Original Article Journal of Apiculture 33(1) : 43~53 (2018) DOI: 10.17519/apiculture.2018.04.33.1.43 Studies on the Organic Compounds and Mineral Constituents of Acanthopanax (Acanthopanax senticosus) and Acacia (Robinia pseudo-acacia) Honey Produced in Korea Weon Ki Paik*, Ae Kyung Kwak, Keun Hong Kim, Myeong Lyeol Lee 1, Yong Soo Choi 1 and Hye Kyung Kim 1 Division of Life Science & Chemistry, Daejin University 1 Department of Agricultural Biology, National Institute of Agricultural Science, RDA (Received 26 March 2018; Revised 25 April 2018; Accepted 26 April 2018) Abstract In order to use as a new functional food material, we analyzed the chemical components including the organic compounds, minerals and Vitamin C of acanthopanax and acacia honey which were produced in South Korea. The condensed rate of methanol extraction in honey was 85.5% of acanthopanax honey and it was 93.06% of acacia honey. In the case of acanthopanax honey, main organic compounds that extract by organic solvents in GC-MS analysis were trichloromethane, phosphine, superpalite, carbon tetrachloride, methyclolpropane, cyclopentane etc. and main aromatic compounds that extract by organic solvents in SPME analysis were dibutyl phthalate, pelargonaldehyde, cyclopentasiloxane, hexasiloxane, pyrrolidine, lauros tearic acid, vulvic acid etc. Also, in case of acacia honey, main organic compounds were trichloromethan, acetoxyethane, hexanaphthene, acetidin etc. and main aromatic compounds were hydrazomethan, azulene, cyclotrisiloxane, hydrazine etc. Proximate composition was crude protein 0.43%, crude fat 0.36%, crude ash 0.04% in acanthopanax honey and crude protein 0.10%, crude fat 0.29%, crude ash 0.06% in acacia honey. Free sugar that analyze by HPLC was fructose 32.38%, glucose 25.25%, total sugars 57.63% in acanthopanax honey and fructose 48.52%, glucose 24.29%, total sugars 72.81% in acacia honey. Vitamin C was not detected in two sample honeys. Minerals by ICP analysis were detected total 23 kinds in acanthopanax honey, K 14.230ppm > Na 6.234ppm > Si 4.206ppm > B 3.461ppm > Ca 2.235ppm > Mg 0.742ppm etc. and total 22 kinds in acacia honey, Na 4.527ppm > Si 3.420ppm > K 3.091ppm > Zn 1.482ppm etc. Key words: Acanthopanax honey, Acacia honey, Organic compounds, Minerals, GC-MS, SPME, ICP *Corresponding author. E-mail: 100@daejin.ac.kr 43
44,. ( ) ( ) (Honey Plants),, (, 2003;, 2007;, 2011),.,,,, (Honey),, (, 2007). (330kcal/100g),, (Ferreres et al., 1991; Sabatier et al., 1992; Chen et al., 2000) (Blaser, 1990; Willix et al., 1992; Molan, 1992, 2001, 2002; Shin and Ustunol, 2005), (, 1994)., hydroxy methyl furfur(hmf), (Kushnir, 1979; White et al., 1962, 1963, 1967, 1979, 1980; Davies, 1975), (1971), (1972) royal jelly, (1984) HMF, diastatic activity,,, (1991), diastase HMF. (2001), (2005), (, 1995;, 2001, 2002;, 2002;, 2003;, 2003;, 2003;, 2008; 2013).,., (Rural Development Administrate RDA, 2015). (Acanthopanax senticosus) (Robinia pseudo-acacia),,,,,, (Leptospermum scoparium). 2012 8 2012 5.
45 Fig. 1. Schematic diagram of solvent extraction of each honey., honeynz (www. honeynz.co.nz) 2013 UMF(Unique Manuka Factor) 15+. 100g 500ml(MeOH 4 : H 2 O 1) 24 Fig. 1 Haxane, Chloroform, Ethyl acetate, Butanol. (SPME) Gas Chromatography SCAN ( : Agilent 6890GC/5973iMSD). ( 2013-203 ). 105 C, Kjeltec 8400 Analyzer unit Foss(Denmark), FOSS Drive unit 2050(Sweden), 500 C. 100g,,,. C Table 1. 5 (fructose, glucose, sucrose, lactose, maltose) (St.Lois, MO, USA) 50% 30 3,590 g 20 (CR-22N, Hitachi, Tokyo, Japan) 0.2µm membrane filter(minisart RC, Sartorious). HPLC(Nanospace SI-2, Shiseido, Tokyo, Japan) (RI-201H, Shodex, Tokyo, Japan). Imtakt Unison UK-Amino(250 3.0mm, 3µm), 60 C, 10µl,
46 Table 1. HPLC operation condition for free sugars and vitamin C Free sugars Vitamin C Instrument Nanospace SI-2, Shiseido, Tokyo, Japan Detector RID(RI-201H,Shodex, Tokyo, Japan) PDA(Thermo Fisher, USA) Wave length Refrative Index 254nm Analytical Column Imtakt Unison Uk-Amino Shiseido Capcellpak MG120 (3.0mm 250mm, 3um) (4.6mm 250mm, 5um) Column Oven Temp. 60 C 40 C Flow rate 0.4ml/min 0.5ml/min Injection vol. 10ul 5ul Mobile Phase 90% ACN, 100 0.05 M KH 2 PO 4 : ACN, 98 : 2 90% 0.4ml 40. C 1g 5% (Metaphosphoric acid, Wako) 20mL (Ultra- Turrax T25, IKA Labo, Germany) 50mL, refrigerated centrifuge(5804r, Eppendorf, Germany) 12,500 g 10 HPLC(Nanospace SI-2, Shiseido, Tokyo, Japan). Shiseido Capcellpak MG 120(250 4.6mm, 5um), 0.05 M KH 2 PO 4 acetonitrile 98:2, 254nm, 5µl, 40 C, 0.5ml/min. (, 2003) 100mL ICP(Inductively coupled plasma) Optical Emission Spectrometer(Model Name: Optima 2000DV, PerkinElmer, USA), forward RF power; 1,300W, pump flow rate; 1.5ml/min, plasma flow; 15L/min, auxiliary flow; 0.2L/min, nebulizer flow; 0.65L/min. 100g (MeOH) 85.50%, 93.06%, H 2 O 75.84g, 83.26g, Butanol 5.74g, 5.01g. Hexane Ethyl acetate Chloroform 0.64g, 2.07g, 1.21g, 1.04g, 3.6g. 0.35g. Haxane, Chloroform, Ethyl acetate, Butanol H 2 O. 87.02% H 2 O 77.63g (, 2014),, (Kim and Rhee, 1996) H 2 O. (MeOH) 91.00%, H 2 O 78.32g Butanol, Hexane, Ethyl acetate Chloroform 7.06g, 0.67g, 4.60g 0.35g (Fig. 2). Fig. 3. GC-MS Chloroform
47 90 80 70 Condensed mass (g) 60 50 40 30 20 Acanthopanax honey Acacia honey Manuka honey 10 0 Hexane Fraction Chloroform Fraction Ethyl acetate Fraction Butanol Fraction H 2 O Fraction Fig. 2. Condensed mass (g) of solvent extractions of acanthopanax (Acanthopanax senticosus), acacia (Robinia pseudo-acacia) and manuka (Leptospermum scoparium) honey 100 (g). Trichloromethane(peak abundance: 5,800, 000), Formyl trichloride, Methenyl trichloride, Superpalite, Carbon Tetrachloride, Butanol Methyclolpropane(peak : 3,200,000), Acetidin, Acetoxyethane, 2- Propenoic acid, Propylcarbinol, Phosphine, Haxane Cyclopentane(peak : 5,800,000), Trimethylene oxide, 3-Methylpentane, Triptane, Hexyl hydride Ethyl acetate Trichloromethane(peak : 5,800,000), Trimethylene oxide, Propanoic acid, 1-Acetoxypropane, 1-Propyl acetate. SPME Dibutyl phthalate(peak : 4,000,000) Pelargonaldehyde, Cyclopentasiloxane, Hexasiloxane, Cycloheptasiloxane, Pyrrolidine, Dodecanoic acid, Lauros tearic acid, Vulvic acid, Dodecylic acid. Fig. 4. GC-MS Chloroform Trichloromethane(peak abundance: 11,000,000), Hexyl hydride, Gettysolve-B, Butanol Propyl carbinol(peak :5,200,000), Acetoxyethane, Acetidin, Haxane Hexanaphthene(peak : 11,600,000), Cyclohexane Ethyl acetate Methane trichloride(peak : 6,000,000), Propanoic acid. SPME Hexyl hydride(peak :31,0000), Hydrazomethan, Cyclotrisiloxane, Cyclopentasiloxane, Hydrazine, Cyclotrisiloxane, Azulene, Dioctyl adipate. (2014) GC-MS Formyl trichloride, Methenyl trichloride, Cyclopentane, Ethyl ethanoate, Trichloromethan, Butyl hydroxide, Butyraldehyde, Methylolpropan, Propyl carbinol, Propanoic acid, Acetoxyethane, Triptane, SPME 1,2-Benzenedicarboxylic acid, Benzaldehyde, Octacosane, Hexatriacontane, Cyclopentasiloxane, Pentanoic acid, Naphthalene, Nonanaldehyde, Cyclopentasiloxane, Pelargonaldehyde, Aldehyde, 3-Pyridinecarbonitrile, Nicotinonitrile, Pyrobenzol, Cyclotrisiloxane, Cyclohexatriene. 100g 21.22%, 0.43%, 0.36%, 0.04%, 77.95%, 18.75%, 0.10%, 0.44%, 0.06%, 80.65%
48 Chloroform Butanol Hexane Ethyl acetate SPME Fig. 3. Organic compound composition spectra of acanthopanax honey by each solvent (Analyzed by Agilent 6890GC/5973iMSD model).
49 Chloroform Butanol Hexane Ethyl acetate SPME Fig. 4. Organic compound composition spectra of acacia honey by each solvent (Analyzed by Agilent 6890GC/5973iMSD model).
50 Table 2. Proximate chemical composition of acanthopanax, acacia and manuka honey (unit: %) Sample Components Moisture Crude protein Crude fat Crude ash Carbohydrate Acanthopanax honey 21.22 0.18 0.43 0.01 0.36 0.02 0.04 0.00 77.95 0.15 Acacia honey 18.75 0.42 0.10 0.01 0.44 0.01 0.06 0.01 80.65 0.39 Manuka honey 19.79 0.07 0.23 0.00 0.34 0.09 0.24 0.00 79.30 0.03 Results are expressed as Mean S.D. Table 3. Contents of free sugars and vitamin C on acanthopanax, acacia and manuka honey Contents Sample Acanthopanax honey Acacia honey Manuka honey Vitamin C (mg/100g) 0.00 0.00 0.00 0.00 0.00 0.00 Total sugars 57.63 3.25 72.81 2.19 70.23 1.53 Fructose 32.38 1.77 48.52 1.85 39.07 2.40 Free sugars (%) Results are expressed as Mean S.D. Glucose 25.25 1.47 24.29 0.33 31.16 0.86 Sucrose 0.00 0.00 0.00 0.00 0.00 0.00 Lactose 0.00 0.00 0.00 0.00 0.00 0.00 Maltose 0.00 0.00 0.00 0.00 0.00 0.00 (Table 2). (2013) (0.28%), (0.57%). (2013)., (1994) 0.26%. (2003) ( 2.71%, 1.06%, 86.41%). 19.79%, 0.23%, 0.34%, 0.24%, 79.30%.,. (1984) 0.02%, 0.57%, 0.10%, 0.12%, 0.0%.. HPLC Table 3. fructose, glucose sucrose, lactose, maltose, 57.63% fructose 32.38%, glucose 25.25%. (2013) (62.27), (35.31%) (26.96%). 72.81% fructose 48.52%, glucose 24.29%, 70.23% fructose 39.07%, glucose 31.16%., C 3. (2003) sucrose 152mg%, glucose 114mg%, fructose 6mg%, Kim Rhee(1996),.
51 Table 4. Mineral contents of acanthopanax, acacia and manuka honey Minerals (ppm) Kind of honey Acanthopanax Acacia Manuka Minerals (ppm) Kind of honey Acanthopanax Acacia Manuka Macrominarals K 14.230 0.764 3.091 0.152 11.865 0.346 Na 6.234 0.302 4.527 0.366 5.573 0.308 Ca 2.235 0.053 0.294 0.013 2.223 0.161 Mg 0.742 0.017 0.492 0.025 0.605 0.006 Microminarals Other microminarals B 3.461 0.624 1.319 0.521 1.754 0.158 Si 4.206 0.024 3.420 0.569 4.487 0.004 Fe 0.465 0.024 0.226 0.005 0.165 0.020 Sb 0.212 0.000 0.107 0.006 0.217 0.000 Se 0.290 0.001 0.017 0.024 0.290 0.000 Ti 0.159 0.000 0.195 0.001 0.236 0.032 Co 0.267 0.000 0.250 0.001 0.269 0.001 Al 0.194 0.003 0.154 0.017 0.220 0.028 Cr 0.266 0.000 0.000 0.000 0.273 0.001 As 0.092 0.002 0.000 0.000 0.064 0.006 Zn 0.239 0.047 1.482 0.197 0.267 0.036 Cd 0.041 0.000 0.058 0.000 0.040 0.000 Cu 0.084 0.008 0.119 0.018 0.035 0.001 Sr 0.026 0.001 0.019 0.001 0.013 0.001 V 0.024 0.001 0.000 0.000 0.024 0.001 Ba 0.017 0.001 0.039 0.009 0.010 0.003 Mo 0.016 0.001 0.056 0.004 0.017 0.001 Li 0.006 0.000 0.099 0.000 0.005 0.000 Ni 0.000 0.000 0.057 0.000 0.000 0.000 Pb 0.003 0.000 0.000 0.000 0.000 0.000 Mn 0.000 0.000 0.011 0.001 0.000 0.000 Be 0.000 0.000 0.118 0.001 0.000 0.000 Results are expressed as Mean S.D. ICP 23 K 14.230ppm > Na 6.234ppm > Si 4.206ppm > B 3.461ppm > Ca 2.235ppm > Mg 0.742ppm, 22 Na 4.527ppm > Si 3.420ppm > K 3.091ppm > Zn 1.482ppm (Table 4). (macrominerals) Mg, Ca, Na, K, (microminerals) Mo, Zn, Cu. K 11.865ppm > Na 5.573ppm > Si 4.487ppm > Ca 2.223ppm. K 4.60, 3.84 Na. (2011) K. Ca 7.60, 7.56 Mg 1.50, 1.23.. WHO, Cd (0.041ppm), (0.058ppm), (0.040ppm) (WHO : 0.3ppm ). (Rashed and Soltan, 2004).
52. 85.50%, 93.06%, GC-MS Trichloromethane, Phosphine, Superpalite, Carbon Tetrachloride, Methyclolpropane, Cyclopentane Trichloromethan, Hexyl hydride, Propyl carbinol, Acetoxyethane, Acetidin, Hexanaphthene, Methane trichloride. SPME Dibutyl phthalate, Pelargonaldehyde, Cyclopentasiloxane, Hexasiloxane, Pyrrolidine, Dodecanoic acid, Lauros tearic acid, Vulvic acid Hexyl hydride, Hydrazomethan, Azulene, Cyclotrisiloxane, Hydrazine. 21.22%, 0.43%, 0.36%, 0.04%, 77.95% 18.75%, 0.10%, 0.44%, 0.06%, 80.65%, (0.23%) (0.34%). HPLC 57.63%, fructose 32.38%, glucose 25.25% 72.81%, fructose 48.52%, glucose 24.29%, 70.23%, fructose 39.07%, glucose 31.16% C 3. ICP 23 K 14.230ppm > Na 6.234ppm > Si 4.206ppm > B 3.461ppm > Ca 2.235ppm > Mg 0.742ppm, 22 Na 4.527ppm > Si 3.420ppm > K 3.091ppm > Zn 1.482ppm. K 11.865ppm > Na 5.573ppm > Si 4.487ppm > Ca 2.223ppm, K 4.6, 3.84 K Na. ( : PJ009378).,,. 1994., HMF. 23: 675-679.,,. 2008.. 21: 15-21.,,,. 1995.. 18: 53-56.,. 1972. free amino acid. 6: 7.,,,,. 2013. ( ). 28: 345-354.,,,. 2014.. 29: 125-135.. 2003.. J. Fd Hyg. Safety 18: 184-194.,,,,,. 2003... pp. 178-184.. 2003.., 2003.. 3p.,,,,,,. 2007.. 22: 147-152.,,,,. 1971.. 3: 168.,,. 2001.. 21: 383-388.,,. 2002.. 22: 66-71.,,,,,,. 2002.. 31: 899-904.,,,,. 2011., Hydroxy Methyl Furfural. 31: 241-249.. 2005.. 34: 162-166.
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