Abstract
It has been widely reported that the Harderian gland, present in most vertebrates, accumulates high levels of porphyrins, particularly protoporphyrin. The present study describes the extraction, identification and characterization of a group of hitherto unreported protoporphyrin glycoconjugates in the rat Harderian gland using HPLC, capillary electrophoresis, on-line HPLC/electrospray ionization MS and tandem MS. The major glycoconjugate was identified as protoporphyrin-1-O-acyl beta-xyloside with a smaller amount of protoporphyrin-1-O-acyl beta-glucoside also detected. In the Harderian glands studied, 50-70% of the porphyrins present were in the form of protoporphyrin glycoconjugates. This is the first reported occurrence of glycoconjugates of porphyrins in Nature and suggests that previous studies have wrongly identified the major porphyrin in the Harderian gland as the unconjugated protoporphyrin.
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- Brun A., Sandberg S. Photodynamic release of protoporphyrin from intact erythrocytes in erythropoietic protoporphyria: the effect of small repetitive light doses. Photochem Photobiol. 1985 May;41(5):535–541. doi: 10.1111/j.1751-1097.1985.tb03523.x. [DOI] [PubMed] [Google Scholar]
- Burns R. B. Histological and immunological studies on the fowl lacrimal gland following surgical excision of Harder's gland. Res Vet Sci. 1979 Jul;27(1):69–75. [PubMed] [Google Scholar]
- Buzzell G. R., Menendez-Pelaez A., Chlumecky V., Reiter R. J. Gender differences and time course of castration-induced changes in porphyrins, indoles, and proteins in the Harderian glands of the Syrian hamster. Can J Physiol Pharmacol. 1991 Dec;69(12):1814–1818. doi: 10.1139/y91-268. [DOI] [PubMed] [Google Scholar]
- Cardalda C. A., Juknat A. A., Princ F. G., Batlle A. Rat harderian gland porphobilinogen deaminase: characterization studies and regulatory action of protoporphyrin IX. Arch Biochem Biophys. 1997 Nov 1;347(1):69–77. doi: 10.1006/abbi.1997.0310. [DOI] [PubMed] [Google Scholar]
- Compernolle F., Van Hees G. P., Blanckaert N., Heirwegh K. P. Glucuronic acid conjugates of bilirubin-IXalpha in normal bile compared with post-obstructive bile. Transformation of the 1-O-acylglucuronide into 2-, 3-, and 4-O-acylglucuronides. Biochem J. 1978 Apr 1;171(1):185–201. doi: 10.1042/bj1710185. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Day R. S., Pimstone N. R., Eales L. The diagnostic value of blood plasma porphyrin methyl ester profiles produced by quantitative TLC. Int J Biochem. 1978;9(12):897–904. doi: 10.1016/0020-711x(78)90067-8. [DOI] [PubMed] [Google Scholar]
- Djeridane Y. The harderian gland and its excretory duct in the Wistar rat. A histological and ultrastructural study. J Anat. 1994 Jun;184(Pt 3):553–566. [PMC free article] [PubMed] [Google Scholar]
- Guo R., Rideout J. M., Lim C. K. Identification of meso-hydroxyuroporphyrin I in the urine of a patient with congenital erythropoietic porphyria. Biochem J. 1989 Nov 15;264(1):293–295. doi: 10.1042/bj2640293. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Honda S., Akao E., Suzuki S., Okuda M., Kakehi K., Nakamura J. High-performance liquid chromatography of reducing carbohydrates as strongly ultraviolet-absorbing and electrochemically sensitive 1-phenyl-3-methyl-5-pyrazolone derivatives. Anal Biochem. 1989 Aug 1;180(2):351–357. doi: 10.1016/0003-2697(89)90444-2. [DOI] [PubMed] [Google Scholar]
- Jansen P. L. beta-Glucuronidase-resistant bilirubin glucuronide isomers in cholestatic liver disease--determination of bilirubin metabolites in serum by means of high-pressure liquid chromatography. Clin Chim Acta. 1981 Mar 5;110(2-3):309–317. doi: 10.1016/0009-8981(81)90360-0. [DOI] [PubMed] [Google Scholar]
- Johnston H. S., McGadey J., Thompson G. G., Moore M. R., Breed W. G., Payne A. P. The Harderian gland, its secretory duct and porphyrin content in the Plains mouse (Pseudomys australis). J Anat. 1985 Mar;140(Pt 2):337–350. [PMC free article] [PubMed] [Google Scholar]
- Johnston R. E. Effects of female odors on the sexual behavior of male hamsters. Behav Neural Biol. 1986 Sep;46(2):168–188. doi: 10.1016/s0163-1047(86)90654-0. [DOI] [PubMed] [Google Scholar]
- Kennedy G. Y. Harderoporphyrin: a new porphyrin from the Harderian glands of the rat. Comp Biochem Physiol. 1970 Sep 1;36(1):21–36. doi: 10.1016/0010-406x(70)90647-x. [DOI] [PubMed] [Google Scholar]
- Kennedy G. Y., Jackson A. H., Kenner G. W., Suckling C. J. Isolation, structure and synthesis of a tricarboxylic porphyrin from the harderian glands of the rat. FEBS Lett. 1970 Jan 15;6(1):9–12. doi: 10.1016/0014-5793(70)80027-8. [DOI] [PubMed] [Google Scholar]
- Lim C. K., Li F. M., Peters T. J. High-performance liquid chromatography of porphyrins. J Chromatogr. 1988 Jul 29;429:123–153. doi: 10.1016/s0378-4347(00)83869-4. [DOI] [PubMed] [Google Scholar]
- Luo J., Lamb J. H., Lim C. K. Analysis of urinary and faecal porphyrin excretion patterns in human porphyrias by fast atom bombardment mass spectrometry. J Pharm Biomed Anal. 1997 Jun;15(9-10):1289–1294. doi: 10.1016/s0731-7085(96)01971-1. [DOI] [PubMed] [Google Scholar]
- Luo J., Lim C. K. Isolation and characterization of new porphyrin metabolites in human porphyria cutanea tarda and in rats treated with hexachlorobenzene by HPTLC, HPLC and liquid secondary ion mass spectrometry. Biomed Chromatogr. 1995 May-Jun;9(3):113–122. doi: 10.1002/bmc.1130090302. [DOI] [PubMed] [Google Scholar]
- Montgomery R. D., Maslin W. R. A comparison of the gland of Harder response and head-associated lymphoid tissue (HALT) morphology in chickens and turkeys. Avian Dis. 1992 Jul-Sep;36(3):755–759. [PubMed] [Google Scholar]
- Payne A. P. The attractiveness of Harderian gland smears to sexually naive and experienced male golden hamsters. Anim Behav. 1979 Aug;27(Pt 3):897–904. doi: 10.1016/0003-3472(79)90027-7. [DOI] [PubMed] [Google Scholar]
- Pevet P., Heth G., Hiam A., Nevo E. Photoperiod perception in the blind mole rat (Spalax ehrenbergi, Nehring): involvement of the Harderian gland, atrophied eyes, and melatonin. J Exp Zool. 1984 Oct;232(1):41–50. doi: 10.1002/jez.1402320106. [DOI] [PubMed] [Google Scholar]
- Rodriguez C., Menendez-Pelaez A., Reiter R. J., Buzzell G. R., Vaughan M. K. Porphyrin metabolism in the harderian glands of Syrian hamsters: in vivo regulation by testicular hormones, lighting conditions, pineal gland, and pituitary hormones. Proc Soc Exp Biol Med. 1992 May;200(1):25–29. doi: 10.3181/00379727-200-43389. [DOI] [PubMed] [Google Scholar]
- Sakai T. The mammalian Harderian gland: morphology, biochemistry, function and phylogeny. Arch Histol Jpn. 1981 Sep;44(4):299–333. doi: 10.1679/aohc1950.44.299. [DOI] [PubMed] [Google Scholar]
- Shirama K., Furuya T., Takeo Y., Shimizu K., Maekawa K. Influences of some endocrine glands and of hormone replacement on the porphyrins of the Harderian glands of mice. J Endocrinol. 1981 Nov;91(2):305–311. doi: 10.1677/joe.0.0910305. [DOI] [PubMed] [Google Scholar]
- Spike R. C., Payne A. P., Thompson G. G., Moore M. R. High-performance liquid chromatographic analyses of porphyrins in hamster Harderian glands. Biochim Biophys Acta. 1990 Apr 23;1034(1):1–3. doi: 10.1016/0304-4165(90)90144-l. [DOI] [PubMed] [Google Scholar]
- Thiessen D. D. Body temperature and grooming in the Mongolian gerbil. Ann N Y Acad Sci. 1988;525:27–39. doi: 10.1111/j.1749-6632.1988.tb38593.x. [DOI] [PubMed] [Google Scholar]
- Thiessen D. D., Kittrell E. M. The Harderian gland and thermoregulation in the gerbil (Meriones unguiculatus). Physiol Behav. 1980 Mar;24(3):417–424. doi: 10.1016/0031-9384(80)90229-2. [DOI] [PubMed] [Google Scholar]