Sie sind auf Seite 1von 10

JFS S: Sensory and Nutritive Qualities of Food

Effect of UV Irradiation on Cut Cantaloupe: Terpenoids and Esters


JOHN C. BEAULIEU
ABSTRACT: Recent studies demonstrated that ultraviolet (UV) radiation enhanced terpenoids and decreased esters in thin-sliced cantaloupe. In preliminary studies treating fresh juices with UV, terpenoid compounds that normally were not isolated, or found in minute quantities, were elevated and only low molecular weight alcohols, ketones, and aldehydes decreased. Subsequently terpenoid induction/oxidation in UV-treated cut cantaloupe was reinvestigated. UV exposure increased the concentrations of terpenoids in cantaloupe tissue. However, UV exposure alone was not the sole factor responsible for enhanced terpenoids. UV-enhanced terpenoid production appears to be both cultivar- and maturity-dependent. Concomitant decreases in the ester content of UV-treated samples occurred using a previously published system. Yet, we established that almost identical ester losses occurred in thinly sliced laminar tissue receiving 60 min UV or air exposure in an open system. Tissue samples that were exposed to UV in a closed system often did not suffer correspondingly equal ester loss. Marked tissue warming (4.3 0.5 C in 60 min) occurred during UV treatments in thin-sliced tissue. Ester loss from cantaloupe tissue was caused by the experimental procedure, but not by UV treatment per se. These findings are supported by the observation that UV is not responsible for chemical transformations to ester bonds, esterase, and lipase decrease in stored cut cantaloupe, and no lipid oxidation volatiles were observed in thin-sliced control tissue, while oxidized terpenoids were recovered. Information gathered indicates that improper cutting, handling, sanitation treatment, and storage can radically alter the desirable volatile aroma profile in cut cantaloupe, and potentially lead to decreased consumer acceptance. Keywords: cantaloupe, Cucumis melo L. Naudin, cucurbitaceae, ester, flavor-aroma, GC-MS, phytoalexins, SPME, terpenoid, volatiles

Introduction
ono-, di-, and tetraterpene compounds found in plants are naturally produced from the methylerythritol phosphate ([MEP] or nonmevalonate) pathway (Bohlmann and others 1998; Dudareva and others 2005) and are considered both primary and secondary metabolites (Hugueney and others 1996). Some secondary metabolites, oftentimes referred to as phytoalexins, predominantly serve to protect plants against herbivores (for example, pyrethroids, C 10 monoterpenes, and C 15 sesquiterpenes), microbial infection, or as attractants for pollinators and seed dispersal (Taiz and Zeiger 2002). Terpenoid production is known to be enhanced by wounding, UV irradiation (Back and others 1998), and general oxidation in plant tissues (Bailey and Mansfield 1982). In preliminary collaborative studies with a fresh juice company, we observed that a vegetable blend (Essential Greens) and watermelon juice exposed to UV passing through transparent tubing in an in-line process (Anonymous 1999a, 1999b) had markedly different volatile profiles compared with those of controls. Specifically, terpenoid compounds that normally were not isolated or found in minute quantities were elevated, while low molecular weight alcohols, ketones, and aldehydes decreased. Recent studies have assessed the effects of UV radiation on thin-sliced cantaloupe (Lamikanra and others 2002) and pineapple (Lamikanra and Richard 2004), prepared in a manner to maximize UV penetration on cut surface area and induce stress conditions.
MS 20060662 Submitted 12/1/2006, Accepted 2/9/2007. Author Beaulieu is with US Dept. of Agriculture, Agricultural Research Service, Southern Regional Research Center, Food Processing & Sensory Quality Unit, 1100 Robert E. Lee Blvd., New Orleans, LA 70124. Direct inquiries to author Beaulieu (Email: beaulieu@srrc.ars.usda.gov).

The presence of several cyclic and acyclic terpenoid compounds was documented in UV-treated cantaloupe, but not in controls. Yet, numerous terpenoids have been isolated in Cucumis melo utilizing a diverse array of methods (Table 1). They were recovered via solid phase microextraction (SPME) coupled to gas chromatography mass spectrometry (GC-MS) in all ripeness stages of 2 cantaloupe cultivars (Beaulieu and Grimm 2001). Interestingly, rapid, corresponding loss of aliphatic esters (up to 60%) was also reported after both 15 and 60 min UV treatments in stored (4 C) UV-treated control tissue (Lamikanra and others 2002; Lamikanra and Richard 2004). Furthermore, substantial ester losses were also reported in control tissue that was prepared in a similar fashion, after 24 h (Lamikanra and Richard 2002; Lamikanra and others 2003; Lamikanra 2004). Thus far, in numerous GC-MS and sensory analyses performed on various fruits that were cut according to fresh-cut industry practices, rapid marked ester or aroma losses were generally not observed in stored apple (Bett and others 2001; Beaulieu 2006a), cantaloupe (Beaulieu and Baldwin 2002; Bett-Garber and others 2003; Beaulieu and Lea 2003a; Beaulieu 2005, 2006a, 2006b), honeydew (Saftner and others 2003; Beaulieu 2006a), mango (Beaulieu and Lea 2003b), and pineapple (Spanier and others 1998). If absorbed, it is theoretically possible for UV light to affect OH, CC, CH, CN, NH, and SS bonds, yet the dissociation energy required is relatively high for some of these bonds (March 1985). In organic compounds, nucleic acid bases are the strongest absorbers of UV-C (Jagger 1967), and roughly 93% of UV light administered to fruit and vegetable juices was absorbed by nucleic acids (Anonymous 1999b). The remaining energy can affect conjugated bonds such as aromatic and unsaturated molecules, aromatic amino acids, and disulfide bonds that are found in some vitamins, cofactors, and pigments (Spikes 1981). According to absorption
No claim to original US government works C 2007 Institute of Food Technologists doi: 10.1111/j.1750-3841.2007.00327.x
Further reproduction without permission is prohibited

S: Sensory & Nutritive Qualities of Food

S272

JOURNAL OF FOOD SCIENCEVol. 72, Nr. 4, 2007

Table 1 --- Terpenoids reported in fresh Cucumis melo (muskmelon and cantaloupe) tissue Common name a Sensory attributesb Citations Homatidou and others 1992 Wyllie and others 1994; Homatidou and others 1992; Beaulieu and Grimm 2001 woody, piney citrus, sweet, lemon, orange, mild, peely camphoreous, cool, spicy, fresh lemon, citrus, herbaceous, sweet, tropical sweet, green, grassy, oral, hay-like lemon lemon, strong rosy, delicate, green, magnolia, fresh --herbaceous, sweet, fresh --warm, woody, dry fruit, balsamic, oral, rosy, raspberry-like, violet black tea black tea honey, oral fragrant, oral, lilac woody, spicy, clove Beaulieu and Grimm 2001 Homatidou and others 1992; Beaulieu and Grimm 2001; Shalit and others 2001; Lamikanra and Richard 2002; Lamikanra and others 2002 Homatidou and others 1992 Shalit and others 2001; Lamikanra and others 2002 Lamikanra and others 2002 Kemp and others 1971, 1972, 1973; Horvat and Senter 1987; Homatidou and others 1992; Beaulieu and Grimm 2001; Shalit and others 2001; Lamikanra and others 2002; Aubert and Bourger 2004 Beaulieu, unpublished Homatidou and others 1992; Nussbaumer and Hostettler 1996; Lamikanra and Richard 2002; Lamikanra and others 2002; Beaulieu, unpublished Shu and others 1995 Shu and others 1995 Shalit and others 2001

IUPAC (chemical) name

Schieberle and others 1990; Homatidou and others 1992; Beaulieu and Grimm 2001; Jordan and others 2001; Lamikanra and Richard 2002 Homatidou and others 1992 Homatidou and others 1992; Beaulieu and Grimm 2001; Lamikanra and others 2002; Aubert and Bourger 2004 Beaulieu and Grimm 2001

Effect of UV irradiation on cut cantaloupe . . .

-pinene (18172-67-3) 6,6-Dimethyl-2-methylenebicyclo-[3.1.1]-heptane limonene (5989-27-5) 1-Methyl-4-isopropenyl-1-cyclohexene 1,8-cineole; eucalyptol (470-67-7) 1-Methyl-4-(1-methylethyl)-7-oxabicyclo[2.2.1]heptane -terpinene (99-85-4) 1-Methyl-4-isopropyl-1,4-cyclohexadiene -cyclocitral 2,6,6-Trimethyl-1-cyclohexene-1-carboxaldehyde Z -neral ( -citral) (106-26-3) (Z) 3,7-Dimethyl 2,6-octadienal E -geranial ( -citral) (141-27-5) (E) 3,7-Dimethyl 2,6-octadienal (E )-geranylacetone c 6,10-Dimethyl 5,9-Undecadie-2-one (E) terpinyl acetone -terpinyl acetate p-Menth-1-en-8-yl acetate (Z)- -ionone, cis (Z) 4-(2,2,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one (E)- -ionone, trans (14901-07-6) (E) 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one

-----

Shalit and others 2001 Horvat and Senter 1987; Beaulieu and Grimm 2001

S: Sensory & Nutritive Qualities of Food

Vol. 72, Nr. 4, 2007JOURNAL OF FOOD SCIENCE

(E)- -ionone epoxide (23267-57-4) (E) -ionone-5, 6 epoxide dihydroactinidiolide (15356-74-8) 2(4H)-Benzofuranone, 5,6,7,8a-tetrahydro-4,4,7a-trimethyl cinnamic acid, cinnamate (140-10-3) 3-Phenyl-2-propenoic acid -terpineol (10482-56-1) 1-Methyl-4-isopropyl-1-cyclohexen-8-ol -caryophyllene (87-44-5) 2-Methylene-6,10,10-trimethyl bicyclo[7.2.0]undec-5-ene or 4,11,11-Trimethyl-8-methylenebicyclo [7.2.0]undec-4-ene -cadinene delta-cadinene -farnesene (502-61-4) 3,7,11-Trimethyl-1,3,6,10-dodecatetraene

a CAS numbers are listed in parenthesis for compounds not reported in Table 2. b Sensory attributes from FlavorWorks version 2.0 (Flavormetrics Inc., Anaheim Hills, c

Calif., U.S.A.), or from references reported herein.

No reports were found for the cis (Z) isomer (nerylacetone)

S273

Effect of UV irradiation on cut cantaloupe . . .


spectra, ultraviolet chromophores are likely candidates for UV-C induced change/degradation (for example, breakage, tautomeric shifts). However, ester- and acetate-associated bonds (C = O, CC, CO, CH) do not have absorption bands in this wavelength range (Scott 1955) and are not cleaved (Jagger 1967). It therefore seems highly improbable that UV per se was responsible for the reported ester loss in thinly sliced cantaloupe tissue. Since numerous terpenoids have been reported in cantaloupe, and are reported to have potential phytoalexic properties, we reinvestigated terpenoid induction/oxidation in UV-treated cut cantaloupe. Furthermore, the effect of UV irradiation on ester loss in UV-treated stored, cut cantaloupe was reevaluated.

Sample preparation
Whole fruit was sanitized in 100 ppm bleach (5.25% ClNaO) and uniformly peeled on a Muro CP-44 melon peeler (Tokyo, Japan). Stem and blossom portions (2 to 3 cm) were cut off, melons sliced in half, seeds removed, and the seed cavity was cleaned free from loose endocarp tissue (1- to 2-mm thickness removed) with a sharp knife. Equatorial mesocarp tissue was used to prepare thinly sliced laminar slices of tissue on a Hobart model 512TMS (Troy, Ohio, U.S.A.) (1.94 0.08 mm thick, n = 18) or via a hand-held mandolin kitchen slicer (Robinson Knife Co., Buffalo, N.Y., U.S.A.) with a straight-edge blade (2.67 0.11-mm thick, n = 40). Slice thickness was measured with an electronic hand-held vernier caliper. Approximately 2 3 2.5 cm cubes were prepared in pie-like wedges as previously described (Beaulieu and Lea 2003a). Cubes were stored in Juice Catcher clamshell containers (Winkler Forming, Carrolton, Tex., U.S.A.) at 4 C for up to 9 d.

Materials and Methods


Cantaloupe fruit material
Fruits used in this study were from 4 different western shipper orange-fleshed cantaloupe (C. melo L. Naudin) cultivars. Various sampling regimes UV treatment were performed on fruits from cv. Esteem that was grown under standard cultural practices with furrow irrigation in California. Ripe fruits were harvested at 3/4- slip, force air cooled, boxed with Styrofoam beads, air freighted overnight to the SRRC, and analyzed within the week. Analyses with Esteem, described below, were carried out on either ripe (3/4-slip, 10.28 0.60 Brix, n = 18) or fully ripe (11.57 0.54 Brix, n = 18) fruit. Two additional unknown cultivars were store bought: cultivar 1 was judged very ripe (10.45 0.05 Brix, n = 10) based on intense aroma and texture upon cutting, whereas the second cultivar was less ripe (10.19 0.52 Brix, n = 10), lacking intense aroma and being more firm upon cutting. Esteem and store bought cultivars were used to assess volatile differences when UV treatments were administered to laminar slices. Sol Real fruit was procured and assessed in maturity-related (1/4, 1/2, 3/4, full slip and over-ripe) experiments, as previously described (Beaulieu 2006b).

Acetylation of GC-MS standards


A mixture of the 2,3-butanediol stereoisomers, the isolated enantiomer (R,R) 2,3-butanediol, -terpineol, and chemical reagents were obtained from Sigma-Aldrich (St. Louis, Mo., U.S.A.). The diols were placed in pyridine in the presence of excess acetic anhydride and heated 4 h at 60 C. Acetylation was complete as no diols were observed in the GC-MS trace in the reaction mixture. Terpinyl acetate was formed similarly: -terpineol was placed in pyridine in the presence of excess acetic anhydride and sodium acetate. The mixture was heated for 4 h at 60 C. Complete acetylation was not observed, as -terpineol was still present in the reaction mixture. However, a sufficient amount of -terpinyl acetate was formed to provide a match with the mass spectral library.

Ultraviolet irradiation
Laminar slices of tissue were carefully placed into 100-cm glass Petri dishes positioned 5 cm above the light source, and exposed

Table 2 --- Target and qualifying ions used for peak area integration of selected volatile and semivolatile compoundsa Compound Ethyl 2-methyl propanoate Methyl 2-methyl butanoate Ethyl butanoate Ethyl 2-methyl butanoate 3-methylbutyl acetate 2-methylbutyl acetate Ethyl hexanoate Hexyl acetate 2,3-butanediol diacetate (meso) c 2,3-butanediol diacetate (R,R) 2,3-butanediol diacetate (S,S) benzyl acetate 1,3-butanediol diacetate d amyl isovalerate (IS) e 1,4-butanediol diacetate d benzothiophene (IS) e -cyclocitral (Z )-nerylacetone -terpinyl acetate (Z )- -ionone (E )-geranylacetone (E )- -ionone RT b (min) 7.61 8.15 8.77 10.29 11.19 11.21 14.49 14.72 15.63 15.89 15.89 16.76 17.35 17.92 18.54 18.83 19.12 19.70 20.86 21.06 21.80 22.19 RI (DB-5) 773 790 811 860 886 887 1004 1016 1059 1071 1071 1112 1145 1176 1210 1229 1247 1283 1372 1388 1469 1518 Target ion (m/z ) 71 88 71 102 70 70 88 84 87 87 87 108 87 85 71 134 137 69 121 177 69 177 Qual. ion (m/z ) 116 101 88 115 101 101 101 61 130 130 130 150 130 70 54 108 152 151 136 192 151 192 CAS nr 97-62-1 868-57-5 105-54-4 7452-79-1 123-92-2 624-41-9 123-66-0 142-92-7 17998-02-6 22152-23-4 73136-10-4 140-11-4 1117-31-3 2445-77-4 628-67-1 95-15-8 432-25-7 3879-26-3 8007-35-0 35031-06-2 3796-70-1 79-77-6 ID MS, RI MS, RI MS, RI MS, RI MS, RI MS, RI MS, RI MS, RI RT, MS RT, MS MS MS, RI RT, MS RT, MS RT, MS RT, MS RT, MS RT, MS RT, MS MS RT, MS RT, MS

S: Sensory & Nutritive Qualities of Food

a Recovery via 100-m PDMS solid phase microextraction (SPME) and GC-MS. Esters displayed correspond with compounds generally considered as avor-important in various muskmelon, according to compiled literature reported in (Beaulieu 2006a). b RT = retention time; RI = retention index, based on mass spectra library matches (MS) and/or an in-house RI via identications (ID) of the target ion and qualifying ion (Qual. ion) at the RT of purchased standards, as previously published (Beaulieu and Grimm 2001), or purchased and synthesized diacetate ester standards according to the Materials and Methods. c Meso stereoisomer; R,S. d Standard only. Not observed in any cantaloupe fruit samples, as previously reported (Lamikanra and others 2002). e IS = internal standard.

S274

JOURNAL OF FOOD SCIENCEVol. 72, Nr. 4, 2007

Effect of UV irradiation on cut cantaloupe . . .


to UV for 0, 15 (UV-15), or 60 min (UV-60) on a Fotodyne 3-3000 Transilluminator (Fotodyne Inc., Hartland, Wis., U.S.A.) as previously described (Lamikanra and others 2002). Samples received UV treatments in open and closed (static) Petri dishes because the original method did not describe this aspect of the system, and it was of interest to investigate volatile changes under possible vapor saturating and desiccating conditions. Controls consisted of freshly sliced laminar slices sampled immediately (control) and after 60 min (CON-60). Internal tissue temperatures and ambient temperatures were measured during UV treatment with an electronic thermocouple (Fluke, Everett, Wash., U.S.A.) equipped with thin-wire probes (Alumel chromel, 0.4-mm dia). volatile response on each day, combining experiments for both maturities. Both absolute and normalized abundance for most compounds on day 0 in slices were substantially higher than the abundances found throughout storage (days 1 and 3), and in some treatments/maturities, leading to nonhomogeneous variance. Therefore, all data were log-transformed, and results are presented in Table 3 and 4. Analyses (PROC MIXED in SAS) were performed on the log-transformed volatile data to meet an assumption of normal distribution and common variance between treatments. To obtain comparisons of days for a given treatment in Table 4, an additional PROC MIXED SAS analysis was performed on the data combined over days, where days was treated as a repeated measure subunit. The unequal variances between the days were modeled using a heterogeneous compound symmetry covariance structure (Littell and others 1996). Treatment and interactions of maturity and treatments were evaluated using an F -test (P 0.05) from the ANOVA and comparisons of treatment means. Log-transformed treatment means were transformed back to the original scale (geometric means) for presentation in Table 3, 4 and 5. Although normalization patterns were statistically very similar, ester and terpenoid recovery on an absolute basis was much greater in more mature fruit compared with less mature fruit, as generally found in cantaloupe (Wyllie and others 1996; Pratt 1971; Beaulieu and Grimm 2001; Beaulieu 2005, 2006b). Subsequently, only data for more mature fruit and the combined analysis were presented in Table 3 and 4.

Volatiles analysis
The sampling and GC-MS method described by Lamikanra and others (2002) was employed for laminar slices, with minor modifications. Roughly 2 mm from the laminar slice edges was removed, tissue was chopped finely, and 3 g was placed in 10-mL vials with 1 g NaCl, 100 ppb (w/w, final concentration) mixed benzothiophene and amyl isovalerate internal standard (IS), magnetic stir bar, and capped with a Teflon/silicone septum. The IS concentration was increased from 1.55 ng/kg to 100 ppb (w/w) since we failed to recover benzothiophene at 1.55 ng/kg by SPME GC-MS with 2 different SPME fibers tested, in both water and cantaloupe homogenate. Samples were agitated so that the magnet pulverized the tissue into a semiliquid state for 15 min on a Combi-Pal (Leap Technologies, Carrboro, N.C., U.S.A.) autosampler with maximum agitation (700 rpm). A 15-min agitation period was employed followed by a 15min SPME adsorption period (100 rpm) while holding the sample at 30 C. SPME was employed using automated 1-cm 100-m PDMS fibers (Supelco Inc., Bellefonte, Pa., U.S.A.). Volatile compounds were thermally desorbed into the injection port of an Agilent 6890 GC for 4 min at 270 C, containing a Zebron ZB-5 (cross-linked 5% phenyl methyl silicone (Phenomenex, Torrance, Calif., U.S.A.) column (30 m, 0.25 mm i.d., 1.0-m film thickness) coupled to an Agilent 5973 MS. Cryofocusing at 70 C was employed during desorption and the GC oven was initially held 1 min at 50 C in the splitless mode. The oven temperature was then increased at 5 C/min to 100 C, then 10 C/min to 190 C and 30 C/min to 250 C, and held for 2.33 min. The quadrupole MS was operated in the electron ionization mode at 70 eV, with a continuous scan from m/z 33 to 300. Samples were run in triplicate and peak areas based on selected ions were normalized on benzothiophene, and averaged. Selected ions used for integrated peak area calculation, retention times (RT), and retention indices (RI) are presented in Table 2. The identification of single components was performed by comparison of mass spectra (NIST Database, v. 1.5, Palisade Corp., Newfield, N.Y., U.S.A.), authentic or synthesized standards, and RI based on nalkanes (heptaneeicosane) as denoted in Table 2. Fresh-cut cubes (cv. Sol Real) were analyzed without cryofocusing as previously described (Beaulieu and Grimm 2001).

Results and Discussion


UV enhances terpenoids and oxidation products
Roughly 20 terpenoids have been reported in the literature in various C. melo (cantaloupe and muskmelon) by several analytical techniques (Table 1). We previously reported numerous terpenoids (for example, limonene; 3-ethyl, 2-methyl-1,3-hexadiene; -cyclocitral; (Z )-neral; (E )-geranial; geranylacetone; -ionone, and -farnesene) in cantaloupe tissue (Beaulieu and Grimm 2001). Terpenoids are secondary metabolites and naturally occurring in cantaloupe. Terpenoids and their oxidation products were observed (Table 2) and were UV-enhanced in all cantaloupe cultivars tested (Table 35), as previously reported (Lamikanra and others 2002). Terpenoids that generally increased significantly because of UV were -cyclocitral, (Z )- -ionone, geranylacetone, and (E )- -ionone (Table 3 and 4). The dominant UV-enhanced terpenoid observed in cantaloupe was geranylacetone. Geranylacetone and (E )- -ionone also increased markedly with increased UV treatment in watermelon juice, independent of added ascorbic acid (data not shown). -cyclocitral, nerylacetone, (Z )- -ionone, geranylacetone, and (E )- -ionone increased significantly after UV exposure in the open system, and often increased significantly in the closed system (Table 3). Nerylacetone increased significantly only after UV treatments in the open system (Table 3). The 15-min UV treatment (UV15) generally yielded comparable levels of terpenoids relative to the 60-min UV (UV-60) treatments (Table 3). UV-enhanced terpenoids were observed in samples treated in open Petri dishes (Table 3), and in sealed dishes (static) (Table 3 and 4). Terpenoids observed in freshly sliced controls, sampled immediately (control 0 min), were generally not significantly different than controls that were air-exposed for 60 min (CON-60) (Table 3). The only exception to this trend occurred with -terpinyl acetate, which was significantly lower after the 60 min air exposure. The highest terpenoid levels in thin-sliced tissue were observed immediately after UV-15 static treatments, and occasionally, after 3-d storage in UV-60 treatments (Table 4). The terpenoids
Vol. 72, Nr. 4, 2007JOURNAL OF FOOD SCIENCE S275

Statistical analysis
Individual repeated experiments were performed with fruits of different maturity, corresponding to each data table presented (Table 3, 4, and 5). Each experiment was a completely randomized design with 3 replicates per treatment. Experimental units to which the treatments were applied were thin slices or cubes of cantaloupe. In data for Table 4, measurements were taken over time (0, 1, and 3 d); however, owing to nonhomogeneous variances between days, each day was analyzed separately to obtain comparisons for treatments for that day. An ANOVA (SAS/STAT Users Guide, Version 8, 1999, SAS Institute Inc., Cary, N.C., U.S.A.) was performed for each

S: Sensory & Nutritive Qualities of Food

Effect of UV irradiation on cut cantaloupe . . .


-cyclocitral, (Z )- -ionone (very mature fruit only), geranylacetone, and (E )- -ionone in static UV-60 increased significantly during storage (Table 4). In UV-15, most enhanced terpenoids significantly decreased through 3-d storage, except for (E )- -ionone and nerylacetone (Table 4). Terpenoids increased slightly after 3-d storage in control tissue and only -cyclocitral increased significantly (Table 4). However, the relative increases observed in control tissue were nominal compared with those increases observed in UV-treated tissue. Almost all UV treatments (15 and 60 min, open and static) invoked significantly similar increases in terpenoids (Table 3); however, an inconsistent trend was observed regarding enhanced terpenoid responses in the storage study with a different cultivar (Table 4). Degree of initial wounding response and/or oxidation, followed by apparent surface desiccation and entrapment of certain volatiles, might explain these differences. Variations observed regarding consistent trends in 15- versus 60-min UV for some terpenoid isomers could likewise be related to the native instability of cis (Z ) and trans (E ) isomers, which tautomerize and/or oxidize spontaneously, or enzymatically convert at inconsistent rates. Furthermore, various factors such as cultivar, maturity, and relative state of desiccation could be responsible for occasional variations in a given trend. Nonetheless, these data indicate that the terpenoids were synthesized in direct response to UV, independent of sampling regime, or cultivar. Yet, some terpenoids also increased during storage in control laminar slices, likely due to wounding and oxidation or stress-induced desiccation.

Predominant terpenoid oxidations in fresh-cut cantaloupe


(E )- -ionone, (Z )- -ionone, -ionone epoxide, and dihydroactinidiolide were observed in various cultivars of freshly sampled cantaloupe tissue (Figure 1; Table 1, 3 to 5). These compounds generally increased significantly immediately following UV-15 and UV-60 exposure (Table 3 and 4), and toward the end (9 d) of storage as freshcut cubes (Figure 1). Several flavor-related terpenoids in plants are secondary oxidation products (Beaulieu and Baldwin 2002), oftentimes derived from -carotene (Isoe and others 1969; Weeks 1986). For example, dihydroactinidiolide and (E ) -ionone-5, 6-epoxide have been associated with the aroma of black tea (Sanderson and Graham 1973). Buttery predicted that oxidative products found in tomato ( -ionone, geranylacetone, and 6-methyl-5-hepten-2-one) would be derived from carotenoids (Buttery and others 1988), and ionone and geranylacetone are in vivo oxidation products in tomato derived from -carotene, and lycopene or -carotene or phytoene, respectively (Simkin and others 2004). -carotene is a strong absorber of UV light (Jagger 1967) and two of the primary oxidation products were (Z ) and (E )- -ionone, which have been reported as -carotene oxidation products. Cantaloupe and fresh-cut cantaloupe possess relatively high carotenoid concentrations that decrease after cutting during storage (Gil and others 2006). Carotenoids are unstable when exposed to light, oxygen, reduced water vapor, metal catalysts, or acidic pH (Klein 1987;

Table 3 --- UV-enhanced terpenoids, oxidative compounds and ester recovery (SPME, GC-MS) in laminar cantaloupe tissue slices sampled immediately after receiving 0, 15 and 60-min UV in an open and static system Compoundsa Very ripe fruitb Ethyl 2-methyl propanoate Methyl 2-methyl butanoate Ethyl butanoate Ethyl 2-methyl butanoate 3-methylbutyl acetate Ethyl hexanoate Hexyl acetate 2,3-butanediol diacetate (meso) 2,3-butanediol diacetate (mix)c Benzyl acetate -cyclocitral (Z )-nerylacetone -terpinyl acetate (Z )- -ionone (E )-geranylacetone (E )- -ionone Combined maturity Ethyl 2-methyl propanoate Methyl 2-methyl butanoate Ethyl butanoate Ethyl 2-methyl butanoate 3-methylbutyl acetate Ethyl hexanoate Hexyl acetate 2,3-butanediol diacetate (meso) 2,3-butanediol diacetate (mix)c Benzyl acetate -cyclocitral (Z )-nerylacetone -terpinyl acetate (Z )- -ionone (E )-geranylacetone (E )- -ionone
a Normalized b

Control (0 min) 154.9Az 71.5A 1678.2A 1788.7A 1211.8A 851.1A 18.0A 4.8A 2.0A 737.0A 0.211B 0.024CD 0.106AB 0.032B 0.360B 0.289B 21.3A 32.0A 164.6A 119.5A 457.2A 43.7A 13.2A 4.1A 1.8A 189.9A 0.119B 0.013C 0.052AB 0.022B 0.205B 0.145B

UV-15 (15 min [open]) 115.1A 56.7A 1372.1A 1427.7A 998.2A 656.9A 15.6A 4.2A 2.3A 680.1A 1.390A 0.103AB 0.054CD 1.861A 13.686A 0.594A 16.9A 26.9A 123.0AB 96.3A 374.0A 33.9A 12.1A 3.1A 1.7A 175.6A 0.691A 0.060AB 0.040B 0.995A 9.124A 0.333A

UV-60 (60 min [open]) 30.4C 17.6B 477.6B 435.2B 382.1B 234.8B 6.2B 4.5A 2.2A 606.3A 1.607A 0.120A 0.084BC 2.121A 17.329A 0.598A 6.0C 9.4C 43.4D 32.8C 156.7C 16.4B 6.4BC 3.7A 1.8A 145.4A 0.749A 0.073A 0.058AB 1.183A 9.479A 0.324A

CON-60 (60 min [open]) 38.3BC 21.9B 577.7B 536.4B 423.4B 281.3B 7.6B 4.2A 2.3A 436.2A 0.235B 0.012D 0.042D 0.027B 0.266B 0.280B 7.5BC 11.6BC 60.6CD 43.7BC 182.4BC 18.2B 6.1C 3.2 A 1.6A 139.6A 0.142B 0.012C 0.029B 0.091B 0.577B 0.147B

UV-60 (60 min [static]) 49.0B 28.5B 821.9AB 625.8B 571.0B 333.8B 11.2AB 4.8A 2.6A 680.7A 1.676A 0.064BC 0.133A 2.432A 17.748A 0.627A 10.2B 14.9B 91.0BC 56.7B 240.2B 22.6B 9.6AB 4.0A 2.1A 177.1A 0.744A 0.033BC 0.079A 1.092A 6.148A 0.324A

S: Sensory & Nutritive Qualities of Food

on the benzothiophene internal standard. Data presented are statistical geometric means (n = 3 per measure) from unknown cultivars of store-bought very ripe fruit, and the combined maturity (ripe fruit plus very ripe fruit), according to the M&M. c Mix indicates that this compound could be the 2,3-butanediol diacetate R,R and/or S,S isomer. Geometric means across rows (per compound) not followed by a common letter are signicantly different (P = 0.05) based on the log transformed values.

S276

JOURNAL OF FOOD SCIENCEVol. 72, Nr. 4, 2007

Effect of UV irradiation on cut cantaloupe . . .


Dorantes-Alvarez and Chiralt 2002), and these events occur during excessive cutting and subsequent UV exposure. Under oxidative stress, -ionone (Isoe and others 1969; Buttery 1981; Kotseridis and others 1998) and other oxidation or enzymatic products such -ionone epoxide (Sanderson and Graham 1973) and the lactonic carotenoid dihydroactinidiolide (Isoe and others 1969; Etoh and Ina 1979) have been observed. In compromised tissue (laminar slices, CON-60), there was not a significant short-term increase in (Z )or (E )- -ionone compared with the controls (Table 3), but (E )- ionone increased markedly from 7 to 9 d during fresh-cut storage (Figure 1). In thin-sliced tissue exposed to UV, (Z )- and (E )- -ionone increased significantly on day 0, and through storage days 1 and 3, except for 1 anomaly; there was decreased recovery of (Z )- -ionone in UV-15 (Table 4). These data indicate generally that the resultant oxidative terpenoids are generated immediately after UV, after stress (desiccation), or after longer-term storage. Various terpenoid synthase reactions, followed by a variety of modifications (for example, deprotonation, hydride shifts, oxidative cleavage, isomerization), are known to generate numerous acyclic and cyclic terpenoid metabolites in plants (Bohlmann and others bler and others 2004), including fatty acyl esters related to 1998; Ga nerol and geraniol (Dunphy 2006). Products such as nerylacetone,

Table 4 --- UV-enhanced terpenoids, oxidative compounds, and ester recovery (SPME, GC-MS) in laminar tissue slices of Esteem cantaloupe receiving 0-, 15-, and 60-min UV in a static system, stored 0, 1, or 3 d at 4 C Full-slip, fully ripea Compounds
b

Combined maturity UV-60 5.6 Ba 0.5Ab 0.4Ab 10.1Ba 5.1Aa 7.6Aa 83.2Ba 35.8Ab 56.4Aab 47.5Ba 4.5Ab 7.8Ab 93.6Ba 22.6Ab 1.5Ac 14.7Bb 45.0Aa 69.2Aa 6.9Ca 1.0Ab 0.3Ac 2.3Ba 1.3Cb 0.6Bb 0.6Cb 1.3Aa 0.9Ca 68.1Ca 37.9ABb 0.2Ac 0.076Bc 0.119Ab 0.166Aa 0.001Aa 0.006Aa 0.005Aa 0.039Aab 0.040Aa 0.020Ab 0.175Bb 0.205Ab 0.272Aa 0.710ABb 2.107Aa 2.483Aa 0.036ABc 0.143Ab 0.411Aa Fresh 6.5Aa 0.7Ac 0.1Be 22.3Aa 14.6Aab 8.7Acd 29.0Aa 18.3Abc 5.1Cd 26.5Aa 6.5Abc 1.0Ce 221.1Aa 7.9ABde 3.3Af 9.8Acd 19.0Aab 6.2Cde 8.6Aa 0.7Acd 0.5Ae 1.4Aab 1.4Aa 0.6Bcd 0.4Bc 0.6Ab 0.9Aa 199.4Aa 20.6Ad 3.3Ae 0.034Ce 0.049Bde 0.095Bb 0.006Ab 0.006Aab 0.011Aab 0.044Aab 0.014Bd 0.013Ad 0.014Ce 0.012Ce 0.023Ce 0.040Be 0.113Ce 0.303Bde 0.029Bd 0.033Bcd 0.044Ccd UV-15 6.9Aa 0.4Acd 0.1Be 21.4Aa 7.2Bcde 4.2Cf 29.1Aa 13.1Ac 13.7Bc 34.5Aa 4.3Acd 3.0Bd 151.8Bb 5.7Be 2.7Af 9.2Ad 15.3Abc 16.9Bb 7.5Aa 0.7Acde 0.5Ade 1.6Aa 1.0Bbc 1.8Aa 0.5Ab 0.5Abc 1.2Aa 145.7Bb 16.6Ad 3.6Ae 0.126Aa 0.067ABcd 0.095Bb 0.011Aab 0.009Aab 0.011Aab 0.040Aabc 0.021ABcd 0.012Ad 0.244Aa 0.123Bc 0.051Bd 1.498Aa 0.602Bbc 0.410Bcd 0.057Ac 0.052Bcd 0.099Bb UV-60 3.4 Bb 0.5Acd 0.3Ad 10.4Bbc 6.2Bdef 5.8Be 15.2Bc 18.8Aab 25.6Aabc 22.7Aa 5.1Abcd 7.2Ab 66.3Cc 13.0Ad 3.2Af 5.2Be 23.2Aab 29.2Aa 3.4Bb 0.9Ac 0.6Ade 0.9Bc 0.6Cd 0.5Bcd 0.3Cd 0.6Ab 0.5Bbc 91.2Cc 22.9Ad 3.5Ae 0.065Bcd 0.085Abc 0.130Aa 0.009Aab 0.012Aab 0.016Aa 0.062Aa 0.033Abc 0.017Ad 0.176Bb 0.183Ab 0.163Ab 0.944Aab 1.181Aa 0.994Aa 0.038ABcd 0.106Ab 0.206Aa

Days

Fresh 42.9Aa 0.4Ab 0.0Bc 67.4Aa 8.6Ab 4.3Bc 523.5Aa 18.0Ab 2.9Bc 350.9Aa 3.7Ab 0.4Bc 651.8Aa 4.2Bb 1.0Ac 98.8Aa 28.2Ab 3.4Bc 45.9Aa 0.8Ab 0.2Ac 4.4Aa 3.7Aa 0.5Bb 1.1Ac 1.2Ab 1.8Ba 357.5Aa 65.3Ab 0.0Ac 0.050Bb 0.049Bb 0.096Ba 0.003Aa 0.004Aa 0.003Aa 0.064Aa 0.005Bb 0.014Ab 0.009Ca 0.009Ba 0.027Ba 0.075Ba 0.124Ca 0.168Ca 0.026Ba 0.037Ca 0.060Ca
z

UV-15 30.8Aa 0.4Ab 0.1Bb 50.1Aa 4.4Ab 6.7ABb 400.4Aa 21.5Ab 36.9Ab 242.8Aa 2.9Ab 4.6Ab 465.9Aa 3.6Bb 0.9Ac 63.6Aa 24.3Ab 45.5Aab 30.9Ba 0.9Ab 0.4Ac 4.2Aa 2.5Bb 4.9Aa 0.9Bb 1.1Ab 3.1Aa 245.3Ba 19.6Bb 0.3Ac 0.174Aa 0.087ABb 0.105Bb 0.005Aa 0.007Aa 0.007Aa 0.040Aa 0.023ABab 0.013Ab 0.322Aa 0.163Ab 0.039Bc 1.315Aa 1.019Ba 0.716Ba 0.077Ab 0.081Bb 0.166Ba

a Data presented are statistical geometric means (n = 3 per measure) from full-slip, fully ripe fruit. The combined maturity indicates 3/4-slip (ripe) plus full-slip fully ripe fruit, according to the Materials and Methods section. b Normalized on the benzothiophene internal standard. c Mix indicates that this compound could be the 2,3-butanediol diacetate R,R and/or S,S isomer. Geometric mean treatment differences (not including time effects) per compound, across rows (treatment effects), not followed by common upper case (A, B, C) letters are signicantly different (P = 0.05) based on the log transformed values. Means not followed by a common lower case letter (a, b, c, etc.), per column, denote signicant differences (P = 0.05) through storage (time), per compound for (maturity treatment days) in full-slip fruit, and for (treatment days) when maturities were combined.

Vol. 72, Nr. 4, 2007JOURNAL OF FOOD SCIENCE

S277

S: Sensory & Nutritive Qualities of Food

0 1 3 Methyl 2-methyl butanoate 0 1 3 Ethyl butanoate 0 1 3 Ethyl 2-methyl butanoate 0 1 3 3-methylbutyl acetate 0 1 3 Ethyl hexanoate 0 1 3 Hexyl acetate 0 1 3 2,3-butanediol diacetate (meso) 0 1 3 2,3-butanediol diacetate (mix)c 0 1 3 Benzyl acetate 0 1 3 -cyclocitral 0 1 3 (Z )-nerylacetone 0 1 3 -terpinyl acetate 0 1 3 (Z )- -ionone 0 1 3 (E )-geranylacetone 0 1 3 (E )- -ionone 0 1 3

Ethyl 2-methyl propanoate

Effect of UV irradiation on cut cantaloupe . . .


geranylacetone, and -cyclocitral were commonly recovered and increased significantly after UV treatments (Table 3), and often increased significantly after UV exposure or storage (Table 4). Terpenoid recovery in cantaloupe was often maturity-dependent (Figure 1) and cultivar-dependent (Table 3 compared with 4), and substantial differences in quality and the concentration of biologically important compounds in a given fruit fluctuate per cultivar, over different growing seasons, and growing regions (Kays 1997). Recently, recovery of a carotenoid cleavage dioxygenase in melon demonstrated putatively in vivo formation of -ionone from carotene (Ibdah and others 2006). Although in vivo cleavage products occur in melon, our data suggest that there is a higher potential for carotenoid oxidation products in cut cantaloupe exposed to UV or desiccating conditions. Subsequently, in properly cut and stored fresh-cut fruits, carotenoid oxidation byproducts should not proliferate so long as shelf-life has not been compromised. Thus, the irregular response to UV-15 compared with UV-60 and accumulation of -ionone (Z an E ) in melon fruit (Table 4) could have been due to limited availability of carotenoid substrate (Ibdah and others 2006) and relative oxidative stress during exposure and/or storage. Several terpenoids increased slightly through 5- to 7-d storage in fresh-cut cantaloupe cubes, then generally increased substantially 9 d into storage (Figure 1). Interestingly, terpenoid increases corresponded with the occurrence of nonmarketability, even though still consumable. These terpenoids have characteristic aroma attributes such as woody, green, grassy, camphoreous, black tea, and herbaceous (Table 1), which are likely undesirable in cantaloupes, especially at elevated concentrations. Nonetheless, oxidation or

Table 5 --- Selected terpenoid and terpenoid oxidation/degradation products recovered (SPME GC-MS) in Sol Real cantaloupe harvested at 5 distinct maturities Compoundsa limonene eucalyptol (1,8-cineole) 2,3-butanediol diacetate (mix) -cyclocitral -terpinyl acetate (Z )-nerylacetone (E )- -ionone (E )- -ionone-5,6-epoxide -farnescene 1/4-slip 8964 B 29150 C 4050 C 17256 B 2027 E 91785 A 45302 B 21348 B 37463 B 1/2-slip 13740 A 53066 B 4836 C 16096 B 4395 D 83316 A 47344 AB 21794 B 70523 A 3/4-slip 12587 AB 56591 AB 15939 B 22281 A 9016 C 89787 A 58076 A 31064 A 94817 A Full-slip 8943 B 72338 A 18481 B 21229 A 15767 B 97890 A 57297 A 32676 A 79547 A Overripe 13669 A 67758 AB 114382 A 12740 C 24837 A 45067 B 49662 AB 24256 B 9370 C

a Averages of selected ion abundance (n = 3). Geometric means across rows (per compound) not followed by a common letter are signicantly different (P = 0.05) based on the log transformed values.

full slip 50,000 A 37,500 25,000 12,500 0 Target Ion Response 80,000 C 60,000 40,000 20,000 0 E

3/4-slip B

1/2-slip

1/4-slip

Figure 1 --- Change in terpenoids and terpenoid oxidation products via SPME, GC-MS in fresh-cut Sol Real cantaloupe cubes prepared from 4 maturities, and stored at 4 C in clamshells. Panel A = -cyclocitral; B = -terpinyl acetate; C = dihydroactinidiolide; D = 2,3 butanediol diacetate (R,R and/or S,S); E = (E )- -ionone; and F = (E )- -ionone-5,6-epoxide.

150,000 120,000 90,000 60,000 30,000 0

S: Sensory & Nutritive Qualities of Food

9 0 Days storage (4C)

S278

JOURNAL OF FOOD SCIENCEVol. 72, Nr. 4, 2007

Effect of UV irradiation on cut cantaloupe . . .


enzymatic processes that generate unique compounds likely have negative effects on the organoleptic property of the cut fruit, similar to typical C 6 and C 9 off-odors associated with gamma irradiation and oxidation of cantaloupe juice (Wang and others 2006). Substantial recovery of apparent oxygenated -carotene breakdown products may indicate that excessive cutting required for UV-exposure, or lengthy fresh-cut storage, coincides with carotenoid loss (Gil and others 2006) and could be deleterious regarding loss of quality and retinol activity equivalents for Vitamin A. Subsequently, a germicidal dose of UV in stored fresh-cut cantaloupe, which should elevate terpenoid concentrations much higher than those reported (Table 3 and 4), might negatively affect organoleptic acceptability. large relative surface area of thinly sliced tissue. This diffusion process is further indicated by the trend established whereby a greater loss was observed in more volatile LMW esters relative to higher molecular weight esters (Table 3 and 4), and 60-min exposure resulted in greater losses compared with 15-min exposure (Table 3). These relative shifts in recovery likely further reflect the differential loading processes occurring on an individual SPME fiber as the concentration of analytes with varying molecular weights changed in the vial head-space and adsorption capacity changed, respectively, as previously reported (Ai 1997; Niedziella and others 2000; Murray 2001). Treatments or conditions resulting in decreased adsorption of LMW esters effectively free up available SPME sites to actively adsorb higher molecular weight compounds onto the fiber. According to Table 3 and 4, one can observe that lower molecular weight esters decreased markedly with UV treatments or CON-60, and the apparent decrease of higher molecular weight esters was much less substantial. This is a logical consequence of improper sample handling, as a concentration gradient and low vapor point would effectively facilitate rapid LMW volatile off-gassing. Reduced ester recovery in UV-treated and 60-min control tissue (CON-60) was hypothetically due to rapid off-gassing, which was driven by moisture loss, and perhaps additional heating during UV exposure. In our analyses, aldehydes were only observed in substantial levels in 1 of the 4 cultivars (Sol Real), as previously reported (Beaulieu and Grimm 2001). An enzymatic, or proposed UVinduced, breakdown of esters (Lamikanra and others 2002) would result in the formation of alcohols and short chain fatty acids. However, neither class of these oxidation products increased in UV-treated thinly cut laminar slices. Furthermore, aldehydes were not recovered in controls of thin-sliced cantaloupe, and terpenoid oxidation was often evident in treated tissue (Table 3 and 4, Figure 1). Esterase activity decreased in cantaloupe exposed to UV (Lamikanra and Watson 2004; Lamikanra and others 2005). Subsequently, this supports the notion that ester loss was due to evaporation rather than decomposition or enzymatic conversion. Nevertheless, tissue sampling, GC-MS regimes, and efficacy of volatile recovery in relation to flavor profiles in cut cantaloupe tissue will be examined elsewhere (Beaulieu, unpublished data).

Ester loss in thin-sliced cantaloupe is not UV-induced


Control laminar slices at time zero had the highest recovery of almost all esters; yet, the levels were generally only significantly higher compared with UV-60 delivered in the static system (Table 3 and 4). In the open system, UV-15 reduced low molecular weight (LMW; <C 9 , not including benzyl acetate) esters by up to 36.1% (average 18.4%), yet these decreases were mainly not significantly different from controls. UV-60 significantly decreased LMW esters by as much as 80.3% (average 64.9%) compared with the controls (Table 3). An extremely similar trend was observed regarding insignificant ester loss in UV-15 versus significant loss in UV-60, compared to the controls, in the static Petri dish system (Table 4). Recovery of most esters reported in laminar slices immediately after 15- and 60-min UV exposure significantly decreased progressively with increasing UV, independent of open versus static exposure system (Table 3 and 4). The apparent ester loss was consistent in 3 cultivars tested. The most significant apparent ester loss occurred in control laminar slices in open Petri dishes for 60 min (CON-60) and slices exposed to UV-60 (Table 3). These 2 treatments had extremely comparable ester profiles, with few exceptions. There were not significant differences between the UV-60 and CON-60 in open systems. If ester loss was UV-induced or a UV stress response, then one should not expect parallel losses in an identical treatment not exposed to UV. Furthermore, in laminate slices receiving UV-60 in the static system, recovery of LMW esters was often slightly (although insignificantly) higher than the UV-60 open system (Table 3). For example, in UV-60 (open), there was on average 70.8% loss of C 8 esters compared to controls, whereas in UV-60 (static) the average ester loss compared to controls was markedly lower at 47.1%. The marked disparity between apparent ester losses in UV-60 in open versus static systems also indicates that UV alone was not the causal factor. A substantial temperature increase (4.3 0.5 C; n = 4), nearly linear for 30 min (y = 0.116x, R2 = 0.978), occurred in laminar slices that were exposed to UV for 60 min. During static UV treatments, condensation was always observed on the lid, indicating a nearly saturated atmosphere within the Petri dish. The relative increase in esters in static UV-60 versus the open system UV-60 (Table 3) could be due to tissue heating or decreased off-gassing since the water potential gradient within the saturated system was less severe. This seems plausible because the apparent LMW ester loss was almost always greater in UV-60 compared with UV-15 (Table 3 and 4). The apparent loss of esters resulting from UV treatments (both 15 and 60 min) decreased markedly at C 8 molecular weights. These data therefore indicate that ester losses were independent of UV treatment. Ester loss might be expected to occur in cantaloupe cut into very thin laminar slices, as a function of time. Rapid off-gassing of LMW volatiles with low vapor pressures and boiling points would be expected on the basis of the water potential gradient (Nobel 1991) and

Microbial load reduction with exogenous terpenoids


The efficacy of employing UV-enhanced terpenoids for antimicrobial capacity is based not only on their chemical make-up but also on the in vivo active concentration formed (Mercier 1997). Exposure of cantaloupe flesh to UV irradiation resulted in an increase in the amount of terpenoid compounds observed. However, these UVenhanced compounds were observed at levels in the cantaloupe, estimated in the low ppb range (ug/kg). UV-enhanced or UV-induced terpenoid must have a residual effect and/or be retained or continually produced in tissue to have long-term antimicrobial action. Data indicate (Table 4) that UV in this system was not highly effective or consistent in achieving this goal. It is therefore improbable that UV-enhanced compounds in the low ppb range could have a comparable in vivo germicidal effect as compared with the results from exogenous application at 300 L/3g (Lamikanra and others 2002), which is a concentration in excess of 6 orders of magnitude higher.

Conclusions

e established that ester losses occurred in laminar tissue slices of cantaloupe that were either UV- or air-exposed for 60 min in uncovered Petri dishes. Tissue samples that were exposed to UV in static Petri dishes did not normally demonstrate corresponding ester loss. UV irradiation in the static system often resulted in slightly
Vol. 72, Nr. 4, 2007JOURNAL OF FOOD SCIENCE S279

S: Sensory & Nutritive Qualities of Food

Effect of UV irradiation on cut cantaloupe . . .


decreased esters relative to the controls, but we hypothesize that the loss was attributed to sample preparation (wounding), off-gassing, and tissue warming. This effect is especially likely since UV is not responsible for chemical transformations to ester bonds, esterase, and lipase activity decreased in cantaloupe exposed to UV (Lamikanra and Watson 2004; Lamikanra and others 2005), and no secondary alcohols or short chain oxidation volatiles were observed, while oxidized/breakdown terpenoid compounds were recovered. Comparing volatile results obtained after UV treatment in open versus static systems to the controls led to the conclusion that the previously reported 60% ester loss in thinly sliced cantaloupe tissue (Lamikanra and others 2002) was not due to UV treatment and, therefore, offered little relevance for the fresh-cut fruit industry. Theoretically, UV treatments might provide germicidal control in fresh-cut fruits. For effective microbial kill rates and UV dose penetration, maximizing total surface area exposure of tissue is critical, and subsequently, the previously reported method was highly logical. The efficacious use of UV was established by UVenhanced terpenoid production in cut cantaloupe, as previously reported (Lamikanra and others 2002). Yet, induced terpenoid levels were likely too low to function as phytoalexins. Furthermore, the tissue preparation method clearly compromised the physiological status of the tissue regarding ester volatiles that likely have aromaimpact. Important flavor-related esters have been thoroughly evaluated in cantaloupe, and their levels remain high in industry style fresh-cut cantaloupe for at least 7 d in optimum storage (Beaulieu 2005; Beaulieu 2006b). In addition, if endogenous terpenoid concentrations become excessively high, off-flavors may result. We have established that the cutting method and treatment system used herein for thin tissue slices would result in severe negative effects regarding keeping quality and flavor loss in fresh-cut cantaloupe. Manufactures of UV equipment for the fresh-cut food industry have a challenge to engineer equipment and technology required to simultaneously protect operators while effectively treating cut fruit tissue to ensure significant and consistent microbial load reduction.
Beaulieu JC, Baldwin EA. 2002. Flavor and aroma of fresh-cut fruits and vegetables. In: Lamikanra O, editor. Fresh-cut fruits and vegetables. Science, technology and market. Boca Raton, Fla.: CRC Press LLC. p 391425. Beaulieu JC, Grimm CC. 2001. Identification of volatile compounds in cantaloupe at various developmental stages using solid phase microextraction. J Agric Food Chem 49(3):134552. Beaulieu JC, Lea JM. 2003a. Aroma volatile differences in commercial orange-fleshed cantaloupes, the inbred parental lines, and stored fresh-cuts. Acta Hortic 628:809 15. Beaulieu JC, Lea JM. 2003b. Volatile and quality changes in fresh-cut mangos prepared from firm-ripe and soft-ripe fruit, stored in clamshell containers and passive MAP. Postharvest Biol Technol 30(1):1528. Bett KL, Ingram DA, Grimm CC, Lloyd SW, Spanier AM, Miller JM, Gross KC, Baldwin EA, Vinyard BT. 2001. Flavor of fresh-cut Gala apples in modified atmosphere packaging as affected by storage time. J Food Qual 24(2):141 56. Bett-Garber KL, Beaulieu JC, Ingram DA. 2003. Effect of storage on sensory properties of fresh-cut cantaloupe varieties. J Food Qual 26:32335. Bohlmann J, Meyer-Gauen G, Croteau R. 1998. Plant terpenoid synthases: molecular biology and phylogenetic analysis. Proc Natl Acad Sci U S A 95(8):412633. Buttery RG. 1981. Vegetable and fruit flavors. In: Teranishi R, Flath RA, Sugisawa H, editors. Flavor researchrecent advances. New York: Marcel Dekker Inc. p 175 216. Buttery RG, Teranishi R, Ling LC, Flath RA, Stern DJ. 1988. Quantitative studies on origins of fresh tomato aroma volatiles. J Agric Food Chem 36(6):124750. Dorantes-Alvarez L, Chiralt A. 2002. Color of minimally processed fruits and vegetables as affected by some chemical and biochemical changes. In: Alzamora SM, Tapia MS, Aurelio L-M, editors. Minimally processed fruits and vegetables: fundamental aspects and applications. Gaithersburg, Md.: Aspen Publishers Inc. p 111 26. Dudareva N, Andersson S, Orlova I, Gatto N, Reichelt R, Rhodes D, Boland W, Gershenzon J. 2005. The nonmevalonate pathway supports both monoterpene and sesquiterpene formation in snapdragon flowers. Proc Natl Acad Sci U S A 102(3):933 8. Dunphy PJ. 2006. Location and biosynthesis of monoterpenyl fatty acyl esters in rose petals. Phytochem 67(11):11109. Etoh H, Ina K. 1979. Photooxygenation of -ionone. Agric Biol Chem 43(12):25935. bler A, Boland W, Preiss U, Simon H. 2004. Stereochemical studies on homoterpene Ga biosynthesis in higher plants; mechanistic, phylogenetic, and ecological aspects. Helvetica Chimica Acta 74(8):177389. Gil MI, Aguayo E, Kader AA. 2006. Quality changes and nutrient retention in fresh-cut versus whole fruits during storage. J Agric Food Chem 54(12):4284 96. Homatidou VI, Karvouni SS, Dourtoglou VG, Poulos CN. 1992. Determination of total volatile components of Cucumis melo var. cantaloupensis. J Agric Food Chem 40(8):13858. Horvat RJ, Senter SD. 1987. Identification of additional volatile compounds from cantaloupe. J Food Sci 52(4):10978. Hugueney P, Bouvier F, Badillo A, Quennemet J, dHarlingue A, Camara B. 1996. Developmental and stress regulation of gene expression for plastid and cytosolic isoprenoid pathways in pepper fruits. Plant Physiol 111(2):61926. Ibdah M, Azulay Y, Portnoy V, Wasserman B, Bar E, Meir A, Burger Y, Hirschberg J, Schaffer AA, Katzir N, Tadmor Y, Lewinsohn E. 2006. Functional characterization of CmCCD1, a carotenoid cleavage dioxygenase from melon. Phytochem 67: 157989. Isoe S, Hyeon SB, Sakan T. 1969. Photo-oxygenation of carotenoids. I. The formation of dihydroactinidiolide and -ionone from -carotene. Tetrahedron Lett 10(4):279 81. Jagger J. 1967. Introduction to research in ultraviolet photobiology. Englewood Cliffs, N.J.: Prentice Hall. n MJ, Shaw PE, Goodner KL. 2001. Volatile components in aqueous essence and Jorda fresh fruit of Cucumis melo cv. Athena (muskmelon) by GC-MS and GC-O. J Agric Food Chem 49(12):592933. Kays SJ. 1997. Postharvest physiology of perishable plant products. Athens, Ga.: Exon Press. p. 532. Kemp TR, Knavel DE, Stoltz LP. 1971. Characterization of some volatile components of muskmelon fruit. Phytochem 10(8):19258. Kemp TR, Knavel DE, Stoltz LP. 1973. Volatile Cucumis melo components: identification of additional compounds and effects of storage conditions. Phytochem 12(12):29214. Kemp TR, Stoltz LP, Knavel DE. 1972. Volatile components of muskmelon fruit. J Agric Food Chem 20(2):1968. Klein BP. 1987. Nutritional consequences of minimal processing of fruits and vegetables. J Food Qual 10:17993. Kotseridis Y, Baumes R, Skouroumounis GK. 1998. Synthesis of labelled [2H4] damascenone, [2H2] 2-methoxy-3- isobutylpyrazine, [2H3] -ionone, and [2H3] -ionone, for quantification in grapes, juices and wines. J Chromat A 824(1):718. Lamikanra O. 2004. The role of esterified compounds in the development of staleness in fresh-cut fruit. In: Hofmann T, Ho CT, editors. Challenges in taste chemistry and biology. Washington, D.C.: American Chemical Society. p 26374. Lamikanra O, Richard OA, Parker A. 2002. Ultraviolet induced stress response in fresh cut cantaloupe. Phytochem 60(1):2732. Lamikanra O, Richard OA. 2002. Effect of storage on some volatile aroma compounds in fresh-cut cantaloupe melon. J Agric Food Chem 50(14):40437. Lamikanra O, Richard OA. 2004. Storage and ultraviolet-induced tissue stress effects on fresh-cut pineapple. J Sci Food Agric 84:18126. Lamikanra O, Juaraez B, Watson MA, Richard OA. 2003. Effect of cutting and storage on sensory traits of cantaloupe melon cultivars with extended postharvest shelf life. J Sci Food Agric 83:7028. Lamikanra O, Kueneman D, Ukuku DO, Bett-Garber KL. 2005. Effect of processing under ultraviolet light on the shelf life of fresh-cut cantaloupe melon. J Food Sci 70(9):C5349.

Acknowledgments
The author expresses thanks to Dean Liere, Syngenta Seeds Inc., ROGERS Brand Vegetable Seeds for supplying cantaloupe cultivars, and California Day-Fresh Foods Inc. for supplying control and UV-treated Essential Greens and Watermelon juice. Thanks to Casey Grimm (USDA, ARS, SRRC) for synthesis of standards and GC-MS support. Statistical support was provided by Debbie Boykin (USDA, ARS, Stoneville, Miss., U.S.A.).

References
Ai J. 1997. Solid phase microextraction for quantitative analysis in nonequilibrium situations. Anal Chem 69(6):12306. Anonymous. 1999a. UV light provides alternative to heat pasteurization of juices. Food Technol 53(9):144. Anonymous. 1999b. A food additive petition for the use of ultraviolet light in the reduction of microorganisms on juice products. Submitted to FDA regarding CFR 21 179. Glendore, Calif.: California Day-Fresh Foods Inc. p 1117. Aubert C, Bourger N. 2004. Investigation of volatiles in Charentais cantaloupe melons (Cucumis melo var. cantalupensis). Characterization of aroma constituents in some cultivars. J Agric Food Chem 52(14):45228. Back K, He S, Kim KU, Shin DH. 1998. Cloning and bacterial expression of sesquiterpene cyclase, a key branch point enzyme for the synthesis of sesquiterpenoid phytoalexin capsidiol in UV-challenged leaves of Capsicum annuum. Plant Cell Physiol 39(9):899904. Bailey JA, Mansfield JW. 1982. Phytoalexins. New York: Wiley. Beaulieu JC. 2005. Within-season volatile and quality differences in stored fresh-cut cantaloupe cultivars. J Agric Food Chem 53(22):867987. Beaulieu JC. 2006a. Effect of cutting and storage on acetate and non-acetate esters in convenient, ready to eat fresh-cut melons and apples. HortSci 41(1):6573. Beaulieu JC. 2006b. Volatile changes in cantaloupe during growth, maturation and in stored fresh-cuts prepared from fruit harvested at various maturities. J Am Soc Hort Sci 131(1):127139.

S: Sensory & Nutritive Qualities of Food

S280

JOURNAL OF FOOD SCIENCEVol. 72, Nr. 4, 2007

Effect of UV irradiation on cut cantaloupe . . .


Lamikanra O, Watson MA. 2004. Storage effects on lipase activity in fresh-cut cantaloupe melon. J Food Sci 69(2):12630. Littell RC, Milliken GA, Stroup WW, Wolfinger RD. 1996. SAS system for mixed models. Cary, N.C.: SAS Inst. Inc. March J. 1985. Advanced organic chemistry. New York: John Wiley & Sons Inc. Mercier J. 1997. Role of phytoalexins and other antimicrobial compounds from fruits and vegetables in postharvest disease resistance. In: Thomas-Barberan FA, Thomas RJ, editors. Phytochemistry of fruit and vegetables. New York: Oxford Science Publications. p 22141. Murray RA. 2001. Limitations to the use of solid-phase microextraction for quantitation of mixtures of volatile organic sulfur compounds. Anal Chem 73(7):16469. Niedziella S, Rudkin S, Cooke M. 2000. Evidence for selectivity of absorption of volatile organic compounds by a polydimethylsiloxane solid-phase microextraction fibre. J Chromat A 885(12):45764. Nobel PS. 1991. Physicochemical and environmental plant physiology. San Diego, Calif.: Academic Press Inc. p 635. Nussbaumer C, Hostettler B. 1996. New flavour compounds of Cucumis melo L. In: Taylor AJ, Mottram DS, editors. Flavour science: recent developments. Cambridge, U.K.: Royal Society of Chemistry. p. 7073. Pratt HK. 1971. Melons. In: Hulme AC, editor. The biochemistry of fruits and their products. New York: Academic Press. p 207232. Saftner RA, Bai J, Abbott JA, Lee YS. 2003. Sanitary dips with calcium propionate, calcium chloride, or a calcium amino acid chelate maintain quality and shelf stability of fresh-cut honeydew chunks. Postharvest Biol Technol 29:25769. Sanderson G, Graham HN. 1973. On the formation of black tea aroma. J Agric Food Chem 21(4):57684. Schieberle P, Ofner S, Grosch W. 1990. Evaluation of potent odorants in cucumbers (Cucumis sativus) and muskmelons (Cucumis melo) by aroma extract dilution analysis. J Food Sci 55(1):1935. Scott JF. 1955. Ultraviolet absorption spectrophotometry. In: Oster G, Pollister AW, editors. Physical techniques in biological research. Volume 1. Optical techniques. New York: Academic Press. p 131203. Shalit M, Katzir N, Tadmor Y, Larkov O, Burger Y, Shalekhet F, Lastochkin E, Ravid U, Amar O, Edelstein M, Karchi Z, Lewinsohn E. 2001. Acetyl-CoA: alcohol acetyltransferase activity and aroma formation in ripening melon fruits. J Agric Food Chem 49(2):7949. Shu CK, Chung HL, Lawrence BM. 1995. Volatile components of pocket melon (Cucumis melo L. ssp. dudaim Naud.). J Essent Oil Res 7:17981. Simkin AJ, Schwartz SH, Auldridge M, Taylor MG, Klee HJ. 2004. The tomato carotenoid cleavage dioxygenase 1 genes contribute to the formation of the flavor volatiles bionone, pseudoionone, and geranylacetone. Plant J 40:88292. Spanier AM, Flores M, James C, Lasater J, Lloyd S, Miller JA. 1998. Fresh-cut pineapple (Ananas sp.) flavor. Effect of storage. In: Contis ET, Ho CT, Mussinan CJ, Parliment TH, Shahidi F, Spanier AM, editors. Developments in food science. Food flavors: formation, analysis, and packaging influences. p 33143. Spikes JD. 1981. Photodegradation of foods and beverages. In: Smith KC, editor. Photochemical and photobiological reviews, Vol. 6. New York: Plenum Press. Taiz L, Zeiger E. 2002. Plant physiology. Sunderland, Mass.: Sinauer Associates Inc., Publishers. p 690. Wang Z, Ma Y, Zhao G, Liao X, Chen F, Wu J, Chen J, Hu X. 2006. Influence of gamma irradiation on enzyme, microorganism, and flavor of cantaloupe (Cucumis melo L.) juice. J Food Sci 71(6):M21520. Weeks WW. 1986. Carotenoids. A source of flavor and aroma. In: Parliment TH, Croteau R, editors. Biogeneation of aromas. Am. Chem. Soc. Symp. Ser. 317. Washington, D.C.: American Chemical Society. Wyllie SG, Leach DN, Wang Y, Shewfelt RL. 1994. Sulfur volatiles in Cucumis melo cv. Makdimon (muskmelon) aroma. Sensory evaluation by gas chromatographyolfactometry. ACS Symp. Ser 564:3648. Sulfur compounds in foods. Washington, D.C.: American Chemical Society. Wyllie SG, Leach DN, Wang Y. 1996. Development of flavor attributes in the fruit of C. melo during ripening and storage. In: Takeoka GR, Teranishi R, Williams PJ, Kobayashi A, editors. Biotechnology for improved foods and flavors. Washington, D.C.: American Chemical Society. p 22839.

Vol. 72, Nr. 4, 2007JOURNAL OF FOOD SCIENCE

S281

S: Sensory & Nutritive Qualities of Food