산 가수분해 방법에 의한 감자 glycoalkaloid성분의 정량성 검토 = Studies on Potato Glycoalkaloid Determination by Acid-hydrolysis Method

국문 초록 (Abstract)

본 연구는 재배종 감자 덩이줄기에 존재하는 glycoalkaloid (PGA) 중특히 α-chaconine, α-solanine, demessine을 산가수분해 처리하여 분해 생성물인 아그리콘 및 배당체를 분석하는 방법으로 PGA의 정량 가능 유무를 조사하였다. 1. 표준품의 solanidine을 1 N-HCl로 가수분해하면 산 가수분해 반응 10분 후부터 solanidine이 급속하게 감소하였고 새로운 피크가 급증하였다. 이 피크를 GC-MS로 분석한 결과, 분자 이온 피크(M+=379)가 검출되어 이 물질을 solanthrene으로 분류하였다. 이 solanidine-solanthrene의 반응은 시간의 경과에 따라 진행되었다. 2. 표준품의 demissidine을 solanidine과 같은 방법으로 가수분해하여 GC-MS로 분석한 결과, solanidine의 경우와는 상이하게 solanthrene는 검출되지 않았고 demissidine (M+=399, 204,150)의 피크만이 검출되었다. 이로써 demissidine은 산 가수분해 처리에 의한 분해가 일어나지 않는 것을 추측 할 수 있었다. 3. α-chaconine, α-solanine, demessine를 산분해하면 α-chaconine과 α-solanine은 solanidine에서 solanthrene으로 분해 반응이 일어났다. 이 두 물질의 아그리콘인 solandine을 측정하는 방법으로는 PGA량을 산출하는 것은 불가능하리라 생각된다. 그러나 산 분해에 의해 생성된 배당체는 매우 안정하여 이 배당체의 당함량을 측정하여 이 두 물질의 PGA 함량을 산출하는 것은 가능하였다. demissine는 산 분해에 의해 생성된 아그리콘(demissidine)은 매우 안정하여 생성된 아그리콘의 양으로부터 demissine 함량을 산출하는 것은 가능하였다.

다국어 초록 (Multilingual Abstract)

This paper was conducted to evaluate aglycones and carbohydrates produced by acid hydrolysis of three potato glycoalkaloids [(PGA); α-chaconine, α-solanine, and demissine] in potatoes. Standard solanidine and demissidine were dissolved in 1N HCl and then heated at 100℃ for 10-120 min. Solanidine was rapidly decomposed during acid hydrolysis and one peak that was identified as solantherene (M+=379) by GC-MS was detected. The transformation solanidine to solanthrene was approximately 50% complete after 10 min, approximately 90% complete after 60 min and 100% complete after 120 min. Demissidine was hydrolyzed using the same method that was used to hydrolyze the solanidine. However, demissidine produced only one peak upon GC-MS (M+=399) analysis and was found to be very stable at increased temperatures. Acidy hydrolysis of α-chaconine, α-solanine and demissine resulted in the decomposition of α-chaconine and α-solanine to solanidine and solanthrene, respectively. Therefore, this hydrolysis method should not be utilized to produce PGA combining with solanidine as aglycone. The individual carbohydrates produced by the two PGAs by hydrolysis were very stable at increased temperatures; therefore, it was possible to quantify these PGAs based on calculation of the individual carbohydrate content. Conversely, because demissidine produced by the hydrolysis of demissine was extremely stable at increased temperatures, it was possible to quantify the PGA based on the aglycone produced by hydrolysis.

참고문헌 (Reference)

1 Friedman M., "α-tomatine determination in tomatoes by HPLC using pulsed amperometric detection" 42 (42): 1959-1964, 1994

2 Cadle LS, "Thin-layer chromatographic system for identification and quantification of potato tuber glycoalkaloids" 26 (26): 1453-1454, 1978

3 Rozumek KE, "Thin-layer chromatographic separation of tomatidenol, solasodine and soladulcidine and yamogenin, diosgenin and tigonenin" 40 (40): 97-102, 1969

4 Keeler RF, "Teratology of steroidal alkaloids. In The Alkaloids" Wiley 389-425, 1986

5 Friedman M., "Steroidal glycoalkaloids. In Naturally Occurring Glycosides: Chemistry, Distribution and Biological Properties" Wiley 311-342, 1999

6 Höhne E., "Solanum alkaloids. IX. X-ray structure analysis of demissidine hydroiodide for the absolute configuration of solanidanes and 22, 26-iminocholestane at C-22" 22 (22): 673-678, 1966

7 Valverde M., "Solamargine: the main glycoalkaloid from the fruits of Solanum paludosum" 59 (59): 483-484, 1993

8 Herbs SF, "Separation of potato glycoalkaloids by gas chromatography" 23 (23): 520-523, 1975

9 Bennett RD, "Separation of closely related steroids by an improved technique for continuous development of thin-layer chromatograms" 21 (21): 488-490, 1966

10 Rayburn JR, "Role of carbohydrate side chains of potato glycoalkaloids in developmental toxicity" 42 (42): 1511-1515, 1994

11 Friedman M., "Reversed-phase high-performance liquid chromatographic separation of potato glycoalkaloids and hydrolysis products on acidic columns" 40 (40): 2157-2163, 1992

12 Crabbe PG, "Rapid quantitative analysis of solasodine, solasodine glycosides and solasodine by high-pressure liquid chromatography" 187 (187): 87-100, 1980

13 Friedman M., "Potato glycoalkaloids: chemistry, analysis, safety, and plant physiology" 16 (16): 55-132, 1997

14 Friedman M., "Postharvest changes in glycoalkaloid content of potatoes. In Impact of Processing on Food Safty" Plenum 121-143, 1999

15 Harvey MH, "Measurement of potato steroidal alkaloids in human serum and saliva by radio immunoassay" 4 (4): 503-512, 1985

16 Kozukue N., "Inheritance of morphological characters and glycoalkaloids in potatoes of somatic hybrids between dihaploid solanum acaule and tetraploid solanium tuberosum" 47 (47): 4478-4483, 1999

17 Mondy NI, "Influence of potassium fertilization on enzymatic activity, phenolic content and discoloration of potatoes" 32 (32): 378-381, 1967

18 Bushway RJ, "Highperformance liquid chromatographic separation of potato glycoalkaloids" 178 (178): 533-541, 1979

19 Gregory P., "Glycoalkaloids of wild, tuber-bearing Solanium species" 29 (29): 1212-1215, 1981

20 "FAOSTAT data"

21 Sinden SL, "Effects of day length and maturity of tomato plants on tomatine content and resistance to Colorado potato beetle" 103 (103): 596-600, 1978

22 King RR, "Analysis of potato glycoalkaloids by gas chromatography of alkaloid components" 63 (63): 1226-1230, 1980

23 Vallejo RP, "Analysis of potato for glycoalkaloid content by radioimmunoassy (RIA). In: Methods and Standards for Environmental Measurments"

24 McMillan M., "An outbreak of suspected solanine poisoning in schoolboys. Examination of criteria of solanine poisoning" 48 (48): 227-243, 1979