Visualizing the structural and chemical heterogeneity of fruit and vegetables using advanced imaging techniques: fundamentals, instrumental aspects, applications and future perspectives.

Fruit and vegetables (F&V) are vastly complicated products with highly diverse chemical and structural characteristics. Advanced imaging techniques either combine imaging with spectral information or can provide excellent tissue penetration, and enable the possibility to target, visualize and even qualify the chemical and physical (structural) heterogeneity within F&V. In this review, visible and/or near infrared hyperspectral imaging, Fourier transform infrared microspectroscopic imaging, Raman imaging, X-ray and magnetic resonance imaging to reveal chemical and structural information in a spatial context of F&V at the macro- (entire products), meso- (tissues), and micro- (individual cells) scales are comprehensively summarized. In addition, their basic concepts and operational procedures, particularly sample preparation and instrumental parameter adjustments, are addressed. Finally, future challenges and perspectives of these techniques are put forward. These imaging techniques are powerful tools to assess the biochemical and structural heterogeneity of F&V. Cost reduction, sensor fusion and data sharing platforms are future trends. More emphasis on aspects of knowledge and extension at the level of academia and research, especially on how to select techniques, choose operational parameters and prepare samples, are important to overcome barriers for the wider adoption of these techniques to improve the evaluation of F&V quality.

Hyperspectral imaging reveals chemical heterogeneity of fruit and vegetables.Imaging techniques provide spatial insights in fruit and vegetables at multiple scales.Future trends are cost reduction, sensor fusion and data sharing.Instrumental adjustment and sample preparation should receive more attention.

A-type proanthocyanidins: Sources, structure, bioactivity, processing, nutrition, and potential applications.

A-type proanthocyanidins (PAs) are a subgroup of PAs that differ from B-type PAs by the presence of an ether bond between two consecutive constitutive units. This additional C-O-C bond gives them a more stable and hydrophobic character. They are of increasing interest due to their potential multiple nutritional effects with low toxicity in food processing and supplement development. They have been identified in several plants. However, the role of A-type PAs, especially their complex polymeric form (degree of polymerization and linkage), has not been specifically discussed and explored. Therefore, recent advances in the physicochemical and structural changes of A-type PAs and their functional properties during extraction, processing, and storing are evaluated. In addition, discussions on the sources, structures, bioactivities, potential applications in the food industry, and future research trends of their derivatives are highlighted. Litchis, cranberries, avocados, and persimmons are all favorable plant sources. Α-type PAs contribute directly or indirectly to human nutrition via the regulation of different degrees of polymerization and bonding types. Thermal processing could have a negative impact on the amount and structure of A-type PAs in the food matrix. More attention should be focused on nonthermal technologies that could better preserve their architecture and structure. The diversity and complexity of these compounds, as well as the difficulty in isolating and purifying natural A-type PAs, remain obstacles to their further applications. A-type PAs have received widespread acceptance and attention in the food industry but have not yet achieved their maximum potential for the future of food. Further research and development are therefore needed.

Plant leaf proanthocyanidins: from agricultural production by-products to potential bioactive molecules.

Proanthocyanidins (PAs) are a class of polymers composed of flavan-3-ol units that have a variety of bioactivities, and could be applied as natural biologics in food, pharmaceuticals, and cosmetics. PAs are widely found in fruit and vegetables (F&Vegs) and are generally extracted from their flesh and peel. To reduce the cost of extraction and increase the number of commercially viable sources of PAs, it is possible to exploit the by-products of plants. Leaves are major by-products of agricultural production of F&Vegs, and although their share has not been accurately quantified. They make up no less than 20% of the plant and leaves might be an interesting resource at different stages during production and processing. The specific structural PAs in the leaves of various plants are easily overlooked and are notably characterized by their stable content and degree of polymerization. This review examines the existing data on the effects of various factors (e.g. processing conditions, and environment, climate, species, and maturity) on the content and structure of leaf PAs, and highlights their bioactivity (e.g. antioxidant, anti-inflammatory, antibacterial, anticancer, and anti-obesity activity), as well as their interactions with gut microbiota and other biomolecules (e.g. polysaccharides and proteins). Future research is also needed to focus on their precise extraction, bioactivity of high-polymer native or modified PAs and better application type.

The Leaf proanthocyanidins (LPAs) are mostly oligomeric procyanidins, with a small proportion of leaves containing A-type procyanidins.Foliage is a sustainable source of PAs.LPAs are a potential source of valuable bioactive compounds.The content, structure, extraction and identification and bio-activity of LPAs are discussed.Processing improvement is beneficial to enhance the production of LPA.

Advances in green solvents for production of polysaccharide-based packaging films: Insights of ionic liquids and deep eutectic solvents.

The problems with plastic materials and the good film-forming properties of polysaccharides motivated research in the development of polysaccharide-based films. In the last 5 years, there has been an explosion of publications on using green solvents, including ionic liquids (ILs), and deep eutectic solvents (DESs) as candidates to substitute the conventional solvents/plasticizers for preparations of desired polysaccharide-based films. This review summarizes related properties and recovery of ILs and DESs, a series of green preparation strategies (including pretreatment solvents/reaction media, ILs/DESs as components, extraction solvents of bioactive compounds added into films), and inherent properties of polysaccharide-based films with/without ILs and DESs. Major reported advantages of these new solvents are high dissolving capacity of certain ILs/DESs for polysaccharides (i.e., up to 30 wt% for cellulose) and better plasticizing ability than traditional plasticizers. In addition, they frequently display intrinsic antioxidant and antibacterial activities that facilitate ILs/DESs applications in the processing of polysaccharide-based films (especially active food packaging films). ILs/DESs in the film could also be further recycled by water or ethanol/methanol treatment followed by drying/evaporation. One particularly promising approach is to use bioactive cholinium-based ILs and DESs with good safety and plasticizing ability to improve the functional properties of prepared films. Whole extracts by ILs/DESs from various byproducts can also be directly used in films without separation/polishing of compounds from the extracting agents. Scaling-up, including costs and environmental footprint, as well as the safety and applications in real foods of polysaccharide-based film with ILs/DESs (extracts) deserves more studies.

Reactivity of flavanols: Their fate in physical food processing and recent advances in their analysis by depolymerization.

Flavanols, a subgroup of polyphenols, are secondary metabolites with antioxidant properties naturally produced in various plants (e.g., green tea, cocoa, grapes, and apples); they are a major polyphenol class in human foods and beverages, and have recognized effect on maintaining human health. Therefore, it is necessary to evaluate their changes (i.e., oxidation, polymerization, degradation, and epimerization) during various physical processing (i.e., heating, drying, mechanical shearing, high-pressure, ultrasound, and radiation) to improve the nutritional value of food products. However, the roles of flavanols, in particular for their polymerized forms, are often underestimated, for a large part because of analytical challenges: they are difficult to extract quantitatively, and their quantification demands chemical reactions. This review examines the existing data on the effects of different physical processing techniques on the content of flavanols and highlights the changes in epimerization and degree of polymerization, as well as some of the latest acidolysis methods for proanthocyanidin characterization and quantification. More and more evidence show that physical processing can affect content but also modify the structure of flavanols by promoting a series of internal reactions. The most important reactivity of flavanols in processing includes oxidative coupling and rearrangements, chain cleavage, structural rearrangements (e.g., polymerization, degradation, and epimerization), and addition to other macromolecules, that is, proteins and polysaccharides. Some acidolysis methods for the analysis of polymeric proanthocyanidins have been updated, which has contributed to complete analysis of proanthocyanidin structures in particular regarding their proportion of A-type proanthocyanidins and their degree of polymerization in various plants. However, future research is also needed to better extract and characterize high-polymer proanthocyanidins, whether in their native or modified forms.

Interactions between cell wall polysaccharides and polyphenols: Effect of molecular internal structure.

Cell wall polysaccharides (CPSs) and polyphenols are major constituents of the dietary fiber complex in plant-based foods. Their digestion (by gut microbiota) and bioefficacy depend not only on their structure and quantity, but also on their intermolecular interactions. The composition and structure of these compounds vary with their dietary source (i.e., fruit or vegetable of origin) and can be further modified by food processing. Various components and structures of CPSs and polyphenols have been observed to demonstrate common and characteristic behaviors during interactions. However, at a fundamental level, the mechanisms that ultimately drive these interactions are still not fully understood. This review summarizes the current state of knowledge on the internal factors that influence CPS-polyphenol interactions, describes the different ways in which these interactions can be mediated by molecular composition or structure, and introduces the main methods for the analysis of these interactions, as well as the mechanisms involved. Furthermore, a comprehensive overview is provided of recent key findings in the area of CPS-polyphenol interactions. It is becoming clear that these interactions are shaped by a multitude of factors, the most important of which are the physicochemical properties of the partners: their morphology (surface area and porosity/pore shape), chemical composition (sugar ratio, solubility, and non-sugar components), and molecular architecture (molecular weight, degree of esterification, functional groups, and conformation). An improved understanding of the molecular mechanisms that drive interactions between CPSs and polyphenols may allow us to better establish a bridge between food processing and the bioavailability of colonic fermentation products from CPSs and antioxidant polyphenols, which could ultimately lead to the development of new guidelines for the design of healthier and more nutritious foods.

Unraveling the pectinolytic function of Bacteroides xylanisolvens using a RNA-seq approach and mutagenesis.

BACKGROUND: Diet and particularly dietary fibres have an impact on the gut microbiome and play an important role in human health and disease. Pectin is a highly consumed dietary fibre found in fruits and vegetables and is also a widely used additive in the food industry. Yet there is no information on the effect of pectin on the human gut microbiome. Likewise, little is known on gut pectinolytic bacteria and their enzyme systems. This study was undertaken to investigate the mechanisms of pectin degradation by the prominent human gut symbiont Bacteroides xylanisolvens. RESULTS: Transcriptomic analyses of B. xylanisolvens XB1A grown on citrus and apple pectins at mid- and late-log phases highlighted six polysaccharide utilization loci (PUL) that were overexpressed on pectin relative to glucose. The PUL numbers used in this report are those given by Terrapon et al. (Bioinformatics 31(5):647-55, 2015) and found in the PUL database: http://www.cazy.org/PULDB/. Based on their CAZyme composition, we propose that PUL 49 and 50, the most overexpressed PULs on both pectins and at both growth phases, are involved in homogalacturonan (HG) and type I rhamnogalacturonan (RGI) degradation, respectively. PUL 13 and PUL 2 could be involved in the degradation of arabinose-containing side chains and of type II rhamnogalacturonan (RGII), respectively. Considering that HG is the most abundant moiety (>70%) within pectin, the importance of PUL 49 was further investigated by insertion mutagenesis into the susC-like gene. The insertion blocked transcription of the susC-like and the two downstream genes (susD-like/FnIII). The mutant showed strong growth reduction, thus confirming that PUL 49 plays a major role in pectin degradation. CONCLUSION: This study shows the existence of six PULs devoted to pectin degradation by B. xylanisolvens, one of them being particularly important in this function. Hence, this species deploys a very complex enzymatic machinery that probably reflects the structural complexity of pectin. Our findings also highlight the metabolic plasticity of B. xylanisolvens towards dietary fibres that contributes to its competitive fitness within the human gut ecosystem. Wider functional and ecological studies are needed to understand how dietary fibers and especially plant cell wall polysaccharides drive the composition and metabolism of the fibrolytic and non-fibrolytic community within the gut microbial ecosystem.

Folates in Fruits and Vegetables: Contents, Processing, and Stability.

Folates play a key role in human one-carbon metabolism and are provided by food. It is well established that folates are beneficial in the prevention of neural tube defects and cardiovascular and neurodegenerative diseases. Fruits and vegetables, and especially green vegetables, are the main sources of folates. In parallel, fruits and vegetables, with high contents of folates, are mostly consumed after processing, such as, canning, freezing, or home-cooking, which involve folate losses during their preparation. Hence, it is important to know the percentage of folate losses during processing and, moreover, the mechanisms underlying those losses. The current knowledge on folate losses from fruit and vegetables are presented in this review. They depend on the nature of the respective fruit or vegetable and the respective treatment. For example, steaming involves almost no folate losses in contrast to boiling. Two main mechanisms are involved in folate losses: (i) leaching into the surrounding liquid and (ii) oxidation during heat treatment, the latter of which depending on the nature of the vitamer considered. In this respect, a vitamer stability decreases in the order starting from folic acid followed by 5-HCO-H4 folate, 5-CH3 -H4 folate, and, finally, H4 folate. Further studies are required, especially on the diffusion of the vitamers in real foods and on the determination of folate degradation products.

Determination of the composition in sugars and organic acids in peach using mid infrared spectroscopy: comparison of prediction results according to data sets and different reference methods.

The prediction of internal quality properties, such as sweetness and acidity, in peach fruit by mid infrared spectroscopy is of interest for rapid determination. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was tested here on two populations of peach fruits issued from contrasting genitors providing a large phenotypic variability. Over two successive years, 284 samples in 2006 and 483 samples in 2007 were characterized for soluble solids content (SSC), titratable acidity (TA), glucose, fructose, sucrose, malic acid, and citric acid contents. Sugar and organic acid composition were determined by three methods: colorimetric enzymatic measurements (ENZ), high-performance liquid chromatography (HPLC), or proton NMR spectroscopy ((1)H NMR), depending on the samples. For all samples, fruit homogenates were analyzed in ATR-FTIR using the same methodology and the same spectrometer. The objective here was to evaluate the effect of reference methods on the prediction performance. The best results were generally observed for SSC and TA, the percentage of the root-mean-square error of cross validation (RMSECV%) ranging respectively between 5.8% and 8.7% and between 5.9% and 8.0%, depending on the samples. For individual sugars and organic acids, the best correlations were obtained between ATR-FTIR data and ENZ reference data followed by HPLC and (1)H NMR ones.

Interactions between pectic compounds and procyanidins are influenced by methylation degree and chain length.

The interactions between procyanidins and pectic compounds are of importance in food chemistry. Procyanidins with low (9) and high (30) average degrees of polymerization (DP9 and DP30) were extracted from two cider apple varieties. Commercial apple and citrus pectins, as well as three pectin subfractions (homogalacturonans, partially methylated homogalacturonans with degree of methylation 30 and 70) at 30 mM galacturonic acid equivalent, were titrated with the two procyanidin fractions (at 30 mM (-)-epicatechin equivalent) by isothermal titration calorimetry and UV-vis spectrophotometry. Slightly stronger affinities were recorded between commercial apple or citrus pectins and procyanidins of DP30 (Ka = 1460 and 1225 M(-1) respectively, expressed per monomer units) compared to procyanidins of DP9 (Ka = 1240 and 1085 M(-1), respectively), but stoichiometry and absorbance maxima differed between apple and citrus pectins. It was proposed that methylated homogalacturonans interacted with procyanidins DP30 mainly through hydrophobic interactions. The stronger association was obtained with the longer procyanidin molecules interacting with highly methylated pectins.

Fate of Amadori compounds in processing and digestion of multi-ingredients tomato based sauces and their effect on other microconstituents.

Amadori compounds (ACs), the first stable products of Maillard reaction, are detected in various products of fruits and vegetables, and show an antioxidant activity which can be related to beneficial effects in human health. In order to optimize the nutritional quality of a multi-ingredient tomato sauce (tomato puree - onion - olive oil - dried pepper), the fate of ACs during processing (drying, heating) and gastrointestinal digestion of a model meal was assessed as well as that of other microconstituents, i.e. carotenoids, phenolic compounds and capsaicinoids. The drying at 50 °C of fresh pepper induced the formation and accumulation of ACs after 6 days. During the heat treatment by microwave of multi-ingredient tomato sauce, Maillard reaction occurs in presence of dried pepper and the content in ACs in the tomato-based sauces increased (+33% to + 53%) depending of quantities of dried pepper added. The bioaccessibility of total ACs was 24-31% in duodenal phase and 18-22% in jejunal phase. Individual ACs have shown variable bioaccessibility, e.g. very high for Fru-Arg (50.8% to 71.3%), and very low for Fru-Met (1.8% to 2.2%). The kinetic monitoring of ACs in digestion medium showed that ACs are not stable (-46% in gastric phase, -49 % in intestinal phase) which indicated their potential degradation in the digestive tract. The presence of ACs in the multi-ingredients tomato sauces had no effect on the content of the other bioactive compounds monitored in the study and even promoted the bioaccessibility of total lycopene (+30%) but decreased the bioaccessibility of total phenolic compounds.

Fruit variability impacts puree quality: Assessment on individually processed apples using the visible and near infrared spectroscopy.

This study was designed to have the absolute definition of 'one apple to one puree', which gave a first insight into the impacts of fruit inter-variability (between varieties) and intra-variability (between individual fruits) on the quality of processed purees. Both the inter-variability of apple varieties and the intra-variability of single apples induced intensive changes of appearance, chemical and textural properties of their corresponding microwave-cooked purees. The intra-variability of cooked purees was different according to apple cultivars. Some strong correlations of visible-near infrared (VIS-NIR) spectra were observed between fresh and cooked apples, particularly in the regions 665-685 nm and 1125-1400 nm. These correlations allowed then the indirect predictions of puree color (a* and b*, RPD ≧ 2.1), viscosity (RPD ≧ 2.3), soluble solids content (SSC, RPD = 2.1), titratable acidity (RPD = 2.8), and pH (RPD = 2.5) from the non-destructive acquired VIS-NIR spectra of raw apples.

Experimental and theoretical investigation on interactions between xylose-containing hemicelluloses and procyanidins.

During processing of plant-based foods, cell wall polysaccharides and polyphenols, such as procyanidins, interact extensively, thereby affecting their physicochemical properties along with their potential health effects. Although hemicelluloses are second only to pectins in affinity for procyanidins in cell walls, a detailed study of their interactions lacks. We investigated the interactions between representative xylose-containing water-soluble hemicelluloses and procyanidins. Turbidity, ITC and DLS were used to determine the relative affinities, and theoretical calculations further ascertained the interactions mechanisms. Xyloglucan and xylan exhibited respectively the strongest and weakest interactions with procyanidins. The different arabinoxylans interacted with procyanidins in a similar strength, intermediate between xyloglucans and xylans. Therefore, the strength of the interaction depended on the structure itself rather than on some incidental properties, e.g., viscosity and molar mass. The arabinose side-chain of arabinoxylan did not inhibit interactions. The computational investigation corroborated the experimental results in that the region of interaction between xyloglucan and procyanidins was significantly wider than that of other hemicelluloses.

Revisiting the contribution of ATR-FTIR spectroscopy to characterize plant cell wall polysaccharides.

The contribution of ATR-FTIR spectroscopy to study cell wall polysaccharides (CWPs) was carefully investigated. The region 1800-800 cm-1 was exploited using principal component analysis and hierarchical clustering on a large range of different powders of CWPs based on their precise chemical characterization. Relevant wavenumbers were highlighted for each CWP: 1035 cm-1 was attributed to xylose-containing hemicelluloses, 1065 and 807 cm-1 to mannose-containing hemicelluloses, 988 cm-1 to cellulose, 1740 and 1600 cm-1 to homogalacturonans according to the degree of methylation. Some band positions were affected by macromolecular arrangements (especially hemicellulose-cellulose interactions). However, as arabinan and galactan did not reveal distinctive absorption bands, ATR-FTIR spectroscopy did not allow the discrimination of cell walls differing by the abundance of these polysaccharides, e.g., those extracted from apple and beet. Therefore, the application of ATR-FTIR could remain sometimes limited due to the complexity of overlapping spectra bands and vibrational coupling from the large diversity of CWP chemical bonds.

Mid-infrared technique to forecast cooked puree properties from raw apples: A potential strategy towards sustainability and precision processing.

The potential of MIRS was investigated to: i) differentiate cooked purees issued from different apples and process conditions, and ii) predict the puree quality characteristics from the spectra of homogenized raw apples. Partial least squares (PLS) regression was tested both, on the real spectra of cooked purees and their reconstructed spectra calculated from the spectra of homogenized raw apples by direct standardization. The cooked purees were well-classified according to apple thinning practices and cold storage durations, and to different heating and grinding conditions. PLS models using the spectra of homogenized raw apples can anticipate the titratable acidity (the residual predictive deviation (RPD) = 2.9), soluble solid content (RPD = 2.8), particle averaged size (RPD = 2.6) and viscosity (RPD ≥ 2.5) of cooked purees. MIR technique can provide sustainable evaluations of puree quality, and even forecast texture and taste of purees based on the prior information of raw materials.

Changes in cell wall neutral sugar composition related to pectinolytic enzyme activities and intra-flesh textural property during ripening of ten apricot clones.

The changes of texture and cell wall characteristics of apricot were investigated in ten clones at two maturity stages. Fruit firmness, cell wall composition and enzyme activity of three apricot flesh zones were analysed. The AIS (alcohol-insoluble solids) were characterised by high amounts of uronic acid (179-300 mg g-1 AIS) and relatively high amounts of cellulosic glucose (118-214 mg g-1 AIS). The methylesterification degree varied significantly among the different clones ranging from 58 to 97 in Ab 5 and Mans 15 respectively. Conversely to zones firmness, enzymatic activity was higher in pistil followed by equatorial and peduncle zones. The ripening effect has been observed in firmness evolution according to enzymatic activity. This correlation allowed a classification of clones depending on softening. Among studied clones, Ab 5, Marouch 16, Mans 15 and Cg 2 were less influenced by softening and have the advantage of a technological valorisation for the processing industry.

A new application of NIR spectroscopy to describe and predict purees quality from the non-destructive apple measurements.

The potential of NIRS was investigated on both apples and purees to (i) examine factors involving quality variability (variety, agricultural practice, cold storage, puree mechanical refining level) and (ii) establish the link between quality traits before and after processing in order to predict the quality characteristics of purees from spectral information of raw apples. Apples and purees were well-classified at over 82% and 88% according to varieties and storage times respectively. The PLS models showed a good ability to estimate puree characteristics from spectra acquired on corresponding apples such as viscosity (R2 > 0.82), cell wall content (R2 > 0.81) and also dry matter (R2 > 0.83), soluble solids content (R2 > 0.80) and titratable acidity (R2 > 0.80). NIR technique should be a useful tool for industry insofar as it can give a reliable assessment of texture and taste of the final products based on the non-destructive fresh materials evaluation.

Multiscale Localization of Procyanidins in Ripe and Overripe Perry Pears by Light and Transmission Electron Microscopy.

Histochemical staining with 4-dimethylaminocinnamaldehyde (DMACA), light microscopy, and transmission electron microscopy (TEM) were applied to characterize procyanidin localization at ripe and overripe stages in perry pear flesh (cv. 'De Cloche'). Pear flesh contained stone cell clusters surrounded by very large parenchyma cells. DMACA staining showed procyanidins mainly located in parenchyma cells from the fruit mesocarp. Under light microscopy and TEM, procyanidins appeared in the vacuole of parenchyma cells as uniformly stained granules, probably tannosomes. They were differently dispersed in ripe and overripe perry pears, as the granules remained free inside the vacuole in ripe pears and mostly attached to the tonoplast in overripe pears.

Impact of onions in tomato-based sauces on isomerization and bioaccessibility of colorless carotenes: phytoene and phytofluene.

Onions as an interesting ingredient have been proved to promote Z-isomerization of lycopene and increase bioaccessibility of total-lycopene. Phytoene (PT) and phytofluene (PTF), the precursors of lycopene, are colorless carotenes, which are attracting much attention and are also abundant in tomatoes. Therefore, onions might also affect the distribution and bioaccessibility of PT and PTF isomers during heating tomato (hot-break and cold-break purees)-onion-extra virgin olive oil (EVOO) sauces. The addition of onions (or diallyl disulfide present in onions) into tomato purees did not cause degradation of PT or PTF; however it favored E/Z-isomerization of PT and PTF by reducing the proportions of their natural Z-isomers (Z-15-PT and Z2,3-PTF) and decreased the bioaccessibility of total-PT and total-PTF. Simultaneously, a complex picture was obtained for the effect of onions on the bioaccessibility of individual PT and PTF isomers, depending on the precise isomer. Bioaccessibility of PT and PTF isomers in tomato-based sauces decreased in the order: 15-Z-PT > all-E-PT; Z2,3-PTF > all-E-PTF > Z4 or Z5-PTF; total-PT > total-PTF. E-isomerization of PT and PTF enhanced by onions during heating tomato-onion purees decreased their bioaccessibility.