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Apples ( Malus × domestica Borkh.) and pears ( Pyrus communis L.) are valuable crops closely related within the Rosaceae family with reported nutraceutical properties derived from secondary metabolites including phloridzin and arbutin, which are distinctive phenolic metabolites characterizing apples and pears, respectively. Here, we generated a de novo transcriptome assembly of an intergeneric hybrid between apple and pear, accumulating intermediate levels of phloridzin and arbutin. Combining RNA-seq, in silico functional annotation prediction, targeted gene expression analysis, and expression-metabolite correlations, we identified candidate genes for functional characterization, resulting in the identification of active arbutin synthases in the hybrid and parental genotypes. Despite exhibiting an active arbutin synthase in vitro , the natural lack of arbutin in apples is reasoned by the absence of the substrate and broad substrate specificity. Altogether, our study serves as the basis for future assessment of potential physiological roles of identified genes by genome editing of hybrids and pears.

The phenolic profiles and other major metabolites in juices made from fruits of 17 cultivars and selections of European pears were investigated using UHPLC-DAD-ESI-QTOF-MS and GC-FID, respectively. A total of 39 phenolic compounds were detected, including hydroxybenzoic acids, hydroxycinnamic acids, flavan-3-ols, procyanidins, flavonols, and arbutin. Among these compounds, 5- O -caffeoylquinic acid was the most predominant, accounting for 14-39% of total quantified phenolic contents (TPA) determined in this study. The variations were mainly cultivar dependent. The genetic background effect on the chemical compositions is complex, and breeding selections from the same parental cultivars varied dramatically in chemical compositions. Putative perry pears contained more 4- O -caffeoylquinic acid, 5- O -caffeoylquinic acid, caffeoyl N -trytophan, caffeoylshikimic acid, coumaroylquinic acid isomer, syringic acid hexoside, procyanidin dimer B2, (+)-catechin, and malic acid, whereas putative dessert pears had higher esters, alcohols, and aldehydes. The results will be helpful in providing industry with phytochemical compositional information, assisting pear selections in commercial utilization.

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.

Lignin content, composition, and linkage types were investigated in pear fruit cultivars and related species. Lignin content increased during early stages and then decreased toward ripening in the core and flesh of "Gold Nijisseiki" and "Alexandrine Douillard". The lignin content was highest at harvest in Chinese quince. Only trace amounts of lignin were detected in apple flesh. The lignin content was low in Japanese pears "Ohshu", "Hosui", and "Kosui", and the noncondensed lignin index was high in flesh. The lignin type was guaiacyl-syringyl (GS) in these pears and related species. The S/G ratio at harvest varied widely (0.75-2.64) and increased during early stages and remained constant toward harvest in "Gold Nijisseiki" and "Alexandrine Douillard". "Gold Nijisseiki" and "Alexandrine Douillard" were determined to be G- and S-lignin-rich types, respectively. β-Aryl ether, phenylcoumaran, and resinol interunit linkage types were detected among monolignol bonds, and β-Aryl ether units were the main linkages in the pear.

The biomimetic enzyme-linked immunosorbent assay (BELISA) is widely used for detection of small-molecule compounds as a result of low cost and reagent stability of molecularly imprinted polymers (MIPs). However, enzyme labels used in BELISA still suffer some drawbacks, such as high production cost and limited stability. To overcome the drawbacks, a biomimetic nanozyme-linked immunosorbent assay (BNLISA) based on MIPs and nanozyme labels was first proposed. For nanozyme labels, platinum nanoparticles (PtNPs) acted as peroxidase by catalyzing the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) into an ideal surface-enhanced Raman scattering (SERS) marker. Blue TMB 2+ and bovine serum albumin (BSA)-hapten showed superior selectivity when competing with targets for binding sites on MIPs, named the Pt@BSA-hapten probe. The BNLISA method was employed to detect triazophos with a limit of detection of 1 ng mL -1 via colorimetric and SERS methods. Replacing traditional enzymes with nanozymes for combination with MIPs may bring about a new prospect for other compound analyses.

The layer of cuticular wax covering fruits plays important roles in protecting against disease, preventing non-stomatal water loss, and extending shelf life. However, the molecular basis of cuticular wax biosynthesis in pear ( Pyrus ) fruits remains elusive. Our study thoroughly investigates cuticular wax biosynthesis during pear fruit development from morphologic, transcriptomic, and gas chromatography-mass spectrometry metabolomic perspectives. Our results showed that cuticular wax concentrations increased during the early stage [20-80 days after full bloom (DAFB)] from 0.64 mg/cm 2 (50 DAFB) to 1.75 mg/cm 2 (80 DAFB) and then slightly decreased to 1.22 mg/cm 2 during the fruit ripening period (80-140 DAFB). Scanning electron microscopy imaging indicated that wax plate crystals increased and wax structures varied during the pear fruit development. The combined transcriptomic and metabolomic profiling analysis revealed 27 genes, including 12 genes encoding transcription factors and a new structural gene ( Pbr028523 ) encoding β-amyrin synthase, participating in the biosynthesis, transport, and regulation of cuticular wax according to their expression patterns in pear fruit. The quantitative real-time polymerase chain reaction experiments of 18 differentially expressed genes were performed and confirmed the accuracy of the RNA-Seq-derived transcript expression. A model of VLCFAs and cuticular wax synthesis and transport in pear fruit is proposed, providing a mechanistic framework for understanding cuticular wax biosynthesis in pear fruit. These results and data sets provide a foundation for the molecular events related to cuticular wax in 'Yuluxiang' pear fruit and may also help guide the functional analyses of candidate genes important for improving the cuticular wax of pear fruit in the future.

In this study, a highly sensitive upconversion fluorescence (FL) biosensor was developed for the detection of organophosphorus pesticides (OPs) based on an acetylcholinesterase (AChE) modulated FL "off-on-off" strategy. The luminescence of synthesized UCNPs could be quenched strongly by Cu 2+ due to an energy transfer effect. Upon addition of AChE and acetylthiocholine (ATCh), the enzymatic hydrolysate (thiocholine) could seize Cu 2+ from UCNPs-Cu 2+ mixture, resulting in the quenched FL triggered on. OPs could irreversibly impede the activity of AChE, which caused the formation of thiocholine to decrease, thus, reduced the recovery of FL. Under the optimum conditions, a linear detection range from 0.1 to 50 ng/mL was achieved for the representative OPs (diazinon) with LOD of 0.05 ng/mL. Furthermore, the ability of the biosensor to detect OPs was also confirmed in adulterated environmental and agricultural samples. In validation analysis, the proposed sensor showed satisfactory results ( p > 0.05) with GC-MS.

In the present study the enzymatic oxidation of gallic acid and catechin catalyzed by nashi pear polyphenol oxidase (PPO) in the presence of the amino acids lysine, arginine, or cysteine was investigated for polyphenol-amino acid adducts. HPLC analyses revealed the formation of two novel dihydrobenzothiazine carboxylic acid derivatives (8-(3',4'-dihydro-2 H-chromene-3',5',7'-triol)-3,4-dihydro-5-hydroxy-2 H-benzothiazine-3-carboxylic acid and 7-(3',4'-dihydro-2 H-chromene-3',5',7'-triol)-3,4-dihydro-5-hydroxy-2 H-benzothiazine-3-carboxylic acid) from 2'-cysteinyl catechin and 5'-cysteinyl catechin in cysteine incubations, respectively. In contrast, arginine and lysine did not lead to any amino acid adducts. Target compounds were separated by high-performance countercurrent chromatography and preparative HPLC and unequivocally characterized by mass spectrometry and nuclear magnetic resonance spectroscopy. Mechanistic incubations starting from the catechin-cysteine adducts showed that both catechin and PPO are crucial components in the formation of the dihydrobenzothiazines. The cysteine incubations showed a red-brown coloration, which coincided with formation and degradation of the dihydrobenzothiazines finally leading to the formation of high-polymeric melanins. Therefore, these compounds might be the key intermediates to understand development of color during cysteine-driven enzymatic browning reactions.

Bitertanol is a widely used triazole fungicide and consists of four stereoisomers. A new high-performance liquid chromatography (HPLC) method was developed for simultaneous analysis of the four stereoisomers in apple, pear, tomato, cucumber, and soil. The mechanism of separation was explained with molecular docking and effects of thermodynamic parameters on the resolution. The absolute configuration and optical rotation of four stereoisomers were confirmed by X-ray diffraction and HPLC tandem circular dichroism, respectively. A good linearity ( R 2 ≥ 0.999) was obtained for four stereoisomers in all matrix-matched calibration curves in the range of 0.02-10 mg/L. The mean recoveries of four stereoisomers in five matrices ranged from 74.6% to 101.0% with an intraday and interday relative standard deviation from 0.6% to 9.9%. Stereoselective degradation of bitertanol in cucumber was observed: (1 R,2 S)-bitertanol and (1 R,2 R)-bitertanol were preferentially degraded with enantiomeric fraction values from 0.5 to 0.43 at 7 d and 0.42 at 5 d, respectively. This research provides a useful tool for the analysis of bitertanol stereoisomers.

A simple method based on surface-enhanced Raman scattering (SERS) was developed for the rapid determination of alternariol (AOH) in pear fruits using an easily prepared silver-nanoparticle (AgNP) substrate. The AgNP substrate was modified by pyridine to circumvent the weak affinity of the AOH molecules to the silver surface and to improve the sensitivity of detection. Quantitative analysis was performed in AOH solutions at concentrations ranging from 3.16 to 316.0 μg/L, and the limit of detection was 1.30 μg/L. The novel method was also applied to the detection of AOH residues in pear fruits purchased from the market and in pear fruits that were artificially inoculated with Alternaria alternata. AOH was not found in any of the fresh fruit, whereas it resided in the rotten and inoculated fruits. Finally, the SERS method was cross validated against HPLC. It was revealed that the SERS method has great potential utility in the rapid detection of AOH in pear fruits and other agricultural products.

In this paper, we first report the development of a highly sensitive and economical method for accurate analysis of pyridaben residues on fruits based on dual-frequency ultrasonic treatment (DFUT) and flow injection chemiluminescence (CL) detection. The DFUT device is made by integrating an ultrasonic bath with an ultrasonic probe. Two quartz glass coils (QGC) with different structures have been designed and applied to evaluate the function of DFUT in the detection process. Recorded data showed that DFUT is an effective method for improving the pyridaben CL signal. The signal of pyridaben in response to DFUT is 2.0-3.3 times stronger than the response to only the ultrasonic probe at 20 kHz or the ultrasonic bath at 40 kHz. In addition, the response obtained from the concentric circle QGC is 2.1 times stronger than the response to the spiral tube QGC. Under the optimized condition, the proposed method has advantages, such as a wide linear range (0.8-100.0 μg L -1 ), a high sensitivity (limit of detection of 0.085 μg L -1 ), and good stability (RSDs ≤ 4.7% in the linear range) for pyridaben determination. We apply this method to monitor the residue pyridaben on some fruits. The data show that the maximum amounts of the residue on fruit surfaces after soaking in water (50 mg L -1 , 5 min) are 0.583 mg kg -1 (apple), 0.794 mg kg -1 (orange), and 0.351 mg kg -1 (pear). However, the concentration of pyridaben in the presence of sunlight decreases rapidly, showing its poor light stability.

An efficient and sensitive chiral analytical method was established for the determination of the chiral fungicide prothioconazole and its major chiral metabolite prothioconazole-desthio in agricultural and environmental samples using ultraperformance liquid chromatography-tandem mass spectrometry. The optical rotation and absolute configuration of enantiomers were identified by optical rotation detector and electronic circular dichroism spectra. The elution order of prothioconazole and its chiral metabolite enantiomers was R-(+)-prothioconazole-desthio, S-(-)-prothioconazole-desthio, R-(-)-prothioconazole, and S-(+)-prothioconazole. The mean recoveries from the samples was 71.8-102.0% with intraday relative standard deviations (RSDs) of 0.3-11.9% and interday RSDs of 0.9-10.6%. The formation of prothioconazole-desthio was studied in soil under field conditions and enantioselective degradation was observed for chiral prothioconazole. Remarkable enantioselective degradation was observed: R-prothioconazole degraded preferentially with EF values from 0.48 to 0.37. Although prothioconazole-desthio is the most remarkably bioactive metabolite, no obvious enantioselective behavior was observed in soil. These results may help to systematically evaluate prothioconazole and its metabolites in food and environmental safety.

Application of aroma extract dilution analysis to Bartlett pears and the fermented mash produced thereof revealed 24 and 34 aroma-active compounds in the flavor dilution (FD) factor range between 8 and 8192. Twenty-eight compounds, which have not been described before in Bartlett pears or in fermented pear mash, were identified. While ethyl (E,Z)-2,4-decadienoate (pear-like, metallic odor impression), hexyl acetate (green, fruity), and acetic acid (vinegar-like) showed the highest concentrations in Bartlett pears, ethanol (ethanolic), acetic acid, 3-methyl-1-butanol (malty), 1-hexanol (grassy, marzipan-like), (S)-2- and 3-methylbutanoic acid (sweaty), and 2-phenylethanol (flowery, honey-like) were present at the highest amounts in the fermented mash. The key aroma compounds were quantitated in each pear brandy production step (pears, fermented mash, distillate, and aged distillate) by stable isotope dilution analysis showing a clear influence of each step on the overall aroma of the spirit and, consequently, revealing clearly changing concentrations (e.g., of ethyl (S)-2-methylbutanoate, (E)-β-damascenone, ethyl (E,Z)-2,4-decadienoate, and ethyl (E,E)-2,4-decadienoate) and different aroma perceptions during the manufacturing process. In addition, the concentrations of the so-called "pear esters" ethyl (E,Z)-2,4-decadienoate and ethyl (E,E)-2,4-decadienoate were determined in 6 different pear varieties (Abate Fetel, Anjou, Bartlett, Forelle, Kaiser Alexander, and Packham's Triumph) clearly demonstrating the aroma potential of the variety Bartlett, which is mostly used for brandy production due to the high amounts of both esters eliciting a typical pear-like odor impression.

This study aimed at understanding the biochemical basis of internal browning disorders (IBDs) in 'Rocha' pear. For this purpose, the effects of storage under normal controlled atmosphere (CA) (3 kPa of O2 + 0.5 kPa of CO2) and IBD-inducing CA (1 kPa of O2 + 10 kPa of CO2) on the antioxidant and fermentative metabolisms and polyphenol oxidase (PPO) activity and phenolics concentration were studied. The higher IBD incidence in high CO2-stored fruits was positively correlated with fermentative metabolites and negatively with ascorbate and H2O2 concentrations, and it was linked to PPO activation. These results indicate that both the antioxidant and fermentative metabolisms are involved in the occurrence of IBD in 'Rocha' pear. From the integration of the biochemical and enzymatic data, a schematic model illustrating the effects of high CO2 and low O2 in 'Rocha' pears during long-term storage was constructed.

The European pear psylla, Cacopsylla pyri L. (Hemiptera: Psyllidae), is one of the most serious arthropod pests of pear. Since proper control of this pest is essential, better understanding of the complex plant-pest relationship is mandatory. This research deals with constitutive polyphenolic profiles in leaves of 22 pear cultivars of diverse origin (P. communis, P. pyrifolia, and P. pyrifolia × P. communis) and different resistance to psylla. The study was designed to show which differences in the polyphenolic profile of leaves from resistant and susceptible pear cultivars could be utilized as information in subsequent breeding programs. The results demonstrated that the leaves of Oriental pear cultivars contained much higher amounts of p-hydroxybenzoic acid, ferulic acid, aesculin, and naringin, that, together with detected 3-O-(6″-O-p-coumaroyl)-hexoside, apigenin, apigenin 7-O-rutinoside, and hispidulin, indicated a clear difference between the species and might represent phenolics responsible for psylla resistance.

A hydrophobic monolith (10 mm × 2.1 mm i.d.) was developed as a reusable online solid-phase extraction (SPE) sorbent coupled with LC-MS/MS for the rapid determination of five avermectin residues in foodstuffs of both plant and animal origin. The online SPE was achieved using a 10 mmol/L ammonium acetate solution as the loading solvent, and acetonitrile (MeCN) was selected for the washing step. After being transferred from the monolith into a C18 analytical column using MeCN, the analytes were analyzed by LC-MS/MS using MeCN/0.1% NH4OH (10:90, v/v) as the mobile phase. The detection limit was 2 μg/kg for five avermectins, and the recoveries in fresh pear, chili seed, bovine muscle, and milk ranged from 71.8% to 101.3% with relative standard deviations of less than 8.94%. The online SPE and determination were achieved within 15 min, and the monolithic extractor was reusable for more than 500 experiments.

Pear juice is predominately composed of carbohydrates/polyols (>95% of the total soluble solids), making it susceptible to adulteration by the addition of less expensive commercial sweeteners. In this research, the major carbohydrate and polyol (fructose, glucose, sucrose, and sorbitol) content of 32 pure pear juices representing five world producing regions and three years of production was determined. Additionally, methods employing oligosaccharide profiling to detect the debasing of these samples with four commercial sweeteners (HFCS 55 and 90, TIS, and HIS) were developed using capillary gas chromatography with flame ionization detection (CGC-FID) and high-performance liquid chromatography with pulsed amperometric detection (HPAE-PAD). Detection limits for the four commercial sweeteners ranged from 0.5 to 5.0% (v/v). In addition, the developed CGC-FID method could be used to (a) detect the addition of pear to apple juice via arbutin detection and (b) determine if a pear juice was produced using enzymatic liquefaction via the presence of O-β-d-glucopyranosyl-(1→4)-d-glucopyranose (cellobiose), all within a single chromatographic analysis.

'Comice' is among the pear varieties most difficult to ripen after harvest. Ethylene, cold temperature, and intermediate (10 °C) temperature conditioning have been successfully used to stimulate the ability of 'Comice' pears to ripen. However, the sensory quality of pears stimulated to ripen by different conditioning treatments has not been evaluated. In this study, a descriptive sensory analysis of 'Comice' pears conditioned to soften to 27, 18, and 9 N firmness with ethylene exposure for 3 or 1 days, storage at 0 °C for 25 or 15 days, or storage at 10 °C for 10 days was performed. Sensory attributes were then related to changes in chemical composition, including volatile components, water-soluble polyuronides, soluble solids content (SSC), and titratable acidity (TA). The sensory profile of fruit conditioned with ethylene was predominant in fibrous texture and low in fruity and pear aroma. Fruit conditioned at 0 °C was described as crunchy at 27 and 18 N firmness and became juicy at 9 N firmness. Fruit conditioned at 0 °C produced the highest quantity of alcohols and fewer esters than fruit conditioned at 10 °C, and they had higher fruity and pear aroma than fruit conditioned with ethylene, but lower than fruit conditioned at 10 °C. Fruit held at 10 °C were predominant in fruity and pear aroma and had the highest concentration of esters. Water-soluble polyuronides were strongly, positively correlated (r > 0.9) with sensory attributes generally associated with ripeness, including juiciness, butteriness, and sweetness and negatively correlated (r > -0.9) with sensory attributes generally associated with the unripe stage, such as firmness and crunchiness. However, water-soluble polyuronides were not significantly different among conditioning treatments. Sensory sweetness was not significantly correlated with SSC, but TA and SSC/TA were significantly correlated with sensory tartness. However, there were no significant differences among the conditioning treatments in sweet or sour taste perception when the fruit fully softened. The results indicate that the various methods of conditioning 'Comice' pear fruits for ripening had different effects on their sensory and chemical properties that may influence their sensory quality.

The aroma compounds in two commercial Bartlett pear brandies clearly differing in their overall aroma profiles were detected in the volatile fractions by the aroma extract dilution analysis. In brandy A eliciting the more intense pear-like, fruity aroma, ethyl (S)-2-methylbutanoate, (E)-β-damascenone, 1,1-diethoxyethane, 2- and 3-methylbutanol, (S)-2- and 3-methylbutanoic acid, and 2-phenylethanol were found with the highest Flavor Dilution (FD) factors. In brandy B judged to have a weaker overall aroma, also (E)-β-damascenone, ethyl (S)-2-methylbutanoate, and 2-phenylethanol revealed high FD factors, while many odorants showed lower FD factors. Fourty-four odor-active compounds were quantitated by stable isotope dilution assays, and the odor activity values (OAVs; ratio of concentrations to odor thresholds) confirmed (E)-β-damascenone and ethyl (S)-2-methylbutanoate as important aroma compounds in brandy A, while the OAVs of most odorants were much lower in brandy B. By aroma recombination studies, the aromas of both brandies could be matched using reference odorants in the same concentrations as they occurred in the spirits. In 15 commercial Bartlett pear brandies ethyl (E,Z)-2,4-decadienoate and (E,E)-2,4-decadienoate eliciting a pear-like aroma showed a reasonable correlation of their concentrations with the overall aroma quality.

After canning, pear pieces turn occasionally from whitish-beige to pink. Conditions were set up to obtain this discoloration systematically and investigate its mechanism. Canned pears showed a significantly lower L* coordinate compared with fresh pears, and the L* coordinate of canned pears decreased with decreasing pH. The values of the a* and b* coordinates increased significantly after processing, the increase being greater for the more acidic pH values, with corresponding redder colors. After canning, polyphenol concentrations decreased significantly, mainly due to loss of procyanidins. This supported the hypothesis of conversion of procyanidins to anthocyanin-like compounds. However, no soluble product was detected at 520 nm, the characteristic wavelength of anthocyanins. When purified procyanidins were treated at 95 °C at three different pH values (2.7, 3.3, and 4.0), procyanidin concentrations decreased after treatment, the more so as the pH was lower, and a pinkish color also appeared, attributed to tannin-anthocyanidin pigment. The pink color was bound to cell walls. Extraction of the neoformed pink entities was attempted by successive solvent extractions followed by cell wall degrading enzymes. The pink color persisted in the residues, and canned pears gave significantly higher amounts of residues after solvent and enzyme treatments than fresh pears. Procyanidins were the entities responsible for the appearance of pink discoloration. However, it seems that this pink discoloration also involved the formation of strong, probably covalent, bonds to the cell wall.

Plant regeneration is a critical step in most in vitro breeding techniques. This paper studies the effects of a low-molecular-weight humic acid (HA) on morphogenesis from pear and quince leaf explants. Variable HA amounts [0 (control), 1, 5, 10, and 20 mg C L(-1)] were added to the regeneration media. A dose-response effect was observed in pear for root and shoot production; it was improved at HA 1 mg C L(-1) and considerably reduced at the highest amounts. HA was, instead, ineffective in quince. The (1)H HR-MAS NMR analyses of calli in the induction phase showed more evident metabolite (asparagine, alanine, and γ-aminobutyric acid) signals in quince than in pear. The assignment of overlapped signals in both genotypes was supported by the 2D NMR analyses. Spectroscopic characterization suggested also an enhancement of asparagine contents in morphogenic calli of pear with respect to the control and higher HA amount treatments.

Pear distillates are generally produced from the Bartlett variety because of its rich aroma. In this study, a chemical and sensorial comparative examination of pear distillates from the three main varieties grown in Spain (Bartlett, Blanquilla, and Conference) using two distillation systems (copper Charentais alembic and packed column) was undertaken. Volatile compounds were identified by gas chromatography to differentiate the spirits according to pear variety and distillation method. The Bartlett distillates from both distillation systems possessed higher ethyl ester and acetate and lower cis-3-hexen-1-ol and 1-hexanol concentrations. Despite these differences, a sensory analysis panel could distinguish only the Bartlett alembic distillate from the alembic distillates of the other varieties. In contrast, the panel rated the packed-column distillates equally. Therefore, less aromatic pear varieties can be used to produce distillates with aromatic characteristics similar to those of the Bartlett variety if a suitable distillation process is used.

Six triterpenes, including three caffeoyl triterpenes, were purified and isolated from pear fruit ( Pyrus pyrifolia Nakai cv. Chuwhangbae) peel extracts using various column chromatography techniques with a guided 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging assay. The isolated compounds were identified as betulinic aldehyde (1), lupeol (2), betulinic acid (3), 3-O-cis-caffeoylbetulinic acid (4), 3-O-trans-caffeoylbetulinic acid (5), and 3-O-trans-caffeoyloleanolic acid (6) on the basis of nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry. Four compounds (1, 4-6) were identified from Asian pear fruit for the first time. In addition, compounds 4-6, containing a caffeic acid moiety, showed higher DPPH radical-scavenging and suppression effects against copper ion-induced oxidation of rat blood plasma than other compounds without a caffeic acid moiety.

Three triterpene-caffeates have been isolated from skins of a russeted apple cultivar "Merton Russet" and identified by LC-MS and NMR as betulinic acid-3-cis-caffeate, betulinic acid-3-trans-caffeate, and oleanolic acid-3-trans-caffeate. Betulinic acid-3-trans-caffeate and oleanolic acid-3-trans-caffeate were also found in russeted pear skins. These compounds have not been previously reported in apples or pears, or in any other foods. Their presence was related to suberized tissue as they were only found in russet portions of the partially russeted apple cultivar "Cox's Orange Pippin" and were not detected in the waxy apple cultivar "Royal Gala". High concentrations of betulinic acid-3-trans-caffeate were found in the bark of both "Merton Russet" and "Royal Gala" trees. The three triterpene-caffeates showed anti-inflammatory activity in vitro, inhibiting NF-κB activation with IC50's of 6-9 μM. Betulinic acid-3-trans-caffeate, the predominant compound in the apples, was immuno-modulatory at around 10 μM in the in vitro and ex vivo bioassays, boosting production of the pro-inflammatory cytokine TNFα in cells stimulated with bacterial lipopolysaccharides.

Engineered nanomaterials such as silver nanoparticles (Ag NPs) have been increasingly used in agriculture owning to their antimicrobial and insecticidal properties. However, the contamination of Ag NPs in foods and water may pose a great risk to public health and the environment. In this study, the contamination of Ag NPs in pears was detected, characterized, and quantified by a combination of techniques, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and inductively coupled plasma optical emission spectrometry (ICP-OES). Pear samples were treated with two different sizes (20 and 70 nm in diameter) of Ag NPs and stored for different times. Quantification results of Ag NPs in pear samples by ICP-OES demonstrate that there is a good linear relationship (R(2) = 0.983) between the spiked values and recovered values. Residual Ag NPs of both 20 and 70 nm were still detected in samples after 4-day treatment followed by rinsing with water. The penetration study reveals that 20 nm Ag NPs might penetrate the pear skin and pulp after 4-day treatment, while this phenomenon was not observed for 70 nm Ag NPs. These results demonstrate that a combination of techniques could provide accurate results for detection, characterization, and quantification of engineered nanoparticles in agricultural products.

The contents of total phenolics, total flavonoids, total anthocyanins, and total triterpenes of eight pear samples were determined, and the monomeric compounds were identified and quantitated using high-performance liquid chromatography. The in vitro antioxidant and in vivo anti-inflammatory activities of the different pear cultivars were compared. Arbutin and catechin were the dominant polyphenol compounds in the eight pear varieties, followed by chlorogenic acid, quercetin, and rutin. In addition, Xuehua pear and Nanguo pear had significantly higher total phenolics and flavonoids contents, while Dangshansu pear had the largest total triterpenes value (209.2 mg/100 g). Xuehua pear and Nanguo pear also were the highest in total anthocyanins. The pears with high total phenolics and total flavonoids contents had significantly higher antioxidant and anti-inflammatory abilities than those of other species. Anthocyanins were correlated to antioxidant capacity in pears, whereas total triterpenoids were strongly correlated to anti-inflammatory activity.

To analyze the accuracy of the Klason lignin method as applied for the determination of lignin contents in plant based-food products, Klason lignin preparations from curly kale, pears, whole wheat grains, and corn bran were chemically characterized. Characterization included routine ash and protein determinations and the extraction of fat/waxes as well as cutin/suberin depolymerization and extraction of the liberated monomers. Fat/wax and cutin/suberin amounts in the Klason lignin preparations were determined gravimetrically, and their compositions were analyzed by using GC-MS. Typical fat, wax, and cutin (and suberin) constituents such as saturated and unsaturated fatty acids, hydroxy and/or epoxy fatty acids, and phenolic acids were identified in all samples, whereas the detection of long-chain hydrocarbons, alcohols, and ketones, sterols, stanols, and dioic acids was dependent on the sample analyzed. Estimation of the contribution of non-lignin compounds to the Klason lignin contents reduced the noncorrected Klason lignin contents of the insoluble fibers from 28.7% (kale), 22.8% (pear), 14.8% (wheat), and 9.9% (corn) to maximum lignin contents of 6.5% (kale), 16.4% (pear), 4.9% (wheat), and 2.3% (corn). These data demonstrate that certain commonly used statements such as "cereal brans are highly lignified" need to be revised.

Preharvest conditions can have a great impact on fruit quality attributes and postharvest responses. Firmness is an important quality attribute in pear, and excessive softening increases susceptibility to bruising and decay, thus limiting fruit postharvest life. Textural characteristics of fruits are determined at least in part by cell wall structure and disassembly. Few studies have analyzed the influence of fruit preharvest environment in softening, cell wall composition, and degradation. In the current work 'Bartlett' pears grown either facing the sun (S) or in the shade (H) were harvested and stored for 13 days at 20 °C. An evaluation of fruit soluble solids, acidity, color, starch degradation, firmness, cell wall yield, pectin and matrix glycan solubilization, depolymerization, and monosaccharide composition was carried out. Sun-exposed pears showed more advanced color development and similar levels of starch degradation, sugars, and acids than shaded fruit. Sunlight-grown pears were at harvest firmer than shade-grown pears. Both fruit groups softened during storage at 20 °C, but even after ripening, sun-exposed pears remained firmer. Sunlight exposure did not have a great impact on pectin molecular weight. Instead, at harvest a higher proportion of water-solubilized uronic acids and alkali-solubilized neutral sugars and a larger mean molecular size of tightly bound glycans was found in sun-exposed pears. During ripening cell wall catabolism took place in both sun- and shade-grown pears, but pectin solubilization was clearly delayed in sun-exposed fruit. This was associated with decreased removal of RG I-arabinan side chains rather than with reduced depolymerization.

Two novel caffeoylmalic acid methyl esters, 2-O-(trans-caffeoyl)malic acid 1-methyl ester (6) and 2-O-(trans-caffeoyl)malic acid 4-methyl ester (7), were isolated from pear (Pyrus pyrifolia Nakai cv. Chuhwangbae) fruit peels. In addition, 5 known hydroxycinnamoylmalic acids and their methyl esters were identified: 2-O-(trans-coumaroyl)malic acid (1), 2-O-(cis-coumaroyl)malic acid (2), 2-O-(cis-coumaroyl)malic acid 1-methyl ester (3), 2-O-(trans-coumaroyl)malic acid 1-methyl ester (4), and 2-O-(trans-caffeoyl)malic acid (phaselic acid, 5). The chemical structures of these compounds were determined by spectroscopic data from ESI MS and NMR. Of all the isolated compounds, five hydroxycinnamoylmalic acids and their methyl esters (2-4, 6, 7) were identified in the pear for the first time.

A liquid chromatography electrospray ionization tandem mass spectrometry method for the determination of patulin in apple- and pear-based foodstuffs was developed. The sample preparation is based on the QuEChERS procedure involving an initial extraction step with water and acetonitrile, followed by a partitioning step after the addition of magnesium sulfate and sodium chloride. The cleanup was performed by using dispersive solid-phase extraction with a mixture of magnesium sulfate, primary secondary amine sorbent, and n-octadecylsiloxane sorbent added together to the extract. The cleaned extract was finally evaporated and reconstituted in water prior to injection. Quantitation was performed by isotope dilution using ((13)C(7))-patulin as internal standard. The method was first fully validated in three different baby food products including apple-pear juice, apple-pear puree, and infant cereals. Then the scope of application of the method was extended to pear concentrate, raw apples, apple flakes (naturally contaminated), dried apples, and yogurt. The sensitivity achieved by the method in all matrices gave limits of detection (LOD) and quantitation (LOQ) of ≤0.5 and ≤10 μg/kg, respectively, which was compliant with maximum levels settled in Commission Regulation (EC) No. 1881/2006. Method performances for all matrices also fulfilled the criteria established in the CEN/TR 16059:2010 document. Indeed, recoveries were within the 94-104% range; relative standard deviations of repeatability (RSD(r)) and intermediate reproducibility (RSD(IR)) were ≤7.5 and ≤13.0%, respectively, and trueness in an infant apple drink (FAPAS 1642) was measured at 99%.

Apple and pear fruits are important sources of secondary plant metabolites and one of the major sources of dietary phenolics consumed all year round. The aim of this work was to identify the main variables influencing phenolic content and antioxidant capacity in apples. Higher phenolic and antioxidant contents were observed in some varieties (such as the Delbar Estival apple and Durondeau pear). Storage conditions were important. Our results also showed that fruits should be consumed rapidly after purchase and with their peel. After one week of domestic storage, the ascorbic acid content was found to decrease by 75%. Peeling led to a more than 25% decrease in total phenolics and ascorbic acid. The harvest time (at normal ripeness) had only a limited impact, but significant year-to-year variations were observed. In conclusion, well-chosen and well-stored apples and pears may contribute to an antioxidant-rich diet if consumed rapidly and with their peel.

Pyrus bretschneideri Rehd., as a pharmaceutical supplement, is widely used in northern China to treat respiratory diseases. Our previous studies showed the ethanol extract of P. bretschneideri had significant anti-inflammatory activity. To isolate and identify the active ingredients, the ethanol extract was separated into petroleum ether, ethyl acetate, n-butanol, and aqueous fractions. The bioactivity of each fraction was investigated using an in vivo model. Results showed that the ethyl acetate fraction exhibited the strongest anti-inflammatory effect. Subsequently, this fraction was subjected to separation and purification using silica gel column chromatography, C18-ODS, and recrystallization, leading to two sterols and two triterpenes, which were identified as β-sitosterol, daucosterol, oleanolic acid, and ursolic acid. Moreover, all of the isolated compounds could significantly inhibit the ear edema induced by xylene. These results indicated that P. bretschneideri had good anti-inflammatory effects and the constituents β-sitosterol, daucosterol, oleanolic acid, and ursolic acid might well account for it.

Erwinia amylovora causes fire blight, a serious disease of apple and pear. The bacterial pathogen colonizes the flower stigma and hypanthium, where it multiplies and then invades through natural openings (nectarthodes). E. amylovora requires nicotinic acid as growth factor, and competition for nicotinic acid is being explored as a novel biocontrol strategy. The ability of E. amylovora to substitute nicotinic acid with analogues or derivates as growth factors has not been investigated yet. Furthermore, the presence and/or variable concentration of nicotinic acid and its analogues/derivates in the hypanthium could be associated with the different susceptibilities to fire blight of hosts and nonhosts and with the differential sensitivity to the disease among apple and pear varieties. Currently, no methods to specifically quantify nicotinic acid and nicotinic acid analogues/derivates in the hypanthium of apple and pear blossoms are available. This study demonstrates that E. amylovora can grow using nicotinamide and 6-hydroxynicotinic acid as alternative growth factors to nicotinic acid, but not using 2-hydroxynicotinic acid. A novel HPLC/ES-MS method was developed for the detection and quantification of nicotinic acid and its analogues/derivates directly in the hypanthium of apple and pear blossoms. Analyses established the presence of nicotinic acid and nicotinamide, whereas no detectable amounts of 6-hydroxynicotinic acid and 2-hydroxynicotinic acid were observed. Mean nicotinic acid content in the pear hypanthium was found to be approximately 2 orders of magnitude higher than in the apple hypanthium, which may contribute to the differential susceptibility of these two host species to fire blight. Contents of nicotinamide were in contrast similar. Nicotinic acid can therefore be considered a relevant factor in the pathogen establishment in pear blossoms, whereas nicotinamide could cover a primary role in apple blossoms.

Cyclodextrins (CDs) are widely used as browning inhibitors in different fruit juices. However, pear juice quality is affected by many properties, such as odor and aroma, and to date, no paper has reported the effect of the addition of CDs on the flavor profile of a fruit juice. In this study, the aroma profile of pear juice was mainly formed by volatile compounds from four chemical families: esters, aldehydes, alcohols, and hydrocarbons. Even though the addition of alpha-CD had a significant effect on both the concentration of individual volatile compounds and their grouping, only the highest concentration, 90 mM, prevented the oxidation of the volatile precursors present in freshly squeezed juice. Moreover, correlation of these results, concerning the color and aroma of pear juice in the presence of CDs, with the consumer preferences has not been reported. A descriptive sensory analysis of pear juices in both the presence and the absence of CDs was carried out, and odor/aroma attributes (fresh, fruity, pear-like, unnatural, etc.), plus global color, odor, aroma, and quality, were quantified using a trained panel of judges. The addition of alpha-CD at 90 mM resulted in pear juices with the best color but with low aromatic intensity and low sensory quality. On the other hand, the addition of alpha-CD at 15 mM led to a pear juice also with an acceptable color but at the same time with a high intensity of fruity and pear-like odors/aromas, making it the best appreciated juice by the panel.

The effect of extreme gas conditions (anoxia and air) on the protein expression profiles of Conference pear slices was assessed with a differential gel electrophoresis (DIGE) approach using robust statistical analysis. Changes in expression, up to 4-fold, were identified in proteins involved in respiration, protein synthesis, and defense mechanisms. In addition, short-term exposure of pear slices to anoxia clearly induced up-regulation of transketolase and polygalacturonase inhibiting protein and down-regulation of several isoforms of the major allergen Pyrc (PR proteins), providing further evidence of the possible involvement of these enzymes in the development of the physiological disorder core breakdown. The role of these PR proteins under anoxia is unknown, but our results suggest that these proteins are involved in protection against abiotic stress such as the anoxic conditions applied.

Polyphenoloxidase (PPO) from Chinese pear ( Pyrus pyrifolia Nakai) was characterized using catechol as a substrate. PPO had a V(max) of 289.2 units/min and a K(m) of 3.8 mmol/L, which indicates that P. pyrifolia Nakai PPO has a great affinity for catechol. The catalyzing reaction velocity was proportional to the PPO concentration. The optimum pH and temperature for PPO activity were 4.5 and 45 degrees C, respectively. In addition, an investigation was made on the effect of high-pressure microfluidization of treatment pressure, treatment pass, and enzyme solution temperature on P. pyrifolia Nakai PPO. As the treatment pressure increased, the PPO relative activity was elevated from 100% untreated to 182.57% treated at 180 MPa. PPO relative activity was enhanced as the treatment pass increased. PPO solution temperature (25, 35, and 45 degrees C) had a significant effect on PPO relative activity when treated at 120 and 140 MPa.

A standardized profiling method based on liquid chromatography with diode array and electrospray ionization/mass spectrometric detection (LC-DAD-ESI/MS) was used to analyze the phenolic compounds in the skins of 16 pears (Pyrus spp.). Thirty-four flavonoids and 19 hydroxycinnamates were identified. The main phenolic compounds (based on peak area) in all of the pear skins were arbutin and chlorogenic acid. The remaining phenolics varied widely in area and allowed the pears to be divided into four groups. Group 1, composed of four Asian pears (Asian, Asian brown, Korean, and Korean Shinko), contained only trace quantities of the remaining phenolics. Yali pear (group 2) contained significant amounts of dicaffeoylquinic acids. Fragrant pear (group 3) contained significant quantities of quercetin glycosides and lesser quantities of isorhamnetin glycosides and the glycosides of luteolin, apigenin, and chrysoeriol. The remaining 10 pears (group 4) (Bartlett, Beurre, Bosc, Comice, D'Anjou, Forelle, Peckham, Red, Red D'Anjou, and Seckel) contained significant quantities of isorhamnetin glycosides and their malonates and lesser quantities of quercetin glycosides. Red D'Anjou, D'Anjou, and Seckel pears also contained cyanidin 3-O-glucoside. Thirty-two phenolic compounds are reported in pear skins for the first time.

The antioxidant content of fresh-cut 'Flor de Invierno' ( Pyrus communis L.) pears dipped into a 0.75% w/v N-acetylcysteine + 0.75% w/v glutathione solution and packaged under 70 kPa of O2 atmospheres (HOA) was evaluated as an alternative to actively modified low-O2 atmosphere (LOA) and passively modified atmospheres (PA). Changes in color, vitamin C, individual phenolic compounds, and antioxidant activity of fresh-cut pears as well as in O2, CO2, and ethylene headspace concentrations inside the packages were assessed for 14 days at 4 degrees C. Not only did the use of antioxidants prevent browning and reduce ethylene production of fresh-cut pears, but also their application under LOA best maintained vitamin C, chlorogenic acid, and antioxidant capacity compared with HOA. The results show that the use of glutathione and N-acetylcysteine enhanced the formation of phenylpropanoids in fresh-cut pears stored under LOA.

Pome trees, apple, pear, and quince, are classified into the subfamily Pomoideae, belonging to the Rosaceae family. Their autumnal fruits are consumed worldwide in different forms, that is, fresh or transformed into jams, jelly, juices, etc. Their well-established beneficial properties to human health were found mainly related to their phenolic content. Pulp and peel aqueous acetone extracts obtained from Tunisian fruits at commercial maturity were comparatively evaluated for their phenolic profiles and antioxidant and antimicrobial potentials. The phenolic compounds present in the extracts were identified and quantified using RP-HPLC-DAD and ESI-MS techniques. Significant differences in the chromatographic profiles among these fruits, as well as between pulp and peel extracts of each fruit, were observed. Quince, followed by 'Red Delicious', peel extracts showed the highest phenolic content (160.33 and 110.90 mg/100 g of fresh weight). The stronger inhibitory effect on DPPH radicals corresponded to those obtained from peel materials. A comparative analysis of the antimicrobial potential against a range of microorganism strains was also carried out. Staphylococcus aureus, Pseudomonas aeruginosa, and Bacillus cereus were the most sensitive to the active extracts. Among the examined phenolic extracts, 'Red Delicious' and quince peels showed the highest effects for inhibiting bacteria growth. Minimum inhibitory and bactericide concentrations ranged from 10(2) to 10(4) microg of polyphenol/mL. Red skin apple and quince peels could be of great interest as important antioxidant and antimicrobial polyphenol sources.

Conjugated triene (CT) oxidation products of the acyclic sesquiterpene (E,E)-alpha-farnesene are thought to induce development of the physiological storage disorder superficial scald in apple and pear fruits of susceptible cultivars. CTs that accumulate in peel tissues of Granny Smith and Delicious apples after several weeks of cold storage are known to be conjugated trienols (CTols) rather than the corresponding hydroperoxides produced by in vitro autoxidation of alpha-farnesene. Here, it is shown that CTols are also the predominant in vivo oxidation products of alpha-farnesene in cold-stored pear fruit of the highly scald-susceptible d'Anjou cultivar. Analysis by octadecylsilane reversed phase high-performance liquid chromatography with diode array detection, gas chromatography with flame ionization detection, gas chromatography-mass spectrometry, and proton nuclear magnetic resonance spectroscopy identified 3,7,11-trimethyldodeca-1,3(E),5(E),10-tetraen-7-ol as the major CT in hexane extracts of peel tissue from d'Anjou pears stored for 3-5 months in air at -1 degrees C. The possible origins of CTols in apples and pears and the hypothesized role of these oxidation products of alpha-farnesene in the induction of scald are discussed. .

Pear juice obtained from pear concentrate was fermented at room temperature using Saccharomyces cerevisiae (BDX, ENOFERM, France) as the fermentation microorganism. During the fermentation process, total sugars were measured. High performance liquid chromatography analyses were used to monitor the fermentation process and to characterize the pear wine. The pear wine obtained was distilled with its lees using three different equipments: a glass alembic (a glass pot still coupled to a glass column), a copper alembic, and a glass alembic with the addition of 5 g/L of copper shavings to the pot still. The same distillations were repeated with the wine without its lees (separated by decanting). Several distillation fractions were collected, up to a total of 500 mL of distillate. Gas chromatography was used to identify and quantify the volatile compounds in each fraction, and the methanol and ethanol contents. Based on these results, the heart fraction was defined. ANOVA tests were performed on the heart fractions to determine quantitative differences between some volatile compounds depending on the equipment used and the presence or absence of the wine lees. From this series of ANOVA tests, it can be concluded that the concentrations of the compounds that are considered to have a negative effect on the quality of the distillates (methanol, ethyl acetate, furfural) decrease or do not change when they are distilled in the presence of lees and in the copper alembic. In addition, the concentrations of the positive compounds (ethyl decanoate and ethyl-2-trans-4-cis-decadienoate) increase in the presence of lees for all of the equipment tested. So, it can be assumed that the distillation of pear wine with its lees in copper alembic leads to a better quality product.

Volatiles from stored Kuerle fragrant pears (Pyrus serotina Reld) were studied using high-resolution gas chromatography and the solid-phase microextraction (SPME) method of gas chromatography/mass spectrometry (GC/MS). The dominant components were hexanal, ethyl hexanoate, ethyl butanoate, ethyl acetate, hexyl acetate, ethanol, alpha-farnesene, butyl acetate, and ethyl (E,Z)-2,4-decadienoate. By using GC-olfactometry, it demonstrated that the volatile compounds from SPME were responsible for the aroma of the Kuerle fragrant pear. The levels of sugars, organic acids, and phenolic acids in Kuerle fragrant pears were investigated using high-performance liquid chromatography (HPLC). Fructose was the dominant sugar, followed by glucose and sucrose. With increasing storage time, sucrose levels decreased; however, changes in fructose and glucose levels were not remarkable. There was a slight decrease in flesh firmness during storage. The general soluble solids concentration (SSC) declined slightly after 5 months storage. Some aroma-related volatile components increased during storage, while others decreased, especially the esters. The organic acids and phenolic acids also changed. The flavor of the Kuerle fragrant pears was affected by the change of volatile compounds and changes in chemical and physical properties.

The structure of a polymeric proanthocyanidin fraction isolated from pear juice was characterized by NMR, ESI/MS, and MALDI-TOF/MS analyses, and its antioxidant activity was investigated using the DPPH free radical scavenging method. The results obtained from 13C NMR analysis showed the predominance of signals representative of procyanidins. Typical signals in the chemical shift region between 70 and 90 ppm demonstrated the exclusive presence of epicatechin units. The results obtained through negative ESI/MS analysis showed singly and doubly charged ions corresponding to the molecular mass of procyanidins with a degree of polymerization up to 22. The spectra obtained through MALDI-TOF/MS analysis revealed the presence of two series of tannin oligomers. Supporting the observations from NMR spectroscopy, the first series consists of well-resolved tannin identified as procyanidin polymers units with chain lengths of up to 25. A second series of monogalloyl flavan-3-ols polymers with polymerization degree up to 25 were also detected. This is the first mass spectrometric evidence confirming the existence of galloylated procyanidin oligomers in pear fruits. Within each of these oligomers, various signals exist suggesting the presence of several oligomeric tannins. The antioxidant properties of the polymeric fraction were investigated through reduction of the DPPH free radical, and the results obtained showed that the polymeric fraction exhibited a higher antioxidant power compared to those of (+)-catechin and B3 procyanidin dimer.

Eight types of microcapsules of European pear (La France) aroma model mixture were prepared, and their retained aroma components and sample microstructures (both surface and cross-section) were compared. The La France pear aroma model mixture was prepared by the mixing of hexanal and five kinds of esters. alpha-Cyclodextrin (alpha-CD), gum arabic (GA), soybean soluble polysaccharide (SSPS), and highly branched cyclic dextrin (HBCD) were used as carrier solids, and spray drying and freeze drying comprised the drying methods. The mean particle size of the microcapsules ranged from 8.34 microm for the microcapsules with alpha-CD to 9.67 microm for those with SSPS. The total aroma contents were different depending upon the microencapsulation systems (1.35 g/100 g of microcapsules for the spray-dried microcapsules with HBCD to 14.1 g/100 g of microcapsules for the freeze-dried microcapsules with GA). The microcapsules with alpha-CD and GA were stable against heat treatment (40, 80, or 120 degrees C for 60 min) under nitrogen gas flow.

Detection of juice-to-juice adulteration based on chemical composition studies is a common method used by government regulatory agencies and food companies. This study investigated the use of major carbohydrate (fructose, glucose and sucrose), polyol (sorbitol), proline, and phenolic profiles as indicators of pear adulteration of apple juice (PAAJ). For this work, a total of 105 authentic apple juice samples from 13 countries and 27 authentic pear juice samples from 5 countries were analyzed. Because the major carbohydrate ranges for these juices showed significant overlap their use as markers for PAAJ detection would be very limited. It was found that sorbitol and proline means for apple and pear were significantly different; however, their broad natural ranges would afford PAAJ at levels up to 30% without detection. In addition, careful selection of the pear juice used as the adulterant would further limit the usefulness of these markers for PAAJ detection. Arbutin was conclusively identified as a marker for pear juice on the basis of its presence in all 27 authentic pear samples and its absence (<0.5 microg/mL) in all 105 apple juice samples analyzed in this study. The application of the developed HPLC-PDA method for arbutin analysis to detect PAAJ at levels as low as 2% (v/v) was demonstrated. A confirmation method for the presence of arbutin in pure pear juice and apple adulterated with pear juice was introduced on the basis of the hydrolysis of arbutin to hydroquinone employing beta-glucosidase, with reactant and product monitoring by HPLC-PDA.

Classifications of geographic growing origin of three fresh fruits combining elemental profiles with various modeling approaches were determined. Elemental analysis (Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, V, and Zn) of strawberry, blueberry, and pear samples was performed using inductively coupled plasma argon atomic emission spectrometer. Bulk stable carbon and nitrogen isotope analyses in pear were performed using mass spectrometry as an alternative fingerprinting technique. Each fruit, strawberry (Fragaria x ananassa), blueberry (Vaccinium caesariense/corymbosum), and pear (Pyrus communis), was analyzed from two growing regions: Oregon vs Mexico, Chile, and Argentina, respectively. Principal component analysis and canonical discriminant analysis were used for data visualization. The data were modeled using linear discriminant function, quadratic discriminant function, neural network, genetic neural network, and hierarchical tree models with successful classification ranging from 70 to 100% depending on commodity and model. Effects of Oregon subregional and variety classification were investigated with similar success rates.

In this work, a single flow injection multicommuted system using solid-surface fluorescence spectroscopy has been explored for the determination of diphenylamine in apples and pears. The native fluorescence signal of diphenylamine retained on the solid support (C18 silica gel) was used for its determination (lambda(exc)/lambda(em) 291/372 nm). The sample treatment consists of a liquid-liquid extraction with acetonitrile followed by a cleanup step using primary-secondary amines. The use of a continuous flow assembly implementing multicommutation, based on a set of three-way solenoid valves controlled by appropriate software, provides the automatic control of sample, carrier, and eluting solution with remarkable advantages in relation to conventional flow injection approaches. Using an optimized sampling time, the proposed method was linear in the range 0.25-5 mg kg(-1) with a detection limit of 0.06 mg kg(-1) and RSD (percent) values better than 3%. The proposed method was successfully applied to the analysis of diphenylamine in different apple and pear samples fortified at different concentrations, and recoveries between 78 and 104% were found. The results obtained illustrate the usefulness of the proposed method for the screening and evaluation of postharvest treatment of crops possibly containing diphenylamine.

The behavior of volatile compounds according to two enzymatic treatments applied during the manufacture of fruit juice is described. More than 80 compounds were detected of a wide range of chemical families (alcohols, aldehydes, ketones, terpenoids, esters, norisoprenoids, ...). Theaspirane and alpha-isophoron were tentatively identified for the first time in apricot and peach fruits. The enzymes used, for extraction or clarification of fruit juices, modified the polysaccharides separated by molecular weight and the content of soluble polysaccharides. This could indicate differences in the fruit juice matrix, which could be related to observed changes in the volatile profile. In apricot, the enzymes enhanced the juice in terpenes and norisoprenoids as varietal compounds. In peach and pear, the enzymes used did not favor the amount of lactones and decadienoate esters, the character impact compounds, respectively.

The interaction between aliphatic acetate esters, which are the major flavor components of La France pear (Pyrus communis L.), and cyclodextrins (CDs) was studied to obtain fundamental data for preparing powdered pear flavor materials. The complexing abilities of alpha-, beta-, or gamma-CD with six kinds of aliphatic acetate esters were compared. alpha-CD formed the highest numbers of complexes with all of the esters. All of the CDs produced complexes more readily with the more hydrophobic esters. Among our samples of freeze-dried pear juice containing dissolved alpha-, beta-, or gamma-CD, the juice with alpha-CD retained the greatest amount of esters. These data demonstrate that alpha-CD is an effective material with which to prepare powdered pear flavor materials. The nuclear Overhauser effect, measured by (1)H NMR spectra, of an alpha-CD-butyl acetate or alpha-CD-hexyl acetate complex showed that these esters were included in the alpha-CD cavity.

Codling moth, Cydia pomonella (L.), is a severe pest of apples, pears, and walnuts worldwide, and new approaches for precise monitoring and management would be beneficial. Ninety-two pome fruit volatiles were formulated in 23 distinct blends, of which a single 4-component blend of 10-carbon esters showed the only significant attraction of moths in field bioassays conducted in both walnut and apple orchards. A single constituent of this blend, ethyl (2E,4Z)-2,4-decadienoate--the "pear ester", was the major contributing attractant. The pear ester attracted both male and female moths in combined numbers that were comparable to the attractiveness of conspecific sex pheromone. Structure-activity tests were conducted in a series of orchard trials to determine the specificity of attraction of codling moths to the pear ester kairomone. No analogue 10-carbon alcohols, aldehydes, acetates, or other esters elicited significant moth capture responses. Tests with various analogue esters with alcohol chain length moiety substitutions of the (2E,4Z)-2,4-decadienoic acid elicited differential capture responses, with the ethyl exceeding the propyl, methyl, butyl, and hexyl analogues. The (E,Z) geometric isomers of this series of (2E,4Z)-2,4-decadienoic acid esters far exceeded the attractiveness of the (E,E) isomers. The pear ester is a potent attractant of both males and females, and codling moths are highly discriminating and specific in their structure-activity-based attraction to this pear-derived kairomone. These specificity attributes should allow this host plant kairomone to contribute to new abilities for female monitoring and the potential of development of novel and highly selective control practices that should decrease the current dependence on the use of broad-spectrum insecticides.