A critical review of a typical research system for food-derived metal-chelating peptides: Production, characterization, identification, digestion, and absorption.

In the past decade, food-derived metal-chelating peptides (MCPs) have attracted significant attention from researchers working towards the prevention of metal (viz., iron, zinc, and calcium) deficiency phenomenon by primarily inhibiting the precipitation of metals caused by the gastrointestinal environment and exogenous substances (including phytic and oxalic acids). However, for the improvement of limits of current knowledge foundations and future investigation directions of MCP or their derivatives, several review categories should be improved and emphasized. The species' uniqueness and differences in MCP productions highly contribute to the different values of chelating ability with particular metal ions, whereas comprehensive reviews of chelation characterization determined by various kinds of technique support different horizons for explaining the chelation and offer options for the selection of characterization methods. The reviews of chelation mechanism clearly demonstrate the involvement of potential groups and atoms in chelating metal ions. The discussions of digestive stability and absorption in various kinds of absorption model in vitro and in vivo as well as the theory of involved cellular absorption channels and pathways are systematically reviewed and highlighted compared with previous reports as well. Meanwhile, the chelation mechanism on the molecular docking level, the binding mechanism in amino acid identification level, the utilizations of everted rat gut sac model for absorption, and the involvement of cellular absorption channels and pathway are strongly recommended as novelty in this review. This review makes a novel contribution to the literature by the comprehensive prospects for the research and development of food-derived mineral supplements.

Characterization of Oyster Protein Hydrolysate-Iron Complexes and their In Vivo Protective Effects against Iron Deficiency-Induced Symptoms in Mice.

Iron is one of the trace mineral elements, and iron deficiency is a common phenomenon that negatively influences human health. Food-derived iron supplements were considered excellent candidates for improving this syndrome. In this work, oyster-protein hydrolysates (OPH) and ferrous chloride successfully formed the OPH-Fe complex (6 mg/mL, 40 °C, 30 min), where the main binding sites involved were the carboxyl and amino groups. The OPH-Fe complex showed no obvious changes in the secondary structure, while the iron changed the morphological appearance and also showed fluorescence quenching, an ultraviolet shift, and an increase in size distribution. The OPH-Fe complex showed better dynamic absorption of iron (64.11 µmol/L) than ferrous sulfate (46.90 µmol/L), and the medium dose had better protective effects against iron-deficiency anemia in vivo. Three representative peptides (DGKGKIPEE, FAGDDAPRA, and VLDSGDGVTH) that were absorbed intact were identified. This experiment provided a theoretical foundation for further study of the digestion and absorption of the OPH-Fe complex.

Response surface methodology-optimized extraction of flavonoids with antioxidant and antimicrobial activities from the exocarp of three genera of coconut and characterization by HPLC-IT-TOF-MS/MS.

Response surface methodology optimization based on central composite design was applied to extract flavonoids from the exocarp of three coconut genera. The antioxidant and antimicrobial activities and structures of the flavonoids were determined. The results indicated that the optimal extraction conditions were ethanol concentration, 60%; temperature, 50 ℃; time, 90 min; liquid/material ratio, 40 mL/g; ultrasonic power, 150 W. Under these conditions, the yields of green, red and yellow coconut exocarp were 366.03 ± 7.57, 596.38 ± 10.32, and 403.78 ± 5.56 mg rutin/g powder, respectively. The flavonoids exhibited eminent DPPH and ABTS radical scavenging activities with IC50 values of 0.01-0.02 mg/mL. At a concentration of 2 mg/mL, they exhibited antimicrobial activity against Vibrio parahaemolyticus, Listeria monocytogenes, Escherichia coli, Staphylococcus aureus, Salmonella and Pseudomonas aeruginosa. In total, 17 flavonoids and 5 phenolic acids were characterized by UPLC-IT-TOF-MS/MS; among them, catechin, kaempferol, and quercetin were abundant. Yellow coconut had a distinct flavonoid spectrogram from other genera and contained more methoxy flavonoids.

Efficient Synthesis of Structured Phospholipids Containing Short-Chain Fatty Acids over a Sulfonated Zn-SBA-15 Catalyst.

Catalytic production of structured phospholipids (SPLs) containing short-chain fatty acids (SCFAs) in an efficient heterogeneous manner is of great importance from the standpoint of food engineering. Herein, a bifunctionalized sulfonated Zn-SBA-15 catalyst was studied for SPL synthesis through interesterification of soybean lecithin with ethyl propionate or methyl butyrate. Various characterization techniques such as pyridine Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet-visible diffuse reflectance spectroscopy were conducted to determine the physicochemical properties, so as to build the possible structure-reactivity relationship of the catalyst. In screening tests with commercial Amberlyst-15 or other SBA-15-type materials, the as-prepared sample showed promising catalytic performance probably owing to its mesoporous structure and cooperative role of Brönsted and Lewis acid sites. Notably, the sample was easily separated and recycled without obvious deactivation. In general, the investigated catalyst was regarded as one of the promising alternatives to otherwise expensive biocatalysts for SCFA-containing SPL production.

Improving oxidative stability and release behavior of docosahexaenoic acid algae oil by microencapsulation.

BACKGROUND: Spray-dried docosahexaenoic acid algae oil (DHA AO) microcapsules were prepared using whey protein isolate and glucose syrup (WPI + GS), or sodium starch octenylsuccinate and glucose syrup (SSOS + GS), or whey protein isolate and lactose (WPI + L). The effect of the formulations on encapsulation properties, oxidative protection and in vitro oil release pattern of the resulting microencapsulates was investigated. RESULTS: A high encapsulation efficiency of over 98% of DHA AO was obtained for microcapsules with all three wall materials. Among the wall materials, SSOS + GS exhibited a better micro-particulation ability reflected by more uniform size and smoother surface of the formed microcapsules and no agglomerates. DHA AO microcapsules with all the wall materials showed good protection of the oil from oxidation during storage with an increasing order of WPI + GS, SSOS + GS and WPI + L. Moreover, microencapsulation significantly increased the release of DHA AO in the intestinal phase of the in vitro digestion process with an increasing order of SSOS + GS, WPI + GS and WPI + L, indicating the increased stability of the oil in the highly acidic gastric environment and the enhanced lipid digestibility in the small intestine. CONCLUSIONS: The results suggest that it is possible to transform a highly oxidizable liquid functional food ingredient such as DHA AO into a stable and easy-to-handle solid powder through spray drying with properly selected wall materials. © 2020 Society of Chemical Industry.

Improving the oxidative stability and lengthening the shelf life of DHA algae oil with composite antioxidants.

Based on various antioxidant mechanisms, four kinds of antioxidants including ascorbyl palmitate (AP), vitamin E (VE), phytic acid (PA) and one of the polyphenols (antioxidant of bamboo leaves, tea polyphenol palmitate or tea polyphenols (TP)) were used in combination to improve oxidative stability of docosahexaenoic acid (DHA) algae oil. To achieve the best effect, the formulations and mixture ratios of the antioxidant combinations were optimized. The effects were monitored by peroxide value, thiobarbituric acid-reactive substances, acid value, free radicals, Rancimat induction time and fatty acid composition of DHA algae oil undergoing accelerated storage. Finally, the DHA algae oil containing 80 mg/kg AP, 80 mg/kg VE, 40 mg/kg PA and 80 mg/kg TP had the highest oxidative stability. Furthermore, the shelf life of DHA algae oil containing the optimum composite antioxidant was predicted by using accelerated shelf life testing coupled with Arrhenius model, which was 3.80-fold longer than the control sample.

Isolation and identification of zinc-chelating peptides from sea cucumber (Stichopus japonicus) protein hydrolysate.

BACKGROUND: Zinc is known to play an essential role in the biological activities in the human body. In this study, a zinc-chelating peptide (ZCP) produced by Alcalase-assisted hydrolysis of the body wall of sea cucumber was isolated and identified. The ZCP was purified stepwise by ultrafiltration, anion-exchange chromatography, and gel filtration chromatography, in conjunction with ultraviolet-visual (UV-visual) spectrophotometry, which was used to analyze each purified fraction. RESULTS: Analysis of the purified ZCP revealed that its zinc-chelating ability was 33.31%. Analysis of isothermal titration calorimetry suggested that the binding of ZCP and zinc (N ≈ 2) was endothermic, with weak binding affinity. Fourier transform infrared spectroscopy spectra (FTIR) indicated that carboxylic and amide groups in ZCP were the primary binding sites of Zn. Sequencing the result by ultra-performance liquid chromatography-quadrupole/time of flight mass spectrometry (UPLC-Q-TOF-MS/MS) showed that a representative ZCP had the sequence WLTPTYPE with a molecular weight of 1005.5 Da. CONCLUSION: These results provide a promising foundation for the production of zinc supplements from sea-cucumber-derived ZCPs. © 2019 Society of Chemical Industry.

Effects of natural phenolics on shelf life and lipid stability of freeze-dried scallop adductor muscle.

Effects of natural phenolics on the shelf life of dried scallop adductor muscle predicted by accelerated shelf life testing (ALST) combined with Arrhenius model were investigated. This allows the food industries to reliably and rapidly determine the shelf life of dried shellfish species treated with antioxidants. The shelf life of dried scallop adductor muscle treated with antioxidants of bamboo leaves (AOB) and tea polyphenols (TP) was more than 1.70-fold that of dried control scallop adductor muscle. Thus, the highly nutritional value of dried scallop adductor muscle, based on its lipid constituents, is maintained during storage. OXITEST method further confirmed the improvement of lipid stability of antioxidant treated dried scallop adductor muscle by protecting polyunsaturated fatty acids, especially eicosapentaenoic and docosahexaenoic acids, against autoxidation. Moreover, the natural phenolics employed effectively limited lipid oxidation by breaking the autoxidative chain reaction and/or inhibiting free radical formation in dried scallop adductor muscle during storage.

Mechanism of antioxidant action of natural phenolics on scallop (Argopecten irradians) adductor muscle during drying process.

Lipid hydrolysis and oxidation occurred in Argopecten irradians adductor muscle during hot air drying. Using an in vivo imaging system, we found that antioxidants of bamboo leaves (AOB) could diffuse into the adductor muscle upon marinating. Both tea polyphenols (TP) and AOB efficiently retarded lipid oxidation but had a slight effect on lipid hydrolysis during drying process. The in situ antioxidant mechanisms of AOB as well as TP were revealed, including quenching of free radicals detected by electron spin resonance, chelating metal ions determined by confocal laser scanning microscopy and inhibiting lipoxygenase. Less than 8% of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in AOB and TP marinated adductor muscle were decreased compared to more than 28% decrease in control adductor muscle during the drying process. Overall, these natural antioxidants, TP and AOB, efficiently maintained high nutritive value of adductor muscle, especially, their lipid quality.

Extraction and detailed characterization of phospholipid-enriched oils from six species of edible clams.

Phospholipid (PL)-enriched oils were recovered from six species of edible clams, namely Cyclina sinensis, Mactra chinensis Philippi, Mactra veneriformis Reeve, Meretrix meretrix, Ruditapes phliippinarum and Saxidomus purpurata, using a mixture of ethanol and hexane (1:1, v/v). The oils contained a high proportion of polyunsaturated fatty acids (PUFA) (26.78-45.36% of total FAs), especially eicosapentaenoic acid (EPA) (8.17-10.48% of total FAs) and docosahexaenoic acid (DHA) (7.83-21.34% of total FAs). The oils also contained a high percentage of PL (39.86-74.05% of total lipids). Among PL, phosphatidylcholine (37.40-52.19mol%) and phosphatidylethanolamine (34.74-43.10mol%) were dominant. At least 435, 442, 513, 438, 433 and 437 glycerophospholipid (GP) molecular species were characterized, respectively, in lipids from Cyclina sinensis, Mactra chinensis Philippi, Mactra veneriformis Reeve, Meretrix meretrix, Ruditapes phliippinarum and Saxidomus purpurata. Most of the predominant GP molecular species contained PUFA, mainly EPA and DHA, indicating that clam is a potential resource of PUFA enriched GP.

Effects of long-term intake of Antarctic krill oils on artery blood pressure in spontaneously hypertensive rats.

BACKGROUND: In recent years, there has been a noticeable increase in research on krill oil (KO) for its health benefits. However, the action of KO in lowering blood pressure (BP) has not been studied yet. Therefore the aim of this study was to assess the ability of long-term KO supplementation to lower systolic BP (SBP) in spontaneously hypertensive rats (SHRs) and Sprague Dawley (SD) rats. RESULTS: Compared with the blank control (BC) SHRs administered edible soybean oil, the high-dose (500 mg kg-1 body weight (BW)) KO-supplemented SHRs in the 2nd, 3rd, 4th and 5th weeks following oral administration, the mid-dose (100 mg kg-1 BW) KO-supplemented SHRs in the 4th and 5th weeks following oral administration and the low-dose (20 mg kg-1 BW) KO-supplemented SHRs in the 5th week following oral administration showed significantly lower SBP (P < 0.05). However, supplementation of KO had no significant effect on the SBP of healthy SD rats. Meanwhile, 5 weeks of KO administration significantly increased the serum levels of nitric oxide (NO) and total NO synthase of SHRs (P < 0.05). CONCLUSION: KO has an antihypertensive effect in SHRs that is associated with an NO-related mechanism. © 2016 Society of Chemical Industry.

Identification of volatile compounds emitted by Artemisia ordosica (Artemisia, Asteraceae) and changes due to mechanical damage and weevil infestation.

Volatiles emitted by healthy, mechanically damaged, and weevil-infested Artemisia ordosica (Asteraceae) were obtained through a dynamic headspace method and analysed by automatic thermal desorption/gas chromatography/mass spectrometry (ATD/GC/MS). Twenty-eight compounds in all were identified, and the qualitative as well as quantitative differences were compared. The green leaf volatiles 2-hexenal, (Z)-3-hexen-1-ol, 2-hexen-1-ol, 1-hexanol, and (Z)-3-hexen-1-ol acetate were present in all of the damaged plants, but in relatively lower portions when plants were infested by the weevil Adosopius sp., while the terpenoids alpha-copaene, beta-cedrene, and (E,E)-alpha-farnesene and the ester methyl salicylate were only present in weevil-damaged plants. The volatiles from healthy and weevil-infested leaves were dominated by D-limonene, whereas mechanically damaged leaves emitted beta-pinene as the dominant compound.

Characterization of polymethoxylated flavones in Fructus aurantii by off-line two-dimensional liquid chromatography/electrospray ionization-ion trap mass spectrometry.

Off-line two-dimensional reversed-phase liquid chromatography (2D-RPLC) coupled to electrospray ionization-ion trap mass spectrometry (ESI-ITMS) was operated in positive mode (PI) to characterize polymethoxylated flavonoids (PMFs) in botanical sample. The fragments of [M+H-nx15](+) produced by loss of one or more methyl group from the protonated molecules, as well as [M+H-14](+), [M+H-29](+), [M+H-33](+), [M+H-43](+), [M+H-46](+) and [M+H-61](+) fragments formed the multiple MS (MS(n)) "fingerprint" of PMFs. 42 target compounds were tentatively identified from the extract of Fructus aurantii (F. aurantii) based on this "fingerprint". Experimental outcomes indicated that the application of 2D separation method can reduce the matrix suppression of analytes caused by the coelution with interferential components and the column overloading of interferential components. 42 versus 23 target compounds were detected through 2D versus 1D method, which confirm the superiority of 2D coupled to MS in elimination of matrix effects.

A new polysaccharide from leaf of Ginkgo biloba L.

A water-soluble polysaccharide, GPB, was obtained from leaf of Ginkgo biloba L by hot water extraction followed by precipitation with ethanol and fractionation with gel chromatography. The results of HPLC with TSK-GEL column and gel filtration chromatography with Sepharose CL-6B analysis indicated GPB was uniform in polarity and its molecular weight (MW) was about 10 kDa. The structure of GPB was analysed using chemical methods, IR spectroscopy, and NMR spectroscopy. GPB has a high branched structure with polygalactose as core part of backbone. The repeating unit of polygalactose consists of 1,6-linked Galactose (Gal) and 1,3,6-linked Gal.

Analysis of iridoid glucosides in Hedyotis diffusa by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry.

An HPLC-DAD-ESI-MS/MS method was developed for analysis of iridoid glucosides (IGs) from Hedyotis diffusa Willd. The optimized separation condition was achieved with the Complex Sample Analysis Software System (CSASS) software, under which the whole analytes were achieved complete resolution especially for some isomeric IGs. Based on the UV and fragmentations, eleven IGs were detected. According to the fragmentation patterns of the three standard IGs, especially those of the isomeric standards, seven IGs including three pairs of isomers were unambiguous/tentatively identified. For the isomeric IGs with methyl ester or carboxyl group at C-4, the extents of the losses of CH3OH and/or H2O from their molecular and/or the aglycone adducts are useful for the differentiation of the stereoisomers in positive ion (PI) mode, which depends on the stereochemistry of the hydroxyl group on the cyclopentanoid unit.

Polymethoxylated flavones metabolites in rat plasma after the consumption of Fructus aurantii extract: analysis by liquid chromatography/electrospray ion trap mass spectrometry.

A LC with full scan MS(n) method was developed in order to investigate the in vivo absorption and biotransformation of polymethoxylated flavones (PMFs) by analysis of plasma samples from rats after ingestion of Fructus aurantii extract. Four parent compounds and six metabolites with intact flavonoid structures were tentatively identified. The metabolites were either glucuronides of parent compounds or glucuronides of demethylated products of parent compounds.

Rapid qualitative and quantitative analyses of flavanone aglycones in Fructus aurantii by HPLC ion-trap MS.

IT-MS operated in the positive mode was applied for the rapid characterization/quantification of the flavanones in extracts from Fructus aurantii. APCI-MS and CID MS/MS provide unequivocal molecular weight (MW) data of these compounds and useful information about their structures (diagnostic fragment ions). Main fragment pathways include neutral losses of H2O, C2H2O, and B-ring as well as a retro-Diels-Alder (RDA) fragment giving rise to [1,3A + H], [1,3B+H]+, and [1,4B-H2 + H]+ ions, which form the characteristic MS/MS "fingerprint" of flavanone aglycones. When screening extracts of F. aurantii for flavanone aglycones, eight target compounds were characterized using this fingerprint. Meanwhile, ESI-MS in full-scan mode was developed and validated for the quantification of the main flavanone aglycones in F. aurantii. This method is simple, accurate, fast and requires only 16 min per sample for direct detection and quantification of naringenin and hesperetin. All the results and these characteristic fragments showed that the IT-MS is a powerful tool for the structural characterization and quantitative determination offlavanone aglycones.

Characterization of polymethoxylated flavones in Fructus aurantii by liquid chromatography with atmospheric pressure chemical ionization combined with tandem mass spectrometry.

Atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was operated in positive mode (PI) to characterize polymethoxylated flavonoids (PMFs) through its specific radical cations by collision-induced dissociation (CID). The fragments of [M + H - n x 15]+ produced by loss of one or more methyl group from the protonated molecule, as well as [M + H - 29]+, [M + H - 31]+, [M + H - 33]+, [M + H - 43]+, [M + H - 46]+, and [M + H - 61]+ fragment ions were detected, which were diagnostic for the polymethoxylated species, and could be adopted to form the multiple MS (MS(n)) "fingerprint" of PMFs. Based on this "fingerprint", 29 PMFs were screened out from extracts of Fructus aurantii, among which two of them were identified as sinensetin and tangeretin. It was proved that the PI was suitable for structural characterization of PMFs by APCI-MS(n).

Identification of O-diglycosyl flavanones in Fructus aurantii by liquid chromatography with electrospray ionization and collision-induced dissociation mass spectrometry.

This study reported the application of LC-ESI/MS method to characterize O-diglycosyl flavanones of traditional Chinese medicine Fructus aurantii(Zhiqiao) and UPLC retention parameters method to expatiate the structure-retention relationship of these O-diglycosyl flavanones. The extract of F. aurantii was found containing neoeriocitrin, isonaringin, naringin, hesperidin, neohesperidin and neoponcirin. Tandem mass spectrometric method has been utilized to elucidate structure and differentiate the interglycosidic linkage of isomeric O-diglycosyl flavanones. Based on the relative abundance of fragments formed by fragmentation at glycosidic bonds in positive ion mode and CID MS spectra of deprotonated molecule [M-H](-) in negative ion mode, the interglycosidic linkage of O-diglycosyl flavanones (flavonoid O-neohesperidosides and O-rutinosides, 1,2- and 1,6-) can be unambiguously differentiated. UPLC and a CSASS software were performed to obtain the retention parameters a, c and k values of these compounds. The Deltaa, Deltac and alpha values within compound pair naringin to neoriocitrin, neoponcirin to neohesperidin, naringin to isonaringin, neohesperidin to hesperidin, hesperidin to isonaringin, neohesperidin to naringin were calculated. We found there were some relationship between structure and retention parameters.