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.

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.

Theoretical X-ray absorption spectroscopy database analysis for oxidised 2D carbon nanomaterials.

In this work we provide a proof of principle for a theoretical methodology to identify functionalisation patterns in oxidised carbon 2D nanomaterials. The methodology is based on calculating a large number of X-ray absorption spectra of individually excited carbon atoms in different chemical environments using density functional theory. Since each resulting spectrum gives a fingerprint of the local electronic structure surrounding the excited atom, we may relate each spectrum to the functionalisation pattern of that excited atom up to a desired neighbourhood radius. These functionalisation pattern-specific spectra are collected in a database, that allows fast composition of X-ray absorption spectra for arbitrary structures in density functional theory quality. Finally, we present an exemplary application of the database approach to estimate the relative amount of functional groups in two different experimental samples of carbon nanomaterials.

Interdependence of ICD rates in paired quantum dots on geometry.

Using state-of-the-art antisymmetrized multiconfiguration time-dependent Hartree (MCTDH) electron dynamics calculations we study the interdependence of the intermolecular Coulombic decay (ICD) process on the geometric parameters of a doubly-charged paired quantum dot (PQD) model system in the framework of the effective mass approximation (EMA). We find that ICD displays a maximum rate for a certain geometry of the electron-emitting quantum dot, which is simultaneously dependent on both the distance between the quantum dots as well as the photon-absorbing quantum dot's geometry. The rate maximum is shown to be caused by the competing effects of polarization of electron density and Coulomb repulsion. The ICD rate-maximized PQD geometry in GaAs QDs yields a decay time of 102.39 ps. It is given by two vertically-aligned cylindrical QDs with radii of 14.42 nm separated by 86.62 nm. The photon absorbing QD then has a height of 46.59 nm and the electron emitting QD a height of 16.33 nm. © 2017 Wiley Periodicals, Inc.

Impact of Xanthylium Derivatives on the Color of White Wine.

Xanthylium derivatives are yellow to orange pigments with a glyoxylic acid bridge formed by dimerization of flavanols, which are built by oxidative cleavage of tartaric acid. Although their structure and formation under wine-like conditions are well established, knowledge about their color properties and their occurrence and importance in wine is deficient. Xanthylium cations and their corresponding esters were synthesized in a model wine solution and isolated via high-performance countercurrent chromatography (HPCCC) and solid phase extraction (SPE). A Three-Alternative-Forced-Choice (3-AFC) test was applied to reveal the color perception threshold of the isolated compounds in white wine. Their presence and color impact was assessed in 70 different wines (58 white and 12 rosé wines) by UHPLC-DAD-ESI-MSn and the storage stability in wine was determined. The thresholds in young Riesling wine were 0.57 mg/L (cations), 1.04 mg/L (esters) and 0.67 mg/L (1:1 (w/w) mixture), respectively. The low thresholds suggest a possible impact on white wine color, but concentrations in wines were below the threshold. The stability study showed the degradation of the compounds during storage under several conditions. Despite the low perception threshold, xanthylium derivatives might have no direct impact on white wine color, but might play a role in color formation as intermediate products in polymerization and browning.

Determination of polyphenol and crude nutrient content and nutrient digestibility of dried and ensiled white and red grape pomace cultivars.

The present study aimed to determine the nutrient and energy content of fresh and ensiled grape pomace (GP) from different grape varieties originating from Germany, and to estimate the feed value of dried white, dried red and ensiled white GP by calculating nutrient digestibility and the content of metabolisable energy (ME) and net energy lactation (NEL) measured in sheep as a ruminant model. GP from red cultivars had higher contents of organic matter (OM), crude protein (CP), ether extract (EE), crude fibre (CF), total phenolic contents (TPC) and ME, whereas the concentrations of ash and sugar were lower than from white cultivars. Compared with untreated GP, ensiled GP had increased concentrations of CP (+19%), ether extract (EE; +23%) and CF (+12%) and a higher ME content (+7%) and markedly decreased concentrations of sugar (-99.6%) and TPC (-48%). The concentrations of dry matter, OM and ash were not different between ensiled and fresh GP. Compared with dried GP, ensiled GP had a higher nutrient digestibility (OM, +32%; CP, +43%; CF, +46%; neutral detergent fibre [NDF], +54%; acid detergent fibre [ADF], +69%) and higher energy values (ME, +16%; NEL, +19%). The digestibility of OM, CP, EE and CF and the energy content were higher for dried red than for dried white GP, whereas the digestibility of NDFOM and ADFOM was lower for dried red than dried white GP. In conclusion, the results show that both red and white GP are suitable dietary sources for enrichment with TPC. Furthermore, compared with drying ensiling of GP improves the feeding value of GP and is a good possibility of preserving the seasonally produced by-product of winemaking for ruminant feeding.

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.

Curse or blessing: Growth- and laccase-modulating properties of polyphenols and their oxidized derivatives on Botrytis cinerea.

Infection of grapevines with the grey mold pathogen Botrytis cinerea results in severe problems for winemakers worldwide. Browning of wine is caused by the laccase-mediated oxidation of polyphenols. In the last decades, Botrytis management has become increasingly difficult due to the rising number of resistances and the genetic variety of Botrytis strains. During the search for sustainable fungicides, polyphenols showed great potential to inhibit fungal growth. The present study revealed two important aspects regarding the effects of grape-specific polyphenols and their polymerized oxidation products on Botrytis wild strains. On the one hand, laccase-mediated oxidized polyphenols, which resemble the products found in infected grapes, showed the same potential for inhibition of growth and laccase activity, but differed from their native forms. On the other hand, the impact of phenolic compounds on mycelial growth is not correlated to the effect on laccase activity. Instead, mycelial growth and relative specific laccase activity appear to be modulated independently. All phenolic compounds showed not only inhibitory but also inductive effects on fungal growth and/or laccase activity, an observation which is reported for the first time. The simultaneous inhibition of growth and laccase activity demonstrated may serve as a basis for the development of a natural botryticide. Yet, the results showed considerable differences between genetically distinguishable strains, impeding the use of a specific phenolic compound against the genetic variety of wild strains. The present findings might have important implications for future understanding of Botrytis cinerea infections and sustainable Botrytis management including the role of polyphenols.

Conformational analysis of δ-lactones by DFT calculations: the parent compound and its monomethyl and selected dimethyl derivatives.

The static and dynamic stereochemistry of unsubstituted δ-valerolactone, all monomethylated δ-lactones, and all nongeminally dimethylated δ-lactones was explored with the B3LYP functional and def2-TZVPP basis set. A search strategy was employed which allowed the entire conformational space of any (poly-)substituted δ-lactone to be scanned. It allowed the lowest threshold conformational interconversion pathways to be mapped. The latter can be visualized in appealingly intuitive yet unprecedented diagrams. They trace the energy versus a circular abscissa which describes the passage of the molecule through one complete conformation interchange. The respective plot is C(2)-symmetrical for the parent compound, which is achiral, and C(1)-symmetrical for all methylated δ-lactones, which are chiral.

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.

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).

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.

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.

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.

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.

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.

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.

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.

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.