Palladium-Catalyzed Asymmetric Decarboxylation of 5-Vinyloxazolidine-2,4-Diones Triggering the Dearomatization of Electron-Deficient Indoles for the Synthesis of Chiral Highly Functionalized Pyrroloindolines.

A catalyst system consisting of a chiral phosphoramidite ligand and Pd2(dba)3·CHCl3 causes the decarboxylation of 5-vinyloxazolidine-2,4-diones to generate amide-containing aza-π-allylpalladium 1,3-dipole intermediates, which are capable of triggering the dearomatization of 3-nitroindoles for diastereo- and enantioselective [3+2] cycloaddition, leading to the formation of a series of highly functionalized pyrroloindolines containing three contiguous stereogenic centers with excellent results (up to 99% yield, 88:12 dr, and 96% ee).

Diastereoselective Formal 1,3-Dipolar Cycloaddition of Trifluoroethyl Amine-Derived Ketimines Enables the Desymmetrization of Cyclopentenediones.

In this research, a metal-free diastereoselective formal 1,3-dipolar cycloaddition of N-2,2,2-trifluoroethylisatin ketimines and cyclopentene-1,3-diones which can efficiently lead to the desymmetrization of cyclopentene-1,3-diones is developed. With the developed protocol, a series of tetracyclic spirooxindoles containing pyrrolidine and cyclopentane subunits can be smoothly obtained with good results (up to 99% yield and 91:9 dr). Furthermore, the methodology can be extended to trifluoromethyl-substituted iminomalonate, and the corresponding formal [3+2] cycloaddition reaction affords bicyclic heterocycles containing fused pyrrolidine and cyclopentane moieties in moderate yields with >20:1 dr. The synthetic potential of the methodology is demonstrated by the scale-up experiment and by versatile transformations of the products.

Catalytic enantioselective hydrophosphinylation of in situ-generated indole-derived vinylogous imines to access 3-(1-diphenylphosphoryl-arylmethyl)indoles.

An efficient organocatalyzed enantioselective hydrophosphinylation of indole-derived vinylogous imines generated in situ from sulfonyl indoles has been developed. Using quinine-derived bifunctional thiourea as the catalyst, a wide range of structurally diverse chiral 3-(1-diphenylphosphoryl-arylmethyl)indoles were obtained with good to excellent results (up to 99% yield and 99% ee). This method represents the first example of the catalytic asymmetric Michael addition of phosphine oxides to vinylogous imine intermediates.

Effects of Lactobacillus plantarum and Saccharomyces cerevisiae co-fermentation on the structure and flavor of wheat noodles.

BACKGROUND: Although traditional fermented noodles possess high eating quality, it is difficult to realize large-scale industrialization as a result of the complexity of spontaneous fermentation. In present study, commercial Lactobacillus plantarum and Saccharomyces cerevisiae were applied in the preparation of fermented noodles. RESULTS: The changes in the structural characteristics and aroma components of noodles after fermentation were investigated via scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), low-field magenetic resonance imaging, electronic nose, and simultaneous distillation and extraction/gas chromatography-mass spectrometry (GC-MS) analysis. SEM images revealed that co-fermentation of the L. plantarum and S. cerevisiae for 10-40 min enhanced the continuity of the gluten network and promoted the formation of pores. FTIR spectra analysis showed that the co-fermentation increased significantly (P < 0.05) the proportion of α-helices of noodles gluten protein, enhancing the orderliness of the molecular structure of protein. After fermentation for 10-40 min, the signal density of hydrogen protons increased from the surface to the core, indicating that the water in the noodles migrated inward during a short fermentation process. The results of multivariate statistical analysis demonstrated that the main aroma differences between unfermented and fermented noodles were mainly in hydrocarbons, aromatic compounds and inorganic sulfides. GC-MS analysis indicated that the main volatile compounds detected were 2, 4-di-tert-butylphenol, bis (2-ethylhexyl) adipate, butyl acetate, dibutyl phthalate, dioctyl terephthalate, bis (2-ethylhexyl) phthalate, pentanol and 2-pentylfuran, etc. CONCLUSION: Co-fermentation with L. plantarum and S. cerevisiae improved the structure of gluten network and imparted more desirable volatile components to wheat noodles. © 2022 Society of Chemical Industry.

Effects of konjac glucomannan on the long-term retrogradation and shelf life of boiled wheat noodles.

BACKGROUND: Starch retrogradation and moisture migration of boiled wheat noodles (BWNs) result in quality deterioration and short shelf life. The objective of this research was to investigate whether konjac glucomannan (KGM) could improve the quality of BWNs and further establish the shelf-life prediction model. RESULTS: The moisture distribution, recrystallization, and thermal properties of BWNs during refrigerated or ambient temperature storage were determined. Low-field nuclear magnetic resonance data showed that KGM addition induced left-shifts of T21 and T22 values, indicating that KGM limited the mobility of bound and immobile water among noodle matrices. X-ray diffraction spectra revealed that KGM did not change the crystal patterns of BWNs but could inhibit the starch recrystallization after refrigerated storage. The Tp and ΔH values of retrograded samples notably (P < 0.05) decreased with the increase of KGM addition, suggesting the hinderance of starch retrogradation behavior by KGM. The shelf life of BWNs was predicted by accelerated storage test combined with the Arrhenius equation. The present data displayed that the predicted shelf life of vacuum-packed and sterilized BWNs with 10 g kg-1 KGM at 25 °C was 733 days, 2.4-fold that of the control group. CONCLUSION: BWNs with KGM addition could inhibit starch retrogradation and improve the storage stability, consequently promoting noodle quality. © 2021 Society of Chemical Industry.

Polarization-Insensitive Broadband THz Absorber Based on Circular Graphene Patches.

A polarization-insensitive broadband terahertz absorber based on single-layer graphene metasurface has been designed and simulated, in which the graphene metasurface is composed of isolated circular patches. After simulation and optimization, the absorption bandwidth of this absorber with more than 90% absorptance is up to 2 THz. The simulation results demonstrate that the broadband absorption can be achieved by combining the localized surface plasmon (LSP) resonances on the graphene patches and the resonances caused by the coupling between them. The absorption bandwidth can be changed by changing the chemical potential of graphene and the structural parameters. Due to the symmetrical configuration, the proposed absorber is completely insensitive to polarization and have the characteristics of wide angle oblique incidence that they can achieve broadband absorption with 70% absorptance in the range of incident angle from 0° to 50° for both TE and TM polarized waves. The flexible and simple design, polarization insensitive, wide-angle incident, broadband and high absorption properties make it possible for our proposed absorber to have promising applications in terahertz detection, imaging and cloaking objects.

Interactions of chlorogenic acid and isochlorogenic acid A with model lipid bilayer membranes: Insights from molecular dynamics simulations.

Because of the negative side-effects of synthetic preservatives, the naturally-occurring polyphenols aroused intense interest of researchers. It has been suggested that chlorogenic acid (CA) and isochlorogenic acid A (iso-CAA) were good candidates to replace the synthetic preservatives. Moreover, the bactericidal activity of iso-CAA was stronger than CA, and the anti-bacterial activities of iso-CAA and CA were highly membrane-dependent. However, the mechanisms were still unclear. Therefore, in the present study, we investigated the mechanisms of the interactions between the two polyphenols and lipid bilayers through molecular dynamics simulations. The results revealed that iso-CAA could be inserted much deeper into POPG lipid bilayer than CA. We also found that hydrophobic interactions and hydrogen bonds both contributed to the insertion of iso-CAA into the POPG lipid bilayer, and the quinic acid moiety was the key structure in iso-CAA to form hydrogen bonds with POPG lipid bilayer. We believed that these findings would provide more useful information to explain the stronger bactericidal activity of iso-CAA than CA at the atomic level.

Influence of the gallate moiety on the interactions between green tea polyphenols and lipid membranes elucidated by molecular dynamics simulations.

Previous studies suggested that naturally occurring EGCG primarily acted on the bacterial cell membrane then damaged the membrane and the gallate moiety in EGCG was very important to its anti-bacterial activity. However, the detailed mechanisms were still poorly understood. In this paper, EGCG and EGC were selected to study the great contribution of gallate moiety on the anti-bacterial activities of polyphenols. The results indicated that EGCG could penetrate deeper into the POPG lipid bilayer and possess more potent structure-perturbing potency on the POPG lipid bilayer than EGC. We also found that EGCG had the ability to form hydrogen bonds with the deeper inside oxygen atoms in the POPG lipid bilayer and the gallate moiety was the key functional group for EGCG forming hydrogen bonds with the POPG lipid bilayer. Moreover, results from the binding free energy analysis demonstrated that the gallate moiety made great contribution to the high affinity between EGCG and the POPG lipid bilayer. We believed that these findings could yield useful insights into the influence mechanisms of gallate moiety on the anti-bacterial activities of polyphenols.

Removal of Alternaria mycotoxins from aqueous solution by inactivated yeast powder.

BACKGROUND: Alternariol (AOH) and alternariol monomethyl ether (AME), produced by Alternaria spp., are the two mycotoxins with the highest outbreak rates in food systems. The purpose of this study was to investigate the removal of AOH and AME from aqueous solutions by inactivated yeast cells. The effects of strains, yeast powder amount, temperature, and pH were evaluated. The kinetics of AOH and AME adsorption on inactivated yeast cells was fitted with four models and a release assay was carried out. RESULTS: All three tested yeasts could remove AOH and AME. GIM 2.119 was the most effective strain. The reduction rate of both AOH and AME could be as much as 100% with 40 g‧L-1 of yeast powder. For both mycotoxins, pH = 9 was the best environment for toxin removal. The pseudo-second-order kinetic model was the best model, with R2 ranging from 0.989 to 0.999. However, the R2 of the pseudo-first-order and Elovich models was also relatively high. Alternariol and AME could be partially eluted by methanol and acetonitrile. CONCLUSION: The inactivated yeast cells could effectively remove AOH and AME. This was best fitted by the pseudo-second-order model. The release assay suggested that the adsorption of Alternaria mycotoxins was partially reversible. The results of this study provide a theoretical basis for the removal of Alternaria mycotoxins from food systems and are useful for the investigation of the mechanisms involved in mycotoxin adsorption by inactivated yeast cells. © 2020 Society of Chemical Industry.

Asymmetric dearomatization of 2-nitrobenzofurans by organocatalyzed one-step Michael addition to access 3,3'-disubstituted oxindoles.

An efficient enantioselective dearomatization of 2-nitrobenzofurans was realized via an organocatalyzed one-step Michael addition process. This method provides a facile strategy to access a range of structurally diverse 3,3'-disubstituted oxindoles, which feature an intriguing combination of two privileged motifs including 3-pyrrolyl-substituted-oxindoles and 2,3-dihydrobenzofurans substructures, in excellent results.

Integrating GWAS and Gene Expression Analysis Identifies Candidate Genes for Root Morphology Traits in Maize at the Seedling Stage.

Root system plays an essential role in water and nutrient acquisition in plants. Understanding the genetic basis of root development will be beneficial for breeding new cultivars with efficient root system to enhance resource use efficiency in maize. Here, the natural variation of 13 root and 3 shoot traits was evaluated in 297 maize inbred lines and genome-wide association mapping was conducted to identify SNPs associated with target traits. All measured traits exhibited 2.02- to 21.36-fold variations. A total of 34 quantitative trait loci (QTLs) were detected for 13 traits, and each individual QTL explained 5.7% to 15.9% of the phenotypic variance. Three pleiotropic QTLs involving five root traits were identified; SNP_2_104416607 was associated with lateral root length (LRL), root surface area (RA), root length between 0 and 0.5mm in diameter (RL005), and total root length (TRL); SNP_2_184016997 was associated with RV and RA, and SNP_4_168917747 was associated with LRL, RA and TRL. The expression levels of candidate genes in root QTLs were evaluated by RNA-seq among three long-root lines and three short-root lines. A total of five genes that showed differential expression between the long- and short-root lines were identified as promising candidate genes for the target traits. These QTLs and the potential candidate genes are important source data to understand root development and genetic improvement of root traits in maize.

Downregulation of serum exosomal miR-150-5p is associated with poor prognosis in patients with colorectal cancer.

Growing evidence have revealed the serum exosomal miRNAs emerged as biomarkers for various cancer types, including colorectal cancer (CRC). Here, we sought to explore the potential clinical significance of serum exosomal miR-150-5p in CRC. A total of 133 CRC patients and 60 healthy volunteers as control group were recruited in this study. Exosomes were isolated from the serum of all the participants. The total RNA was isolated from the exosomes and the serum exosomal miR-150-5p levels were measured by quantitative reverse transcription-polymerase chain reaction. The findings showed that the serum exosomal miR-150-5p levels were significantly reduced in CRC cases compared with those in the control group. Serum exosomal miR-150-5p levels in post-operative blood samples were greatly upregulated one month after surgical treatment. In addition, decreased serum exosomal miR-150-5p expression was closely correlated with poorly differentiation, positive lymph node metastasis and advanced TNM stage. Moreover, receiver operating characteristic (ROC) curve analysis showed serum exosomal miR-150-5p level had good performance to identify CRC cases from healthy volunteers, and a combination of serum exosomal miR-150-5p and carcinoembryonic antigen (CEA) could improve the diagnostic accuracy with an increased the area under the ROC curve (AUC) value. Furthermore, the survival time of patients with higher serum exosomal miR-150-5p expression was significantly longer than those with lower expression. Serum exosomal miR-150-5p was confirmed as an independent prognostic indicator in CRC. Mechanistically, ZEB1 was identified as a direct downstream target of miR-150-5p. Collectively, serum exosomal miR-150-5p might be a novel noninvasive biomarker for CRC diagnosis and prognosis.

Comparison of the effects of dynamic high-pressure microfluidization and conventional homogenization on the quality of peach juice.

BACKGROUND: Dynamic high-pressure microfluidization (DHPM) is an emerging and promising technique for continuous production of fluid foods. This study aimed to investigate the influence of DHPM and conventional homogenization (CH) on the quality of peach juice. Processing was performed by passing peach juice through CH at 20 MPa and DHPM at 20-160 MPa for one or three passes. The effect of DHPM pressure and passing number were also assessed. RESULTS: The results indicate that DHPM could maintain the antioxidant activity of peach juice much better than CH processing. Total phenolic compounds were decreased by 11.7% and 7.9%-15.8% through CH and DHPM processing in different conditions. Moreover, particle size, non-enzymatic browning index and turbidity decreased significantly under DHPM and CH processing, and decreased more and more with the increasing of DHPM pressure and treatment times. However, vitamin C content and zeta-potential did not reveal remarkable variation before and after these two types of processing. CONCLUSION: Taken together, DHPM is able to maintain the quality and stability of peach juice, which can be a reliable technological alternative to CH to produce fresh-like peach juices. © 2019 Society of Chemical Industry.

Purification of Polyphenols from Distiller's Grains by Macroporous Resin and Analysis of the Polyphenolic Components.

We aimed to purify polyphenols from distiller's grain extract using macroporous resins and to identify its polyphenolic components. The influence of operational parameters on purification efficiency was investigated. The polyphenolic composition was analyzed by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) and then quantified by UPLC-MS using authenticated standards. The results showed that the optimal purifying conditions were D101 resin with a dosage of 3 g, four hours adsorption, three hours desorption time, and 60% ethanol as the eluent, producing the highest purification rate of 51%. The purified distiller's grain extract exhibited stronger antioxidant activity than the unpurified extracts, which was assessed using DPPH and ABTS methods (IC50 DPPH = 34.03 and 16.21 µg/mL, respectively; IC50 ABTS = 20.31 and 5.73 µg/mL, respectively). UPLC-MS results indicated that (-)-epicatechin is the major compound found in distiller's grain extract which was quantified as 562.7 µg/g extract, followed by ferulic acid (518.2 µg/g), p-hydroxybenzoic acid (417.7 µg/g), caffeic acid (217.1 µg/g), syringic acid (158.0 µg/g) and quercetin (147.8 µg/g). Two compounds, vanillic acid (66.5 µg/g) and gallic acid (41.4 µg/g), were found in lower concentrations. The findings of this study suggest that purification of polyphenolic compounds from distiller's grain by macroporous resins is feasible, providing a new and effective method for the secondary use of distiller's grain resources.

Understanding the shielding effects of whey protein on mulberry anthocyanins: Insights from multispectral and molecular modelling investigations.

Assembling between polyphenols and proteins has been recently spotlighted and this binding is of specific importance in food chemistry since these complexes are typically used in different foodstuffs. A study on the copigmentation among three encapsulation wall-materials, including maltodextrin, gum Arabic, and whey proteins, with mulberry anthocyanins (AC) proved that whey protein (WP) is an outstanding wall-material due to its wrapping and hyperchromicity effects. Additionally, high binding ability of WP with AC was shown to be responsible for its superior copigmentation effects. Accordingly, the underlying shielding mechanism of WP on AC based on their non-covalent assembling was deeply studied using multispectral and computational assays. The fluorometric results demonstrated that a static and heat-stable binding between WP and AC occurred, leading to modification in size, hydrophobicity, and secondary structures of WP. The docking results explained that WP-AC complex was mainly molded via hydrophobic effects of WP surface and subsequently be stabilized by H-bonding and van der Waals forces. These results may contribute to a better understanding on the enhanced colouring proprieties of anthocyanins by using whey proteins.

Interactions between highly galloylated persimmon tannins and pectins.

The interactions between pectins of different degrees of esterification (DE) and highly galloylated persimmon tannins with average degrees of polymerisation (DP26 and DP5) were investigated by UV-Vis spectrophotometry, dynamic light scattering, transmission electron microscopy, isothermal titration calorimetry and pyrene fluorescence methods Pectins displayed strong effects on the self-aggregation of persimmon tannins and improved the homogeneity of condensed tannin aggregates. The interaction between tannins and pectins may result from hydrogen bonding and hydrophobic interactions; by contrast, electrostatic interactions, which involve charged molecules in general, played no dominant role. In addition, the presence of gallate moieties in the high-polymerisation proanthocyanidin could enhance affinity with highly methylated pectins. Stronger association was observed with the high-polymerisation tannins (DP26) with high-methoxyl pectin (DE74) (Ka=(8.50±3.0)×103M-1) than with low-methylated pectin (DE30) (Ka=(3.62±1.92)×103M-1). The present results are expected to promote the application of the formed complexes as functional ingredients in food.

Comparison of disaggregative effect of A-type EGCG dimer and EGCG monomer on the preformed bovine insulin amyloid fibrils.

In the present study, the disruptive effects of epigallocatechin-3-gallate (EGCG) and A-type dimeric epigallocatechin-3-gallate (A-type EGCG dimer) on the preformed bovine insulin amyloid fibrils were studied by several biophysical methods including thioflavin-T (ThT) fluorescence assay, 1-anilinonaphthalene-8-sulfonic (ANS) fluorescence assay, Congo red (CR) binding assay, dynamic light scattering (DLS), transmission electron microscopy (TEM), Gel electrophoresis (SDS-PAGE) and Bradford assay. Our results demonstrated that A-type EGCG dimer showed significantly more potential disaggregative effects on the bovine insulin amyloid fibrils than EGCG. A-type EGCG dimer could not only dramatically promote the disaggregation of the preformed bovine insulin amyloid fibrils, but also restructure the amyloid fibrils into amorphous aggregates. While, EGCG could only shorten and thin the fibrils, but induce no small amorphous aggregates. Our present results provided additional evidence for the more potent disaggregation effects of dimeric polyphenols than monomeric polyphenols and suggested that A-type EGCG dimer seems to have potential application as an excellent anti-amyloidogenic agent.

Hepatotoxicity in Rats Induced by Aqueous Extract of Polygoni Multiflori Radix, Root of Polygonum multiflorum Related to the Activity Inhibition of CYP1A2 or CYP2E1.

The objective of this study is to investigate the relationship between the hepatotoxicity induced by Polygoni Multiflori Radix (PMR, root of Polygonum multiflorum Thunb., He Shou Wu) and the activity of CYP1A2 or CYP2E1 in the rat liver. Levels of rat serum transaminases ALT and AST were not altered but the activity of CYP1A2 or CYP2E1 in the rat liver was significantly inhibited after oral administration of aqueous extract of PMR under the experimental dosage. However, levels of ALT and AST were significantly increased and the activity of CYP1A2 or CYP2E1 was significantly decreased after injection of specific inhibitor for CYP1A2 or CYP2E1 combined with oral administration of aqueous extract of PMR, especially under the repeated treatment over interval times. Liver histopathological observation showed that a moderate liver injury occurred in rats receiving PMR treatment with the activity of CYP1A2 or CYP2E1 inhibited, but there was no significant liver damage in rats receiving PMR treatment or CYP inhibitor alone. These suggested that low level activity of CYP1A2 or CYP2E1 from genetic polymorphism among people might be one of the important reasons for the hepatotoxicity induced by PMR in clinical practice.

Adiponectin Suppresses T Helper 17 Cell Differentiation and Limits Autoimmune CNS Inflammation via the SIRT1/PPARγ/RORγt Pathway.

T helper 17 (Th17) cells are vital components of the adaptive immune system involved in the pathogenesis of most autoimmune and inflammatory syndromes, and adiponectin(ADN) is correlated with inflammatory diseases such as multiple sclerosis (MS) and type II diabetes. However, the regulatory effects of adiponectin on pathogenic Th17 cell and Th17-mediated autoimmune central nervous system (CNS) inflammation are not fully understood. In this study, we demonstrated that ADN could inhibit Th1 and Th17 but not Th2 cells differentiation in vitro. In the in vivo study, we demonstrated that ADN deficiency promoted CNS inflammation and demyelination and exacerbated experimental autoimmune encephalomyelitis (EAE), an animal model of human MS. Furthermore, ADN deficiency increased the Th1 and Th17 cell cytokines of both the peripheral immune system and CNS in mice suffering from EAE. It is worth mentioning that ADN deficiency predominantly promoted the antigen-specific Th17 cells response in autoimmune encephalomyelitis. In addition, in vitro and in vivo, ADN upregulated sirtuin 1 (SIRT1) and peroxisome proliferator-activated receptor γ (PPARγ) and inhibited retinoid-related orphan receptor-γt (RORγt); the key transcription factor during Th17 cell differentiation. These results systematically uncovered the role and mechanism of adiponectin on pathogenic Th17 cells and suggested that adiponectin could inhibit Th17 cell-mediated autoimmune CNS inflammation.

Comparison of sensory and compositions of five selected persimmon cultivars (Diospyros kaki L.) and correlations between chemical components and processing characteristics.

Persimmon is one of the most popular and valuable fruits in markets because of its distinguished flavor as well as its significant benefits to health. The present study systematically compared the sensory characteristics and chemical compositions of five commercial persimmon fruits, and the correlations between chemical components and processing characteristics were also included. Our results showed that obvious differences in aroma and taste were found among the cultivars. Likewise, the contents of chemical components including sugar, total phenol, ß-carotene and ascorbic acid, varied significantly (p < 0.05) across different persimmon cultivars. The processing characteristics of persimmon fruit closely correlated with the chemical compositions. Pectin (r = 0.76, p < 0.01) and total phenol (r = 0.576, p < 0.05) were found to enhance the viscosity of persimmon pulp, and the colour of persimmon powder was greatly influenced by ß-carotene, ascorbic acid and sugar contents (r = 0.823, -0.729 and -0.685, p < 0.01, respectively). Powder recovery of persimmon was positively correlated with pectin content (r = 0.503, p < 0.05) and negatively related to total sugar content (r = -0.668, p < 0.01). Pectin content exerted positive effect (r = 0.719, p < 0.01) on hygroscopicity of persimmon powder, and the powder solubility showed a positive correlation to sugar and a negative relationship to pectin contents (r = 0.662 and -0.716, p < 0.01, respectively). In addition, a positive correlation (r = 0.642, p < 0.01) of the content of ascorbic acid to phenolic retention was also observed.