of Highland Barley Starch.

This study evaluated the effects of four highland barley proteins (HBPs), namely, albumin, globulin, gliadin and glutenin, on the short-term retrogradation of highland barley starch (HBS). The findings reveal that HBPs could reduce the viscosity, storage modulus and hardness of HBS, with albumin and globulin showing more prominent effects. Furthermore, with the addition of HBPs, the loss tangent (tan δ) of HBS loss increased from 0.07 to 0.10, and the enthalpy of gelatinization decreased from 8.33 to 7.23. The degree of retrogradation (DR%) of HBS was 5.57%, and the DR% decreased by 26.65%, 38.78%, 11.67% and 20.29% with the addition of albumin, globulin, gliadin and glutenin, respectively. Moreover, the relative crystallinity (RC) and the double helix structures were inhibited with the HBPs' incorporation. Meanwhile, the HBPs also could inhibit water migration and improve the structure of HBS gels. In summary, HBPs could inhibit the retrogradation behavior of HBS, which provides new theoretical insights for the production studies of highland barley foods.

Study on the anti-retrogradation of wheat amylopectin by addition of alkali-soluble glutenin.

The retrogradation of wheat amylopectin during cold storage is the main reason for the increasing hardness of flour products such as steamed bread, bread and pastries, etc. Addition of gluten protein components is a green, safe, cheap and efficient method to inhibit the retrogradation of wheat amylopectin. In this paper, as being stored at 4 °C for 7 d, retrogradation rate of wheat amylopectin decreased from 55.02 % to 14.37 % after it was mixed with 20 % alkali-soluble glutenin (ASG) at 30 °C for 90 min, a 73.8 % reduction. The infrared results showed that the intensity of bending vibration of water molecules and intra-molecular ß-sheet content of ASG decreased during the interaction between amylopectin and ASG. Meanwhile, intermolecular ß-sheet and random coil contents of ASG increased. The results of 13C Solid-state NMR indicated that Qß, Pγ and Lγ of ASG involved in interaction of wheat amylopectin, ASG and molecule of water. Under the optimal conditions, the interaction of wheat amylopectin and ASG began to form spheres containing disulfide bonds, resulting in the attenuation or disappearance of the diffraction peak at 2θ 19.7°, which may be marked as the criterion for the best mixing time of wheat amylopectin and ASG. The retrogradation kinetic index (n) of wheat amylopectin decreased significantly with the addition of ASG and formation of disulfide bond was the key factor. ASG could be potentially used as an anti-retrogradation agent for amylopectin.

Effects of three glutenins extracted in acidic, neutral and alkaline urea solutions on the retrogradation of wheat amylose and amylopectin.

Three glutenins (glutenin 1, glutenin 2, and glutenin 2) were extracted in acidic, neutral and alkaline urea solutions respectively. All of the three glutenins are rich in glutamic acid (Glu, >30 %) and proline (Pro, >20 %). Glutenin 1, extracted at pH 5, shows higher contents of hydrophilic amino acids as serine (Ser, 5.25 %), aspartic acid (Asp, 2.99 %), tyrosine (Tyr, 3.11 %), arginine (Arg, 2.09 %) and threonine (Thr, 2.11 %) than the other two glutenins. The retrogradation of three glutenins with amylose/amylopectin indicated that glutenin 1 showed significant inhibition effect on the retrogradation of wheat amylose. The characterizations of amylose retrograded with glutenin 1 by FT-IR, XRD, DSC and solid 13C NMR showed that new hydrogen bonds between Glu, Tyr and wheat amylose were formed, which prevented the formation of hydrogen bonds between amylose themselves. Glycosidic bonds between some hydroxyl groups of C6 in wheat amylose and certain hydroxyl groups of Ser and Thr in glutenin with specific chain length were present. The macromolecules with steric hindrance prevented the rearrangement of amylose into regular crystals. The retrogradation of wheat amylose was inhibited in this way. This study provides a key targeting step to control the retrogradation of amylose.

Effects of Amylopectins from Five Different Sources on Disulfide Bond Formation in Alkali-Soluble Glutenin.

Wheat, maize, cassava, mung bean and sweet potato starches have often been added to dough systems to improve their hardness. However, inconsistent effects of these starches on the dough quality have been reported, especially in refrigerated dough. The disulfide bond contents of alkali-soluble glutenin (ASG) have direct effects on the hardness of dough. In this paper, the disulfide bond contents of ASG were determined. ASG was mixed and retrograded with five kinds of amylopectins from the above-mentioned botanical sources, and a possible pathway of disulfide bond formation in ASGs by amylopectin addition was proposed through molecular weight, chain length distribution, FT-IR, 13C solid-state NMR and XRD analyses. The results showed that when wheat, maize, cassava, mung bean and sweet potato amylopectins were mixed with ASG, the disulfide bond contents of alkali-soluble glutenin increased from 0.04 to 0.31, 0.24, 0.08, 0.18 and 0.29 µmol/g, respectively. However, after cold storage, they changed to 0.55, 0.16, 0.26, 0.07 and 0.19 µmol/g, respectively. The addition of wheat amylopectin promoted the most significant disulfide bond formation of ASG. Hydroxyproline only existed in the wheat amylopectin, indicating that it had an important effect on the disulfide bond formation of ASG. Glutathione disulfides were present, as mung bean and sweet potato amylopectin were mixed with ASG, and they were reduced during cold storage. Positive/negative correlations between the peak intensity of the angles at 2θ = 20°/23° and the disulfide bond contents of ASG existed. The high content of hydroxyproline could be used as a marker for breeding high-quality wheat.

Progress of Microencapsulated Phycocyanin in Food and Pharma Industries: A Review.

Phycocyanin is a blue fluorescent protein with multi-bioactive functions. However, the multi-bioactivities and spectral stability of phycocyanin are susceptible to external environmental conditions, which limit its wide application. Here, the structure, properties, and biological activity of phycocyanin were discussed. This review highlights the significance of the microcapsules' wall materials which commonly protect phycocyanin from environmental interference and summarizes the current preparation principles and characteristics of microcapsules in food and pharma industries, including spray drying, electrospinning, electrospraying, liposome delivery, sharp-hole coagulation baths, and ion gelation. Moreover, the major technical challenge and corresponding countermeasures of phycocyanin microencapsulation are also appraised, providing insights for the broader application of phycocyanin.

The anti-retrogradation properties of maize amylopectin treated by being co-crystallized with NaCl.

Long-term retrogradation of amylopectin always leads to the quality deterioration of starch-based food. In this paper, the purified maize amylopectin was co-crystallized with NaCl to obtain anti-retrograded amylopectin. The results showed that the retrogradation rate of maize amylopectin dropped directly from 27.92 % to 19.05 % at the conditions of amylopectin: 5 % NaCl (m/v) = 1.7:10, eutectic times 24 h at 4 °C. The co-crystals with a dendritic shape consisted of a center and several large branches and the length of the largest branch reached up to 10,000 µm. The results of the maximum absorbance of iodine-attached amylopectin, molecular weight and chain length distributions showed that hydrolysis and graft of amylopectin happened in the eutectic process. Residues produced by acid hydrolysis linked to the main chains via α-1,6 glycosidic linkage at the late stage of eutectic reaction. The marked signs for single helix of maize amylopectin with Mw >20 × 105 g/mol were the enhancement of weak resonance at 100.0 ppm (104.1, 100.0, 94.6, 82.9 ppm). Single-helix maize amylopectin was more likely to form sharp X-ray diffraction during being dried without gelatinization. The possible mechanism for anti-retrogradation of maize amylopectin by co-crystal treatment was deduced. Co-crystallization with NaCl to produce single-helix amylopectin was a promising strategy to prepare anti-retrogradation amylopectin.

Research on the influences of two alcohol soluble glutenins on the retrogradation of wheat amylopectin/amylose.

Two alcohol soluble glutenins (ASGLUs) were extracted from gluten and further separated by column chromatography. The ASGLUs with Mw lower than 20,000 (ASGLU 1) and Mw higher than 70,000 (ASGLU 2) show the total amino acid contents of 86.71 g/100 g and 62.847 g/100 g respectively. Both of them are rich in Glu (45.574% and 43.224%) and Pro (15.447% and 16.370%) while poor in cys-s, met and lys (less than 1%). When wheat amylopectin/amylose retrogrades with those ASGLUs, the retrogradation rate of amylopectin with ASGLU 1 enhances significantly. UV-Vis, X-ray diffraction, FT-IR, DSC, CD and solid 13C NMR suggest that the double helixes of amylopectin short-chain branching are unwound during gelatinization. The hydrogen bonds of ASGLU 1 between amide and carbonyl oxygen are destroyed, meanwhile, ß-sheets are unfolded. During retrogradation, ASGLU 1 with less steric hindrance gets into the crevice of amylopectin and combines with the short-chain branching by hydrogen bond. The retrogradation dynamics show that the nucleation type of amylopectin-ASGLU 1 changes from instantaneous to rod-like growth during the process of retrogradation. ß-sheet of ASGLU 1 changes to ß-turn and random conformations at the meantime. The results provide a key targeting to control retrogradation of dough.

Identification of the main retrogradation-related properties of rice starch.

The retrogradation of rice in shelf life is the biggest barrier to the industrial production of traditional foods using rice as material. Many rice breeders have tried their best to screen low-retrogradation rice cultivars without a specific indicator. To identify the main retrogradation-related properties of rice, the starch, amylose, and amylopectin from 16 rice cultivars were extracted from rice powder and their physicochemical properties, such as visible absorbance, infrared, average molecule weight (amylopectin), chain-length distribution (amylopectin), X-ray diffraction, and differential scanning calorimetry, were determined. The correlation between starch retrogradation rates and those physicochemical properties was investigated. The results show that a significant positive correlation (R(2) = 0.85; r = 0.926; p < 0.01) exists only between proportions of the chains [degree of polymerization (DP) > 10] in amylopectin and the retrogradation rates of different rice starches. The findings in the paper offer a shortcut for rice breeders to screen cultivars with a low retrogradation rate. Because the genes related to the branching enzyme control the DP of amylopectin, they can be exploited as molecular markers to screen low-retrogradation rice cultivars.

Retrograded maize starch used as a medium to enrich Monascus from the air in winter.

Red pigments extracted from fungus Monascus are used for food coloration in China. Wild-growing Monascus spores are usually enriched in the yeast and mold media in the air, but those media are also favorable for yeast and bacteria. In the paper, Monascus species have grown in retrograded maize starch lain in air outdoors in winter, molds, yeast or bacteria colonies have been absent. Then a medium of the retrograded maize starch for enriching Monascus in the air is explored and its physicochemical properties are determined by ordinary camera photos, NMR, SEM spectra and X-ray diffraction. The lamellar structure of frozen retrograded maize starch, whose interlamellar spacing is about 2µm, provides a favorable condition for Monascus spore to germinate and grow.

The properties of different cultivars of Jinhai sweet potato starches in China.

IR, (13)C NMR, X-ray diffraction and DSC applied to study the physicochemical properties of starches from six different cultivars of Jinhai (I-VI) sweet potato strains in China. Jinhai II showed the highest rate of retrogradation while Jinhai III showed the lowest in all studied cultivars. The hydrolysis rates of those starches by α-amylase were from 98.1% in Jinhai II to 99.9% in Jinhai VI with a mean value of 99.3%. The ratio of R (1158/991cm(-1)) in IR spectra of those six different sweet potato starches could be the feature to identify them. All of the six studied Jinhai sweet potato starches showed strong peak at diffraction angle (2θ) of 17°, 15° and 23°, meanwhile an extremely weak peak at 2θ around 5.5° was also identical. XRD pattern of Jinhai II and IV starch also gave strong diffraction peaks at 26.6°, which could be the characteristics of them. The enthalpy and Tp of Jinhai II were especially lower than other cultivars. Jinhai IV revealed two Tp of 128.0°C and 140°C, respectively. The second Tp was maybe the characteristic of Jinhai IV starch. IR and DSC were the most effective methods to distinguish different cultivars of sweet potato.

The retrogradation properties of glutinous rice and buckwheat starches as observed with FT-IR, 13C NMR and DSC.

The experiment was conducted to study the retrogradation properties of glutinous rice and buckwheat starch with wavelengths of maximum absorbance, FT-IR, (13)C NMR, and DSC. The results show that the starches in retrograded glutinous rice starch and glutinous rice amylopectin could not form double helix. The IR results show that protein inhabits in glutinous rice and maize starches in a different way and appearance of C-H symmetric stretching vibration at 2852 cm(-1) in starch might be appearance of protein. Retrogradation untied the protein in glutinous amylopectin. Enthalpies of sweet potato and maize granules are higher than those of their retrograded starches. The (13)C NMR results show that retrogradation of those two starches leads to presence of ß-anomers and retrogradation might decompose lipids in glutinous rice amylopectin into small molecules. Glutinous rice starch was more inclined to retrogradation than buckwheat starch. The DSC results show that the second peak temperatures for retrograded glutinous rice and buckwheat starches should be assigned to protein. The SEM results show that an obvious layer structure exists in retrograded glutinous rice amylopectin.

Screening of seeds prepared from retrograded potato starch to increase retrogradation rate of maize starch.

In this paper, retrograded potato starches treated by oxalic, hydrochloric and citric acids and/with amylase respectively, as seed crystals, are added into maize starch paste to increase maize starch retrogradation rate. The results show that addition of seed accelerates maize starch retrogradation greatly. Seed prepared from retrograded potato starch treated by oxalic acid increases maize starch retrogradation rate most, from 1.5% to 49%. The results of IR spectra of retrograded maize starch derived from different seeds show that double helix, not hydrogen bond, probably forms at stage of seed growth during retrogradation. The results of IR spectra, X-ray and SEM indicate that treatment of retrograded potato starch with oxalic acid leads to formation of more hydrogen bonds and an increase of seed crystal planes, which markedly promotes the growth of the seed. Retrogradation of maize starch by seeding method surely includes a stage of crystal growth through double helix in a way different from normal maize starch retrogradation.

Effects of soy protein hydrolysates on maize starch retrogradation studied by IR spectra and ESI-MS analysis.

Starch retrogradation is the main cause of quality deterioration of starch-containing foods during storage. The purpose of this study is to find out whether certain soy protein polypeptide in hydrolysates will retard maize starch retrogradation. The results show that all soy protein hydrolysates retard maize starch retrogradation to a certain extent. The IR spectra of hydrolysates and the blends of hydrolysates and maize starch show that the polypeptides might act with reducing end of maize starch during retrogradation. The results of electrospray ionization-mass spectrometry [ESI-MS] show that the polypeptide (m/z 863) is present in all three hydrolysates remarkedly retarding maize starch retrogradation and its relative abundence is also the highest. So the polypeptide containing seven amino acids probably is the key component to significantly inhibit maize starch retrogradation.

Retrograded starches as potential anodes in lithium-ion rechargeable batteries.

Retrograded starch is a crystal formed by starch molecules with hydrogen bonds. Many literatures have reported its physicochemical character, but its crystal structure is so far unclear. As we isolate amylose and amylopectin from retrograded maize, sweet potato and potato starches in 4.0 M KOH solutions and make them retrograde alone in neutral solution (adjusted by HCl) to form crystal, a new phenomenon appears, crystals of KCl do not appear in retrograded potato amylose, potato amylopectin, and maize amylose, indicating that those crystals may absorb K⁺ and (or) Cl⁻, and those ions probably act with aldehyde of starch or hydroxy of fatty acid attached in starch, such characteristic may make retrograded starches replace graphite as anode with high-capacity in lithium-ion rechargeable batteries.

A possible structure of retrograded maize starch speculated by UV and IR spectra of it and its components.

"Retrogradation" has been used to describe the changes that occur in starch after gelatinization, from an initially amorphous state to a more ordered or crystalline state, which has a significant impact on starch application in food, textiles and materials fields. But mechanism of starch retrogradation is still unclear until now and there is no breakthrough in this area. Here we are speculating a possible structure of retrograded maize starch by UV (binding with iodine) and IR spectra of it and its compositions. We speculate that nucleation of retrograded starch origins from combination of reducing end of amylopectin and non-reducing end of amylose, and retrogradation terminates at combining of non-reducing end of amylopectin and reducing end of amylose. The chain length of resistant digestion retrograded starch should be nearly same. The hydroxyl associated with sixth carbon atoms of glucan must form hydrogen bond with other hydroxyl of starch.

A photographic approach to the possible mechanism of retrogradation of sweet potato starch.

Although the subject of starch retrogradation has been studied for about 20 years, the mechanism of starch retrogradation seems not yet to be completely established. In this paper, the possible retrogradation mechanism of sweet potato starch was postulated from four optical micrographs at the stages of melting of the starch granules, autoclaving treatment and aging. The possible process of retrogradation consists of three stages. Firstly, starch granules was swelled and melted with loss of X-ray crystallinity and formation of both crystalline and amorphous lamellae; secondly, in crystalline lamellae, amylopectin began to form nucleation when they were autoclaved; finally, the nucleus grew up to great rod-like crystals as the result of congregating of amylose on plates which were composed of and prolongated by amylopectin.