Pectin forms polymeric pigments by complexing anthocyanins during red winemaking and ageing.

The long-term stability of red wine color depends on the formation of polymeric pigments from anthocyanins. Although there is still a lot of uncertainty about the specific structure of this diverse group of pigments, there is consensus that they are reaction products of anthocyanins and other polyphenols. Interactions between anthocyanins and pectic polysaccharides have been suggested to stabilize anthocyanins. This study explores the impact of such interactions by adding pectin during red winemaking. The results demonstrate that these interactions induce the formation of additional polymeric pigments which enhance the pigment stability during fermentation and aging. While initial pigment formation is higher in wines with added pectin, a notable proportion of the complexes degrades in the later stages of fermentation. Presumably, tannins form insoluble complexes with pectin, reducing tannin concentration by more than 300 mg/L. Anthocyanin concentrations decrease by over 400 mg/L, and polymeric pigments double. Anthocyanins that form polymeric pigments with pectic polysaccharides expand the range of pigments in red wines with possible consequences for the sensory properties of the wine. These findings highlight the complex interactions between pectin, anthocyanins, and tannins, and their influence on pigment formation and wine composition during fermentation and aging.

Influence of Potential Alcohol in Grapes on Phenolic and Sensory Characteristics of Red Wine.

Potential alcohol, as obtained by grape maturity, affects the extraction of phenolics during winemaking. The extent to which potential alcohol is correlated to phenolic and sensory characteristics of red wine was investigated. Decoupling of the ripening kinetics of grape constituents due to climate change emphasizes this question. The impact of potential alcohol, as naturally obtained by grape maturity or adjusted by sugar addition, representing high sugar but low phenolic maturity, on wine characteristics was investigated for two varieties over two vintages. Enhancement of potential alcohol to late harvest conditions did not achieve the sensory characteristics of wine made from phenolic mature grapes. An experimental model was developed revealing the contribution of potential alcohol to phenolic and sensory characteristics. In Pinot noir, anthocyanins correlated well with natural potential alcohol but were not influenced by enhanced potential alcohol. In Cabernet Sauvignon, polymeric pigments provided the most accurate information about grape maturity perception in wine.

Toward gentle chokeberry juice production by ultrasound-assisted enzymatic maceration.

Sustainable processes accompanied by high extraction yields and minimized amounts of by-products are a major goal of current fruit juice production. Controlled degradation of cell wall polysaccharides, in particular pectin, may contribute to reduced emergence of side streams. Possible strategies for the optimization are the selection of enzyme preparations based on comprehensive studies of their activities, the adjustment of maceration temperature toward more gentle conditions, and the application of alternative technologies such as ultrasound (US) during maceration. The present study provides insights into the effects of ultrasound-assisted enzymatic maceration (UAEM) on pectin degradation, total anthocyanin content, thermal and storage stability, and juice yield during chokeberry juice production on pilot-plant scale. The two enzyme preparations applied predominantly possessed polygalacturonase or pectin lyase activity. Cell wall polysaccharide degradation was improved by US and resulted in a 3% increase in juice yield by UAEM using an enzyme preparation that shows mostly polygalacturonase activity. Thermostability of anthocyanins was improved in juices produced using pectin lyase and applying US and matched the stability of anthocyanins in juices produced using polygalacturonase. Storage stability of anthocyanins was improved in juice produced using polygalacturonase during UAEM. UAEM also resulted in lower yields of pomace making the production more resource-efficient. Overall, the use of polygalacturonase has promising potential to advance conventional chokeberry juice production by applying US at gentle conditions.

StressLife: A Short-Time Approach for the Determination of a Trend S-N Curve in and beyond the HCF Regime for the Steels 20MnMoNi5-5 and SAE 1045.

Within the scope of this research, a new short-time procedure designated as StressLifeHCF was developed. Through a combination of classic fatigue testing and non-destructive monitoring of the material response due to cyclic loading, a process-oriented fatigue life determination can be carried out. A total of two load increases and two constant amplitude tests are required for this procedure. By using data from non-destructive measurements, the parameters of the elastic approach according to Basquin and the plastic approach according to Manson-Coffin were determined and combined within the StressLifeHCF calculation. Furthermore, two additional variations of the StressLifeHCF method were developed in order to be able to accurately describe the S-N curve over a wider range. The main focus of this research was 20MnMoNi5-5 steel, which is a ferritic-bainitic steel (1.6310). This steel is widely used for spraylines in German nuclear power plants. In order to validate the findings, tests were also performed on an SAE 1045 steel (1.1191).

Generation and structure elucidation of a red colorant formed by oxidative coupling of chlorogenic acid and tryptophan.

In view of the poor acceptance of synthetic food colorants by consumers, there is intense interest in novel natural compounds, preferably from plant-derived sources. We oxidized chlorogenic acid using NaIO4 and reacted the resultant quinone with tryptophan (Trp) to obtain a red-colored product. The colorant was precipitated, freeze-dried, purified by size exclusion chromatography, and subsequently characterized using UHPLC-MS, high-resolution mass spectrometry, and NMR spectroscopy. Additional mass spectrometric studies were performed on the reaction product generated with Trp educts labeled with 15N and 13C. The data obtained from these studies allowed the identification of a complex compound consisting of two Trp and one caffeic acid moieties, and the proposition of a tentative pathway of its formation. Thus, the present investigation expands our knowledge about the formation of red colorants based on the reaction of plant phenols and amino acids.

Grape-derived pectic polysaccharides alter the tannin and pigment composition of Cabernet Sauvignon red wines.

Tannins, anthocyanins, and polymeric pigments are essential phenolic constituents of red wine because they provide color, color stability, and mouthfeel properties like astringency. The behavior of these compounds is significantly affected by pectic polysaccharides, whereby the extent of their influence on red wine quality depends on their structural features and their interactions with the polyphenols. In the present study, the composition of the pectic polysaccharides of commercially available Cabernet Sauvignon wines and their impact on anthocyanin, tannin, and polymeric pigment analyses was characterized. This was accomplished by preparation of polysaccharide deprived wines and comparison of the polyphenolic composition of both, the wines and their corresponding polysaccharide-free counterparts. The results show that the cell wall fragments enhance the spectral absorbance of anthocyanins by facilitating anthocyanin self-association, leading to a co-pigmentation-like effect. Low molecular weight pectins like rhamnogalacturonan II and polygalacturonic acids with a low degree of esterification are assumed to form soluble complexes with anthocyanins and also prevent protein precipitation of tannins, which was reduced by 6-13%. High molecular weight pectins with a high degree of esterification lead to the increased precipitability of pigments and tannins by a factor of 1.3 to 32.4 and 1.1 to 1.9, respectively, seemingly impairing the incorporation of anthocyanins in tannins to form precipitable polymeric pigments that are responsible for the longevity of red wine color. The increased precipitability of the pigments due to the interactions with the polysaccharides may indicate the formation of pigmented yet non-covalent aggregates that show comparable properties to the covalently formed precipitable pigments. The formation of those non-covalent structures may affect red wine color stability and astringency.

Effects of flavonoids on membrane adaptation of food-associated bacteria.

The effects of naringenin and the biflavonoids amentoflavone and tetrahydroamentoflavone on select bacterial lipids (carotenoids, fatty acids, and menaquinones) and membrane fluidity based on Laurdan generalized polarization were investigated. For this purpose, the pigment-forming food-associated microorganisms Staphylococcus xylosus (DSM 20266T and J70), Staphylococcus carnosus DSM 20501T, and Micrococcus luteus (ATCC 9341 and J3) were studied. The results suggest an envelope stress response by microorganisms due to flavonoids and an employment of adaptive mechanisms using carotenoids, fatty acids, and menaquinones. The flavonoid monomer naringenin impacted carotenoids, fatty acids, menaquinones, and membrane fluidity. Naringenin significantly influenced the carotenoid profile, particularly by an increase in the relative proportion of 4,4'-diaponeurosporenoic acid in Staphylococcus xylosus. Amentoflavone caused changes mainly in the membrane of Micrococcus luteus and decreased the menaquinone content. Tetrahydroamentoflavone mainly affected the carotenoids in the investigated strains. The noticeably different CCS value of tetrahydroamentoflavone compared to naringenin and amentoflavone revealed further insights into the structure-dependent effects of flavonoids. This study provides valuable insights into the response of pigment-forming food-associated microorganisms to naringenin, amentoflavone, and tetrahydroamentoflavone, which is important for the targeted and safe application of the latter as natural preservatives and useful for further research on the mechanisms of action.

On donor-acceptor-bridging intramolecular hydrogen bonds in NIR-TADF molecules.

Following a report that highlights the importance of intramolecular hydrogen bonds for improved NIR-TADF efficiency in CAT-1 [Leng et al., J. Phys Chem. A, 2021, 125, 2905], an intramolecularly doubly hydrogen-bonded base design is investigated and compared to singly and non-bonded derivatives. It is found that the potential to form more intramolecular hydrogen bonds correlates with decreasing internal reorganization energies in most of the designed structures. In addition, our proposed base design facilitates the desired interlocking of charge transfer donor-, linker- and acceptor-planes through steric gauche-interactions to both linker-plane sides, allowing to trap also smaller heterocyclic linkers.

Influence of Grape Cell Wall Polysaccharides on the Extraction of Polyphenols during Fermentation in Microvinifications.

Grape cell wall polysaccharides influence the extraction of phenolic compounds during winemaking and consequently polyphenol concentrations in the final wine. During ripening, both compound groups undergo pronounced structural and compositional changes, resulting in a dynamic change of extractability. Grape cell wall polysaccharides from different ripe grapes were added to fermentations of Cabernet Sauvignon and Pinot noir grapes. Polyphenol-polysaccharide interactions affected the concentrations of tannins and monomeric flavanols in the wines depending on the maturity of the added polysaccharides. With higher polysaccharide maturity, the effects became more pronounced. Polysaccharides protected monomeric flavanols and tannin in Pinot noir, thereby increasing the concentrations, but they precipitated or masked these compounds in Cabernet Sauvignon. The added polysaccharides affected the concentrations in anthocyanins and polymeric pigments much less compared to the ripening status of the grapes. It was concluded that structural changes of polysaccharides during ripening affect the extraction of tannins and monomeric flavanols the most.

Real-Time Spiral CMR Is Superior to Conventional Segmented Cine-Imaging for Left-Ventricular Functional Assessment in Patients with Arrhythmia.

(1) Background: Segmented Cartesian Cardiovascular magnetic resonance (CMR) often fails to deliver robust assessment of cardiac function in patients with arrhythmia. We aimed to assess the performance of a tiny golden-angle spiral real-time CMR sequence at 1.5 T for left-ventricular (LV) volumetry in patients with irregular heart rhythm; (2) Methods: We validated the real-time sequence against the standard breath-hold segmented Cartesian sequence in 32 patients, of whom 11 presented with arrhythmia. End-diastolic volume (EDV), end-systolic volume (ESV), stroke volume (SV), and ejection fraction (EF) were assessed. In arrhythmic patients, real-time and standard Cartesian acquisitions were compared against a reference echocardiographic modality; (3) Results: In patients with sinus rhythm, good agreements and correlations were found between the segmented and real-time methods, with only minor, non-significant underestimation of EDV for the real-time sequence (135.95 ± 30 mL vs. 137.15 ± 31, p = 0.164). In patients with arrhythmia, spiral real-time CMR yielded superior image quality to the conventional segmented imaging, allowing for excellent agreement with the reference echocardiographic volumetry. In contrast, in this cohort, standard Cartesian CMR showed significant underestimation of LV-ESV (106.72 ± 63.51 mL vs. 125.47 ± 72.41 mL, p = 0.026) and overestimation of LVEF (42.96 ± 10.81% vs. 39.02 ± 11.72%, p = 0.039); (4) Conclusions: Real-time spiral CMR improves image quality in arrhythmic patients, allowing reliable assessment of LV volumetry.

Noncovalent Polyphenol-Macromolecule Interactions and Their Effects on the Sensory Properties of Foods.

Noncovalent interactions between food macromolecules like proteins and polysaccharides with polyphenols have a broad and extensive impact on the sensory properties of food. Because of the structural diversity of the interaction partners and the corresponding variety of binding mechanisms, the determination of the distinct sensorial consequences and the correlation with molecular features is complicated. Well-documented examples include the attenuation of astringency elicited by tannins in the presence of polysaccharides or the precipitation of anthocyanins by cell-wall polysaccharides during fruit juice processing. The proposed mechanism suggests that there exist additional intricate interactions including ternary complexes. The analytical characterization of the formed complexes is difficult due to the reversible nature of these interactions.

Short-Time Fatigue Life Estimation for Heat Treated Low Carbon Steels by Applying Electrical Resistance and Magnetic Barkhausen Noise.

Tensile tests and fatigue tests on differently heat-treated low carbon (non- and low-alloy) steels were conducted and accompanied by non-destructive electrical resistometric (ER) and magnetic Barkhausen noise (MBN) measuring devices, in order to establish an improved short-time fatigue life estimation method according to StressLife. MaRePLife (Material Response Partitioning) is the hereby proposed method for calculating S-N curves in the HCF regime, based on the partitioning of material responses acquired during the above-mentioned mechanical tests. The rules were set to make use of the information gathered from pre-conducted tensile tests, which helps to determine the parameters of two load increase tests (LIT) and two constant amplitude tests (CAT). The results of the calculated S-N curves were satisfactory and could be verified by more separately conducted fatigue tests on specimens under different material conditions.

Application of Crude Pomace Powder of Chokeberry, Bilberry, and Elderberry as a Coloring Foodstuff.

Berry pomace, rich in polyphenols, especially anthocyanins, accumulates during the production of red juices. Pomace from chokeberry (Aronia melanocarpa Michx.), bilberry (Vaccinium myrtillus L.), and elderberry (Sambucus nigra L.) represent good sources of coloring foodstuffs. Pomace powders (PP) were prepared by milling the seedless fractions of the three dried berry pomaces (50 °C, 8 h). Techno-functional properties of the powders such as particle size distribution, bulk density, sedimentation velocity, and swelling capacity were determined to evaluate the powders for possible food applications. Total anthocyanin content was quantified by UHPLC-DAD before and during a storage experiment to monitor the degradation of anthocyanins in the PP and in a yogurt model application. The high content of phenolic compounds and the still intact cell structure ensured high stability of anthocyanins over 28 days of storage. In the model application, color saturation was stable over the whole storage time of 14 days. Regarding the techno-functional properties, only a few differences between the three PP were observed. The particle size of elderberry PP was larger, resulting in lowest bulk density (0.45 g/mL), high cold-water solubility (16.42%), and a swelling capacity of 10.16 mL/g dw. Sedimentation velocity of the three PP was fast (0.02 mL/min) due to cluster formation of the particles caused by electrostatic and hydrophobic properties. Compared to other high-intensity coloring foodstuffs, the use of PP, showing acceptable color stability with potential health-promoting effects, represents a wide applicability in different food applications and especially in products with a longer shelf-life.

Effects of ultrasound on the enzymatic degradation of pectin.

Ultrasound-assisted enzymatic maceration (UAEM) has gained considerable interest in the fruit juice industry, owing to its potential to increase juice yield and content of polyphenols while simultaneously saving time and energy. In this study, the effects of UAEM (ultrasonic probe, 20 kHz, 21 W*cm-2 and 33 W*cm-2) on pectin degradation in a continuous circulation system were investigated over 60 and 90 min. Main pectinolytic enzymes activities of (polygalacturonase, pectin lyase and pectin methylesterase) of a commercial enzyme preparation were examined for individual synergistic effects with US. Pectin hydrolysis by UAEM differed significantly compared to treatment with ultrasound or enzymes alone regarding the profile of degradation products compared to treatment with ultrasound or enzymes alone. Ultrasound fragmented pectin to less branched oligomers of medium molecular weight (Mp approx. 150 kDa), which were further degraded by pectinolytic activities. The low molecular weight fraction (<30 kDa), which is known to be beneficial for juice-quality by adding nutritional value and stabilizing polyphenols, was enriched in small oligomers of homogalacturonan-derived, rhamnogalacturonan I-derived, and rhamnogalacturonan II-derived residues. Synergistic effects of ultrasound application enhanced the effective activities of polygalacturonase and pectin lyase and even prolonged their performance over 90 min, whereas the effective activity of pectin methylesterase was not affected. Final marker concentrations determined by each enzyme assay revealed a considerable higher total process output after UAEM treatment at reduced temperature (30 °C) comparable to the output after conventional batch maceration at 50 °C. The obtained results demonstrate the high potential of UAEM to produce high-quality juice by controlling pectin degradation while reducing process temperature and equally highlight the matrix and enzyme specific effects of a simultaneous US treatment.

HPLC-DAD-MS and Antioxidant Profile of Fractions from Amontillado Sherry Wine Obtained Using High-Speed Counter-Current Chromatography.

In the present work, the polyphenolic profile of a complex matrix such as Amontillado sherry has been processed by means of high-speed counter-current chromatography (HSCCC) and characterized by HPLC-DAD-MS. An Amberlite XAD-7 column was used to obtain the wine extract, and three different biphasic solvent systems were applied for HSCCC separation: MTBE (methyl tert-butyl ether)/n-butanol/acetonitrile/water (1.1/3/1.1/5+0.1% trifluoroacetic acid), MTBE/n-butanol/acetonitrile/water (2/2/1/5), and hexane/ethyl acetate/ethanol/water (1/5/1/5). As a result, 42 phenolic compounds and furanic derivatives have been identified by means of HPLC-DAD-MS, with 11 of them being identified for the first time in Sherry wines: 3-feruloylquinic acid, isovanillin, ethyl vanillate, furoic acid, dihydro-p-coumaric acid, 6-O-feruloylglucose, ethyl gallate, hydroxytyrosol, methyl protocatechuate, homoveratric acid and veratraldehyde. In addition, the antioxidant capacity (ABTS) of the obtained fractions was determined, revealing higher values in those fractions in which compounds such as gallic acid, protocatechuic acid, protocatechualdehyde, trans-caftaric acid, syringic acid, isovanillin or tyrosol, among others, were present. This is the first time that HSCCC has been used to characterize the phenolic composition of Sherry wines.

Profiling of phenolic compounds in desiccation-tolerant and non-desiccation-tolerant Linderniaceae.

INTRODUCTION: Craterostigma plantagineum and Lindernia brevidens are resurrection plants, so these plants can tolerate desiccation of their vegetative tissues. Different components and mechanisms contribute to desiccation tolerance and secondary plant metabolites, like phenolic compounds, may play a role during these processes. OBJECTIVES: Secondary plant metabolites of the two resurrection plants, C. plantagineum and L. brevidens as well as the closely related desiccation sensitive species, L. subracemosa, were investigated regarding the polyphenol profile. MATERIAL AND METHODS: Secondary plant compounds were extracted with acidified methanol and analysed with ultra-high-performance liquid chromatography electrospray ionisation mass spectrometry (UHPLC-ESI-MS). Phenolic compounds were identified by comparing of ultraviolet (UV) and MSn -spectra with published data. All compounds were quantified as verbascoside equivalents by external calibration at the compound specific wavelength. RESULTS: In total, eight compounds that belong to the subclass of phenylethanoid glycosides and one flavone, luteolin hexoside pentoside, were identified. Two of these compounds exhibited a fragmentation pattern, which is closely related to phenylethanoid glycosides. The predominantly synthesised phenylethanoid in all of the three plant species and in every stage of hydration was verbascoside. The total content of phenolic compounds during the three stages of hydration, untreated, desiccated, and rehydrated revealed differences especially between C. plantagineum and L. brevidens as the latter one lost almost all phenolic compounds during rehydration. CONCLUSION: The amount of verbascoside correlates with the degree of desiccation tolerance and verbascoside might play a role in the protective system in acting as an antioxidant.

Effects of carrier agents on powder properties, stability of carotenoids, and encapsulation efficiency of goldenberry (Physalis peruviana L.) powder produced by co-current spray drying.

Maltodextrin, modified starch, inulin, alginate, gum arabic, and combinations thereof were used as carrier agents for spray drying of carotenoid-rich goldenberry (Physalis peruviana L.) juice and compared to cellobiose as an alternative carrier. Powders were analyzed with respect to particle size and morphology, yield, moisture content, cold water solubility, suspension stability, hygroscopicity, carotenoid encapsulation efficiency, and carotenoid retention during storage. A high initial carotenoid concentration after spray drying, a high encapsulation efficiency of 77.2%, and a slow carotenoid degradation kinetics favored the high carotenoid content of the cellobiose powder at the end of the storage. Cellobiose might protect the carotenoids from degradation processes by light exposure, high temperature, and oxygen due to a tighter particle crust and larger particle sizes. Therefore, cellobiose may be considered a potential carrier agent for the encapsulation of carotenoid-rich fruit juices.

Impact of Different Pasteurization Techniques and Subsequent Ultrasonication on the In Vitro Bioaccessibility of Carotenoids in Valencia Orange (Citrus sinensis (L.) Osbeck) Juice.

The effects of traditional pasteurization (low pasteurization, conventional pasteurization, hot filling) and alternative pasteurization (pulsed electric fields, high pressure processing), followed by ultrasonication on the carotenoid content, carotenoid profile, and on the in vitro carotenoid bioaccessibility of orange juice were investigated. There was no significant difference in the total carotenoid content between the untreated juice (879.74 µg/100 g juice) and all pasteurized juices. Significantly lower contents of violaxanthin esters were found in the high thermally-treated juices (conventional pasteurization, hot filling) compared to the untreated juice, owing to heat-induced epoxy-furanoid rearrangement. The additional ultrasonication had almost no effects on the carotenoid content and profile of the orange juices. However, the in vitro solubilization and the micellarization efficiency were strongly increased by ultrasound, the latter by approximately 85.3-159.5%. Therefore, among the applied processing techniques, ultrasonication might be a promising technology to enhance the in vitro bioaccessibility of carotenoids and, thus, the nutritional value of orange juice.

Pecan (Carya illinoinensis (Wagenh.) K. Koch) Nut Shell as an Accessible Polyphenol Source for Active Packaging and Food Colorant Stabilization.

Herein, the antioxidant and food stabilizing properties of a pecan nut shell (PNS) hydroalcoholic extract (PNSE) are reported. Chemical degradation of PNSE demonstrated the presence of condensed tannins as the main phenolic components. PNSE showed remarkable antioxidant properties in the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay (EC50 = 0.004 mg/mL). PNSE was initially tested as an inhibitor of mushroom tyrosinase, exhibiting a quite low IC50 value (0.055 mg/mL) against the enzyme diphenolase activity, suggesting its use in enzymatic browning inhibition. The anthocyanin stabilization properties were evaluated under accelerated aging conditions of both pure pigments and commercial fruit juices, and PNSE was found to be effective at concentrations (0.05 mg/mL) at which well-known stabilizers such as chlorogenic and ferulic acids proved to fail. PNSE also performed well in the stabilization of spray-dried anthocyanins for use as a food colorant, increasing the half-life of blackberry anthocyanins up to 20%. In order to explore the possibility of using PNSE as a functional additive for active packaging, polylactic acid (PLA) films containing PNSE were prepared by solvent casting, and no substantial alteration of the mechanical properties was found on addition of the extract up to 10% w/w. The films showed remarkable antioxidant properties (DDPH reduction >60% with a 3% w/w loading, at a dose of 1 mg/mL in the DPPH solution) and delayed the onset of browning of apple smoothies (ca. 30% inhibition with a 10% w/w loading). These results highlight the exploitation of PNS as a low-cost polyphenol source for food industry applications.

Influence of Glutathione on Yeast Fermentation Efficiency under Copper Stress.

Copper in grape musts can influence the fermentation efficiency of Saccharomyces cerevisiae during winemaking. The present study revealed the impact of glutathione addition on yeast strains with variable copper sensitivity. The antioxidant glutathione increased yeast vitality and fastened sugar metabolism at copper concentrations up to 0.39 mM. A significant accumulation of acetaldehyde at high copper concentrations was mitigated by the addition of 20 mg L-1 glutathione. Low recovery of glutathione added implicated a complexation of both compounds. Specific alcohol dehydrogenase (ADH) activity was inhibited or reduced in the enzyme extracts of the copper-stressed yeast cells. The activity was restored in fermentations with glutathione at a copper concentration of 0.16 mM. At low copper concentrations, glutathione decreased ADH activity presumably due to complexation of essential copper amounts. Results provide important information on the use of glutathione as an antioxidant in winemaking to counteract negative effects of copper-rich musts on copper-sensitive yeast strains.