Main conclusion Du ring on-tree ripening, the pectin distribution changed from polydispersed in cell wall to cumulated in cell wall corners. During apple storage, the pectin distribution returned to evenly dispersed along the cell wall. The plant cell wall influences the texture properties of fruit tissue for example apples become softer during ripening and postharvest storage. This softening process is believed to be mainly connected with changes in the cell wall composition due to polysaccharides undergoing an enzymatic degradation. These changes in polysaccharides are currently mainly investigated via chemical analysis or monoclonal labeling. Here, we propose the application of Raman microscopy for evaluating the changes in the polysaccharide distribution in the cell wall of apples during both ripening and postharvest storage. The apples were harvested 1 month and 2 weeks before optimal harvest date as well as at the optimal harvest date. The apples harvested at optimal harvest date were stored for 3 months. The Raman maps, as well as the chemical analysis were obtained for each harvest date and after 1, 2 and 3 months of storage, respectively. The analysis of the Raman maps showed that the pectins in the middle lamella and primary cell wall undergo a degradation. The changes in cellulose and hemicellulose were less pronounced. These findings were confirmed by the chemical analysis results. During development changes of pectins from a polydispersed form in the cell walls to a cumulated form in cell wall corners could be observed. In contrast after 3 months of apple storage we could observe an substantial pectin decrease. The obtained results demonstrate that Raman chemical imaging might be a very useful tool for a first identification of compositional changes in plant tissue during their development. The great advantage Raman microspectroscopy offers is the simultaneous localization and identification of polysaccharides within the cell wall and plant tissue.

The nanostructure of polysaccharides is supposed to determine properties such as stiffness or diffusivity of cell walls and their functionality for various tailored properties of food. However, at present, a relation of these nano-properties with sensory texture and firmness remains to some degree unknown. In this work, water (WSP), calcium chelator (CSP) and sodium carbonate (DASP) soluble pectins, hemicellulose and cellulose, extracted from cell walls of two pear cultivars ‘Xenia’ and ‘Conference’ at their harvest times, were studied. An atomic force microscope and image analysis were used to evaluate diameter and branching of the molecules. Sensory texture of ‘Xenia’ was considered as better and its firmness (87 N) was higher than ‘Conference’ (76 N). WSP molecules were present as short molecules with a height of about 0.5 nm for both cultivars. A chain-like and branched CSP fraction had diameter of about 0.3–0.4 nm for both cultivars with a pronounced contribution of molecules with diameter of about 1 nm for ‘Xenia’, which had also higher branching index. DASP revealed similar regular structures for both cultivars however the network was much denser for ‘Xenia’. A rod-like hemicellulose molecules had length of about 20–400 nm and diameter of 1 nm for ‘Xenia’ and 1–4 nm for ‘Conference’. Cellulose diameter for both cultivars was about 23 nm. This study showed that less degraded, thicker and more branched pectin molecules were associated with higher firmness and more favourable texture. Hemicellulose provided a positive contribution to texture when they were thinner and more flexible.

Main conclusion The Young’s modulus of the primary cell walls of pears decreases linearly during the pre-harvest on-tree maturation and increases during postharvest storage, and does not correlate with firmness of fruit. The determination of mechanical properties of cell walls is indispensable for understanding the mechanism of physiological softening and deterioration of quality of fruits during postharvest storage. The Young’s modulus of the primary cell walls from pear fruit (Pyrus communis L., cultivars ‘Conference’ and ‘Xenia’) during pre-harvest maturation and postharvest storage in an ambient atmosphere at 2 °C followed by shelf life was studied using atomic force microscopy (AFM). The results were related to the firmness of fruits, galacturonic acid content in water, chelator, sodium carbonate and insoluble pectin fractions, polygalacturonase and pectin methylesterase activities. The Young’s modulus of the primary cell walls decreased linearly during the last month of pre-harvest maturation from 3.2 ± 1.8 to 1.1 ± 0.7 MPa for ‘Conference’ and from 1.9 ± 1.2 to 0.2 ± 0.1 MPa for ‘Xenia’ which correlated with linear firmness decrease. During postharvest storage the cell wall Young’s modulus increased while firmness continued to decrease. Correlation analysis for the entire period of the experiment showed a lack of straightforward relation between the Young’s modulus of primary cell walls and fruit firmness. The Young’s modulus of cell walls correlated negatively either with galacturonic acid content in sodium carbonate soluble pectin (‘Conference’) or with insoluble pectin fractions (‘Xenia’) and positively with polygalacturonase activity. It was therefore evidenced that covalently linked pectins play the key role for the stiffness of fruit cell walls. Based on the obtained results, the model explaining the fruit transition from firm and crispy to soft and mealy was proposed.