Analysis of Bitter Principles in Citrus

  • S. Hasegawa
  • M. A. Berhow
  • C. H. Fong
Part of the Modern Methods of Plant Analysis book series (MOLMETHPLANT, volume 18)

Abstract

Bitterness is a major problem to the citrus industry. It is of economic importance because bitter juices have a lower market value. Bitterness is mainly caused by the accumulation of two different chemical compounds: limonin from the limonoid terpine group and naringin from the flavonoid phenolic group in the fruit tissues. The highest concentrations of the bitter compounds are generally found in immature fruits. As the fruits mature, the concentrations of the bitter compounds decrease.

Keywords

Glycoside Quercetin Lactone Rutin Chalcone 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Albach RF, Redman GH (1969) Composition and inheritance of flavanones in citrus fruit. Phytochemistry 8:127–143CrossRefGoogle Scholar
  2. Albach RF, Wutscher HK (1988) Flavanone content of whole grapefruit and juice as influenced by fruit development. J Rio Grande Val Hortic Soc 41:89–95Google Scholar
  3. Albach RF, Juarez AT, Lime BJ (1969) Time of naringin production in grapefuit. J Am Soc Hortic Sci 94:605–609Google Scholar
  4. Alford AR, Bentley MD (1986) Citrus limonoids as potential antifeedants for the spruce budworm ( Lepidoptera:Torticidae). J Econ Entomol 79:35–38Google Scholar
  5. Anis M, Aminuddin (1981) Flavonoid patterns of leaves of some Citrus species and their hybrids. Plant Biochem J 8:56–60Google Scholar
  6. Arnao MB, Casas JL, del Rio JA, Acosta M, Garcia-Canovas F (1990) An enzymatic colorimetric method for measuring naringin using 2,2’-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) ( ABTS) in the presence of peroxidase. Anal Biochem 185:335–338PubMedCrossRefGoogle Scholar
  7. Attaway JA (1977) Factors influencing the flavor of grapefruit juice. Proc Int Soc Citricult 3:816–820Google Scholar
  8. Berhow MA, Vandercook CE (1989) Biosynthesis of naringin and prunin in detached grapefruit. Phytochemistry 28:1627–1630CrossRefGoogle Scholar
  9. Berthow MA, Vandercook CE (1991) Sites of naringin biosynthesis in grapefruit seedlings. J Plant Physiol 138:176–179Google Scholar
  10. Castillo J, Benavente O, del Rio JA (1992) Naringin and neohesperidin levels during development of leaves, flower buds, and fruits of Citrus aurantium. Plant Physiol 99:67–73PubMedCrossRefGoogle Scholar
  11. Coffin DE (1971) A method for the isolation and identification of the flavanone glycosides of citrus juices. J Agric Food Chem 19:513–516CrossRefGoogle Scholar
  12. Creaser CS, Koupai-Abyazani MR, Stephenson GR (1992) Gas chromatographic-mass spectrometric characterization of flavanones in citrus and grape juices. Analyst 117:1105–1109PubMedCrossRefGoogle Scholar
  13. Dass HC (1977) Phylogenetic studies in Citrus reticulata and related types. Euphytica 26:805–810CrossRefGoogle Scholar
  14. Dass HC, Weaver GM (1972) Cellulose thin-layer chromatography of phenolic substances. J Chromatogr 67:105–111CrossRefGoogle Scholar
  15. Dass HC, Randhawa GS, Prakash D (1978) Leaf flavonoid patterns of some importan Citrus species. Indian J Exp Bot 16:62–65Google Scholar
  16. Davis WB (1947) Determination of flavanones in citrus fruits. Anal Chem 19:467–478CrossRefGoogle Scholar
  17. del Rio JA, Benavente O, Castillo J, Borrego F (1992) Neodiosmin, a flavone glycoside of Citrus aurantium. Phytochemistry 31:723–724CrossRefGoogle Scholar
  18. Fisher JF (1968) A procedure for obtaining radioactive naringin from grapefruit leaves fed Lphenylalanine-14C. Phytochemistry 7:769–771CrossRefGoogle Scholar
  19. Fisher JF (1973) Fluorometric determination of limonin in grapefruit and orange juice. J Agric Food Chem 21:1109–1110CrossRefGoogle Scholar
  20. Fisher JF (1977) Review of quantitative analyses for limonin, naringin, naringenin rutinoside, hesperidin, and neohesperidin dihydrochalcone in citrus juice by high performance liquid chromatography. Proc Int Soc Citricult 3:813–816Google Scholar
  21. Fisher JF, Wheaton TA (1976) A high-pressure liquid chromatographic method for the resolution and quantitation of naringin and naringenin rutinoside in grapefruit juice. J Agric Food Chem 24:898–899CrossRefGoogle Scholar
  22. Fisher JF, Nordby HE, Kew TJ (1966) A thin-layer chromatographic-colorimetric method for determining naringin in grapefruit. J Food Sci 31:947–950CrossRefGoogle Scholar
  23. Fong CH, Hasegawa S, Herman Z, Ou P (1991) Biosynthesis of limonoid glucosides in lemon (Citrus limon). J Sci Food Agric 54:393–398CrossRefGoogle Scholar
  24. Fong CH, Hasegawa S, Miyake M, Ozaki Y, Coggins CW, Atkin DR (1992) Contents of limonoids and limonin 17–13-D-glucopyranoside in fruit tissue of Valencia orange during fruit growth and maturation. J Agric Food Chem 40:1178–1181CrossRefGoogle Scholar
  25. Gaffield W, Lundin RE, Gentili B, Horowitz RM (1975) C-2 sterochemistry of naringin and its relation to taste and biosynthesis in maturing grapefruit. Bioorg Chem 4:259–269CrossRefGoogle Scholar
  26. Gengross O, Renda N (1966) Occurance and quantitative estimation of naringin in citrus species. Justus Liebigs Ann Chem 691:186–189CrossRefGoogle Scholar
  27. Guadagni DG, Maier VP, Turnbaugh JG (1973) Effect of some citrus juice constituents on taste thresholds for limonin and naringin bitterness. J Sci Food Agric 24:1277–1288CrossRefGoogle Scholar
  28. Guadagni DG, Maier VP, Turnbaugh JG (1974a) Some factors affecting sensory thresholds and relative bitterness of limonin and naringin. J Sci Food Agric 25:1199–1205CrossRefGoogle Scholar
  29. Guadagni DG, Maier VP, Turnbaugh JG (1974b) Effect of subthreshold concentrations of limonin, naringin and sweeteners on bitterness perception. J Sci Food Agric 25:1349–1354CrossRefGoogle Scholar
  30. Hadj-Mahammed M, Meklati BY (1987) Qualitative determination of polymethoxylated flavones in Valencia orange peel oil and juice by LC-UV/VIS and LC-MS techniques. Lebensm-Wiss Technol 20:111–114Google Scholar
  31. Hagen RE, Dunlap WJ, Mizelle JW, Wender SH, Lime BJ, Albach RF, Griffiths FP (1965) A chromatographic-fluorometric method for detemination of naringin, naringenin rutinoside, and related flavanone glycosides in grapefruit juice and juice sacs. Anal Biochem 12:472–482PubMedCrossRefGoogle Scholar
  32. Hagen RE, Dunlap WJ, Wender SH (1966) Seasonal variation of naringin and certain other flavanone glycosides in juice sacs of Texas Ruby Red grapefruit. J Food Sci 31:542–547CrossRefGoogle Scholar
  33. Hahlbrock K, Scheel D (1989) Physiology and molecular biology of phenylpropanoid metabolism. Annu Rev Plant Physiol Plant Mol Biol 40:347–369CrossRefGoogle Scholar
  34. Hasegawa S, Herman Z (1992) Biosynthesis of limonoids in Citrus. In: Petroski RJ, McCormick SP (eds) Secondary-metabolite biosynthesis and metabolism. Plenum Press, New York, pp 305–317CrossRefGoogle Scholar
  35. Hasegawa S, Maier VP (1981) Some aspects of citrus biochemistry and juice quality. Proc Int Soc Citricult 2:914–918Google Scholar
  36. Hasegawa S, Pelton VA (1983) Reduction of nomiiin bitterness in citrus juices and juice serum with Arthrobacter globiformis cells immobilized in acrylamide gel. J Agric Food Chem 31:178–180CrossRefGoogle Scholar
  37. Hasegawa S, Bennett RD, Verdon CP (1980) Limonoids in citrus seeds:origin and relative concentration. J Agric Food Chem 28:922–925CrossRefGoogle Scholar
  38. Hasegawa S, Bennett RD, Maier VP (1984) Biosynthesis of limonoids in Citrus seedlings. Phytochemistry 23:1601–1603CrossRefGoogle Scholar
  39. Hasegawa S, Herman Z, Orme E, Ou P (1986) Biosynthesis of limonoids in Citrus:sites and translocation. Phytochemistry 25:2783–2785CrossRefGoogle Scholar
  40. Hasegawa S, Bennett RD, Herman Z, Fong CH, Ou P (1989) Limonoid glucosides in citrus. Phytochemistry 28:1717–1720CrossRefGoogle Scholar
  41. Hasegawa S, Ou P, Fong CH, Herman Z, Goggins CW, Atkin DR (1991) Changes in the limonoate A-ring lactone and limonin 17-β-D-glucopyranoside content of navel oranges during fruit growth and maturation. J Agric Food Chem 39:262–265CrossRefGoogle Scholar
  42. Hashinaga F, Ejima H, Nagahama H, Itoo S (1977) Studies on the limonoids in citrus fruits. I. Seasonal changes of limonoid components in ponkan, tankan, early satsuma mandarin and natsudaidai fruits. Kagoshima Daigaku Nogakubu Gakujutsu Hokoku 27:171–180Google Scholar
  43. Heller W, Forkmann G (1988) Biosynthesis. In: Harborne JB (ed) The flavonoids. Chapman and Hall, London, pp 399–425Google Scholar
  44. Hendrickson R, Edwards GJ (1958) Ultraviolet absorption technique to determine the naringin content of grapefruit juice. Proc Fla State Hortic Soc 71:194–198Google Scholar
  45. Herman Z, Hasegawa S, Fong CH, Ou P (1989) Limonoids in Citrus ichangensis. J Agric Food Chem 37:850–851CrossRefGoogle Scholar
  46. Herman Z, Fong CH, Hasegawa S (1992) Analysis of Limonoids in Citrus Seeds. In: Linskens HF, Jackson JF (eds) Seed analysis. Modern methods of plant analysis new series, vol 14. Springer, Berlin Heidelberg, New York, pp 361–375Google Scholar
  47. Hidaka T, Omura M, Ugaki M, Tomiyama M, Kato A, Ohshima M, Motoyoshi F (1990) Agrobacterium-mediated transformation and regeneration of Citrus spp. from suspension cells. Jpn J Breed 40:199–207Google Scholar
  48. Horowitz RM (1957) Detection of flavanones by reduction with sodium borohydride. J Org Chem 22:1733–1734CrossRefGoogle Scholar
  49. Horowitz RM, Gentili B (1959) Use of the Davis method to estimate flavanones. Food Res 24:757–759Google Scholar
  50. Horowitz RM, Gentili B (1977) Flavonoid constituents of Citrus. In: Nagy S, Shaw PE, Velduis MK (eds) Citrus science and technology. AVI Publishing, Westport, CT, pp 397–426Google Scholar
  51. Horowitz RM, Gentili B (1986) Dihydrochalcone sweeteners from citrus flavanones. In: O’Brien-Nabors L, Gelardi RC (eds) Alternative sweeteners. Marcel Dekker, New York, pp 135–153Google Scholar
  52. Johnson RL (1988) Bitterness in fruit juices:assay of bitter principles in citrus juices. In: Linskens HF, Jackson JF (eds) Analysis of nonalcoholic beverages. Springer, Berlin Heidelberg New York, pp 80–103Google Scholar
  53. Jourdan PS, Mansell RL, Weiler EW (1982) Radioimmunoassay for the citrus bitter principle, naringin, and related flavonoid-7-O-β-neohesperidosides. J Med Plant Res 44:82–86CrossRefGoogle Scholar
  54. Jorudan PS, Mansell RL, Oliver DG, Weiler EW (1984) Competitive solid phase enzyme-linked immunoassay for the quantification of limonin in citrus. Anal Biochem 138:19–24CrossRefGoogle Scholar
  55. Jourdan PS, Weiler EW, Mansell RL (1985a) Naringin levels in citrus tissues. I. Comparison of different antibodies and tracers for the radioimmunoassay of naringin. Plant Physiol 77:896–902PubMedCrossRefGoogle Scholar
  56. Jourdan PS, McIntosh CA, Mansell RL (1985b) Naringin levels in citrus tissues. II. Quantitative distribution of naringin in Citrus paradisi Macfad. Plant Physiol 77:903–908PubMedCrossRefGoogle Scholar
  57. Kamiya S, Esaki S, Konishi F (1979) Flavonoids in citrus hybrids. Agric Biol Chem 43:1529–1536CrossRefGoogle Scholar
  58. Kefford JF, Chandler BV (1970) The chemical constituents of Citrus fruits. Academic Press, New YorkGoogle Scholar
  59. Kimball DA (1991) Citrus processing:quality control and technology. Van Nostrand Reinhold, New YorkGoogle Scholar
  60. Kirchner JR (1967) Thin layer chromatography. John Wiley, New YorkGoogle Scholar
  61. Krause M, Galensa R (1991) High-performance liquid chromatography of diastereomeric flavanone glycosides in Citrus on a beta-cyclodextrin-bonded stationary phase ( Cyclobond I ). J Chromatogr 588:41–45CrossRefGoogle Scholar
  62. Kruger AJ, Colter CE (1972) Gas chromatographic identification of limonin in citrus juice. Proc Fla State Hortic Soc 85:206–210Google Scholar
  63. Kwierty A, Braverman JB (1959) Critical evaluation of the cyanidin reaction for flavonoid compounds. Bull Res Counc Isr Sect C 7:187–196Google Scholar
  64. Lam LKT, Hasegawa S (1989a) Inhibition of benzof a]pyrene-induced forestomach neoplasia in mice by citrus limonoids. Nutr Cancer 12:43–47PubMedCrossRefGoogle Scholar
  65. Lam LKT, Li Y, Hasegawa S (1989b) Effects of citrus limonoids on glutathione S-transferase activity in mice. J Agric Food Chem 37:878–880CrossRefGoogle Scholar
  66. Liu Y, Alford AR, Rajab MS, Bentley MD (1990) Effects and modes of action of citrus limonoids against Leptinotarsa decemlineata. Physiol Entomol 15:37–45CrossRefGoogle Scholar
  67. Maier VP, Beverly GD (1968) Limonin monolactone, the nonbitter precursor responsible for delayed bitterness in certain citrus juices. J Food Sci 33:488–492CrossRefGoogle Scholar
  68. Maier VP, Grant ER (1970) Specific thin-layer chromatography assay of limonin, a citrus bitter principle. J Agric Food Chem 18:250–252CrossRefGoogle Scholar
  69. Maier VP, Hasegawa S, Hera E (1969) Limonin D-ring-lactone hydrolase. A new enzyme from Citrus seeds. Phytochemistry 8:405–407CrossRefGoogle Scholar
  70. Mansell RL, Weiler EW (1980) Radioimmunoassay for the determination of limonin in citrus. Phytochemistry 19:1403–1407Google Scholar
  71. Matsumoto R, Okudai N (1991a) Early evaluation of citrus bitter component, flavanone neohesperidosides by enzyme immunoassay using anti-naringin antibody. J Jpn Soc Hortic Sci 60:191–200CrossRefGoogle Scholar
  72. Matsumoto R, Okudai N (1991b) Inheritance of flavanone neohesperidoside in Citrus. J Jpn Soc Hortic Sci 60:201–207CrossRefGoogle Scholar
  73. Miller EG, Fanous R, Rivera-Hidalgo F, Binnie WH, Hasegawa S, Lam LKT (1989) The effect of citrus limonoids on hamster buccal pouch carcinogenesis. Carcinogenesis 10:1535–1537PubMedCrossRefGoogle Scholar
  74. Miller EG, Gonzales-Sanders AP, Courillon AM, Wright JM, Hasegawa S, Lam LKT (1992) Inhibition of hamster buccal pouch carcinogenesis by limonin 17-β-D-glucopyranoside. Nutr Cancer 17:1–7PubMedCrossRefGoogle Scholar
  75. Miyake M, Ayano S, Ozaki Y, Maeda H, Ifuku Y, Hasegawa S (1991) Extraction of neutral limonoids from citrus seeds. Nippon Nogeikagaku Kaishi 65:987–992CrossRefGoogle Scholar
  76. Mizelle JW, Dunlap WJ, Hagen RE, Wender SH, Lime BJ, Albach RF, Griffiths FP (1965) Isolation and identification of some flavanone rutinosides of the grapefruit. Anal Biochem 12:316–324PubMedCrossRefGoogle Scholar
  77. Mouly P, Gaydou EM, Estrienne J (1993) Column liquid chromatographic determination of flavanone glycosides in Citrus. J Chromatogr 634:129–134PubMedCrossRefGoogle Scholar
  78. Nishiura M, Esaki S, Kamiya S (1969) Flavonoids in Citrus and related genera. I. Distribution of flavonoid glycosides in Citrus and Poncirus. Agric Biol Chem 33:1109–1118CrossRefGoogle Scholar
  79. Nishiura M, Kamiya S, Esaki S, Ito F (1971a) Flavonoids in Citrus and related genera. II. Isolation and identification of isonaringin and neoeriocitrin from Citrus. Agric Biol Chem 35:1683–1690CrossRefGoogle Scholar
  80. Nishiura M, Kamiya S, Esaki S (1971b) Flavonoids in Citrus and related genera. III. flavonoid pattern and Citrus taxonomy. Agric Biol Chem 35:1691–1706CrossRefGoogle Scholar
  81. Ou P, Hasegawa S, Herman Z, Fong CH (1988) Limonoid biosynthesis in the stem of Citrus limon. Phytochemistry 27:115–118CrossRefGoogle Scholar
  82. Park GL, Avery SM, Byers JL, Nelson DB (1983) Identification of bioflavonoids from Citrus. Food Technol 37:98–105Google Scholar
  83. Pietta PG, Mauri PL, Rava A, Sabbatini G (1991) Application of micellar electrokinetic capillary chromatography to the determination of flavonoid drugs. J Chromatogr 549:367–373CrossRefGoogle Scholar
  84. Rouseff RL (1982) Nomilin, a new bitter component in grapefruit juice. J Agric Food Chem 30:504–507CrossRefGoogle Scholar
  85. Rouseff RL (1988) Differentiating citrus juices using flavanone glycoside concentration profiles. In: Nagy S, Attaway JA, Rhodes ME (eds) Adulteration of fruit juice beverages (Food science and technology, vol 30 ) Marcel Dekker, New York, pp 49–66Google Scholar
  86. Rouseff RL (ed) (1990) Bitterness in foods and beverages. (Developments in Food Science, vol 18 ) Elsevier, New YorkGoogle Scholar
  87. Rouseff RL, Fisher JF (1980) Determination of limonin and related limonoids in citrus juices by high performance liquid chromatography. Anal Chem 52:1228–1233CrossRefGoogle Scholar
  88. Rouseff RL, Mansell RL (1982) Comparison of high performance liquid chromatographic and radioimmunoassay limonin values from commercial grapefruit juice. Proc Fla State Hortic Soc 95:249–252Google Scholar
  89. Rouseff RL, Matthews RF (1984) Nomilin, taste threshold and relative bitterness. J Food Sci 49:777–779CrossRefGoogle Scholar
  90. Rouseff RL, Nagy S (1982) Distribution of limonoids in citrus seeds. Phytochemistry 21:85–90CrossRefGoogle Scholar
  91. Seitz U, Oefner PJ, Nathakarnkitkool S, Popp M, Bonn GK (1992) Capillary electrophoretic analysis of flavonoids. Electrophoresis 13:35–38PubMedCrossRefGoogle Scholar
  92. Sendra JM, Navarro JL, Izquierdo L (1988) C18 solid-phase and high performance liquid chromatography/ultraviolet diode array determination of fully methoxylated flavones in citrus juices. J Chromatogr Sci 26:443–448PubMedGoogle Scholar
  93. Shaw PE (1986) Use of a simple solvent optimization program to improve separation of limonin in citrus juices. J Chromatogr Sci 24:364–366Google Scholar
  94. Shaw PE (1990) Cyclodextran polymers in removal of bitter compounds in citrus juices. In: Rouseff R (ed) Bitterness in foods and beverages. Elsevier, New York, pp 309–324Google Scholar
  95. Shaw PE, Wilson CW (1984) A rapid method for determination of limonin in citrus juices by high performance liquid chromatography. J Food Sci 49:1216–1218CrossRefGoogle Scholar
  96. Shaw PE, Calkins CO, McDonald RE, Greany PD, Webb JC, Nisperos-Carriedo MO, Barros SM (1991) Changes in limonin and naringin levels in grapefruit albedo with maturity and the effects of gibberellic acid on these changes. Phytochemistry 30:3215–3219CrossRefGoogle Scholar
  97. Stafford HA (1990) Flavonoid metabolism. CRC Press, Boca Raton, FLGoogle Scholar
  98. Tatum JH, Berry RE (1973a) Method for estimating limonin content of citrus juices. J Food Sci 38:1244–1246CrossRefGoogle Scholar
  99. Tatum JH, Berry RE (1973b) Method for determining naringin content in grapefruit juice. J Food Sci 38:340–341CrossRefGoogle Scholar
  100. Ting SV, Rouseff RL (1986) Citrus fruits and their products. (Food Science and Technology, vol 18 ) Marcel Dekker, New York, pp 135–153Google Scholar
  101. Ting SV, Rouseff RL, Dougherty MH, Attaway JA (1979) Determination of some methoxylated flavones in citrus juices by high performance liquid chromatography. J Food Sci 44:69–71CrossRefGoogle Scholar
  102. Van Beek TA, Blaakmeer A (1989) Determination of limonin in grapefruit juice and other citrus juices by high-performance liquid chromatography. J Chromatogr 464:375–386PubMedGoogle Scholar
  103. Vandercook CE, Tisserat B (1989) Flavonoid changes in developing lemons grown in vivo and in vitro. Phytochemistry 28:799–803CrossRefGoogle Scholar
  104. Vardi A, Bleichman S, Aviv D (1990) Genetic transformation of Citrus protoplasts and regeneration of transgenic plants. Plant Sci 69:199–206CrossRefGoogle Scholar
  105. Weiler EW, Mansell RL (1980) Radioimmunoassay of limonin using a tritiated tracer. J Agric Food Chem 28:543–545CrossRefGoogle Scholar
  106. Widmer WW (1991) Improvements in the quantitation of limonin in citrus juice by reversed-phase high-performance liquid chromatography. J Agric Food Chem 39:1472–1476CrossRefGoogle Scholar
  107. Widmer WW, Rouseff RL (1991) Quantitative analysis of limonin in grapefruit juice using an enzyme-linked immunoassay:collaborative study. J Assoc Off Anal Chem 74:513PubMedGoogle Scholar
  108. Wilson KW, Crutchfield CA (1968) Spectrophotometric determination of limonin in orange juice. J Agric Food Chem 16:118–124CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1996

Authors and Affiliations

  • S. Hasegawa
  • M. A. Berhow
  • C. H. Fong

There are no affiliations available

Personalised recommendations