1 Nippon Shouhin Kagau Kogau Kaishi Vol. /1, No. 1,,1/,21 (,+) 275 Engineering Studies on Extraction and Separation of Food Substances Shuji Adachi Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Sayo-u, Kyoto 002/, Basic food engineering studies have been carried out on extraction of food materials using subcritical water and chromatographic separation of sugars. An equation for describing the arent distribution coe$ cient of a sugar to a cation-exchange resin was proposed. The equation allowed us to estimate the equilibrium constant for ligand exchange between various inds of sugars and counter-ions, and the swelling pressure of the resin. Two mathematical models were proposed for calculating the concentration profiles of solutes in a simulated moving-bed chromatograph, by which two solutes can be continuously separated. A criterion for achieving good separation was also determined. Materials having functionalities such as emulsifying or antioxidative ability could be extracted from unused bioresources by their subcritical water treatment. Many reactions would occur during the treatment. Therefore, catalytic properties of subcritical water were inetically investigated for decomposition or degradation of various compounds. (Accepted Apr.,,,+) Keywords : chromatographic separation, simulated moving-bed, subcritical water, unused bioresources, extraction : + + -1. - + 002/, Corresponding authoradachi@ais.yoto-u.ac.jp
276 /1 1,+ 1 2,,+,++ K + S v P K +. / M B SM + K SSM, - K -01 CE CS B 2 3+ vs B K K + BC e BCEep KK+ + BKC Se K p K g exp PvSRT C e K R T e K g K v,+- S, +, K K P B K v K K P S p S + S, M SM K B E p E p.3+
3 : 277 +. +/ +0 - +2 ++ +, K Freundlich. 3+ +- K, K, Langmuir Langmuir Freundlich,+.,,. Ca Glc Man Fru +1 bodo no, K K,. Ca,,+ K +, Z b, Ca K ZZ, Ca ZZ e K K, K, K, K Ca - b BKC e K K S p b K +3,, Z e - a K ao +
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5 : 279 + Ka n + + + + + + + + C C z C C C C eb vn KfavCC t z C + ebm KfavCC t C C,, t av K v n,,- f m SMBC K K m K f b n C C u u + e m b n,, b A B b + f n,,, Ca SMBC u,,. +,, dc un KfavCC dz dc + ebmu s Ka f vcc dt,- u SMBC L T SMBC u,,. v u v e LT, ao C C v s n n n n b f s +, b,.,/,0, + b b An Bn b n n s b n n n n,, SMBC
280 /1 1,+ 1 6 SMBC,1,3 SMBC,2 -, SMBC - -- - -+ -, -- SMBC,, / + SMBC / SMBC -. SMBC -. / SMBC -3 - -+ + -1. SMBC -1..+ 0 /, - SMBC, +., + mol L, - ++, / + mol L SMBC - -. -/ -0-1. -2
7 : 281 0 VC C -,.0 1 +/ -, +,,/ DPPH +/ +2,/ 1.,...1./, / HMF DPPH 1 -,,.- DPPH, Lowry-Folin, OW,.. Umulac AT,/ DPPH.+, DPPH DPPH,0 1.- DPPH.2 0/ 2./, /., +., +
282 /1 1,+ 1 8 2,0 /./ 3 +, C +/ C +2 C MD,/ ++ C /+ DPPH,/.3 / /- /. // Ka$ r lime /0 OW,,/ +, +/ +2 --,/ -- + /+ ++ 3 +2 /1 /2,/ +/, - + + +/ wv /, -,-
9 : 283 + methyl methacrylate.. 0 mmf+/ mm 0, +/ vv., mlmin. /3 OW + nm 0 0. --, 0/ 0/ 01 HMF HMF HMF 0. 0/ 01 0+ 0-0, + HPLC +/ vv 02 1 +- +. 03 03 ++ a-, + + ++,, + MPa 03 -. -.+, a-, +. b-, +0 + Weibull
284 /1 1,+ 1 10 n CC expt C t C + 1. n ph 1 Weibull 10 + ph + CC 1+ 11. 1,, -.-, 0 1-1/ +, a-, +. + exo endo c3 t++ t+ c+, 13 -. 2 1/ ph / -., -. 12
11 : 285 + Adachi, S., Watanabe, T. and Kohashi, M., Role of swelling pressure on the distribution coe$ cient of maltooligo- saccharide in a cation-exchange resin. Agric. Biol. Chem., /-, -,--,2 ( +323)., Adachi, S. and Matsuno, R., E# ect of eluent composition on the distribution coe$ cient of saccharides onto a cation-exchange resin in sodium-ion form. Biosci. Biotech. Biochem., 0+, +,30 +-+ ( +331). - Adachi, S., Yoshino, T. and Matsuno, R., Estimation of the binding constant of a saccharide to sodium-ion using cation-exchange resins with di# erent divinylbenzene contents. J. Chem. Eng. Japan, -,, 01202- ( +333).. Adachi, S., Mizuno, T. and Matsuno, R., Concentration dependence of the distribution coe$ cient of maltooligo- saccharides on a cation-exchange resin. J. Chromatogr. A, 12, +11 +2/ ( +33/ ). / Adachi, S., Mizuno, T. and Matsuno, R., Temperature dependence of the distribution coe$ cient of maltooligo- saccharides on cation-exchange resin in Na form. Biosci. Biotech. Biochem., 0, --2-. ( +330). 0 Adachi, S. and Matsuno, R., Estimation of the binding constants of hexoses to the counter-ion of a cationexchange resin based on their arent distribution coe$ cients to the resin. Japan J. Food Eng., +,./.3 (,). 1 Maeda, A., Adachi, S. and Matsuno, R., Estimation of the binding constant of --etocellobiose to a cation from the arent distribution coe$ cient onto cationexchange resin in the ionic form. Japan J. Food Eng.,., +3,- (,-). 2. D,+1,2. 3 Adachi, S. and Matsuno, R., Apparent distribution coe$ cients of glucose and fructose to cation-exchange resins in some ionic forms. J. Appl. Glycosci.,.0, 3+. ( +333). + Adachi, S. and Matsuno, R., Apparent distribution coe$ cients of glucose and fructose onto cation-exchange resin in calcium-ion form with di# erent divinylbenzene contents. Food Sci. Technol. Res., 0, -- --. (,). ++ Naanishi, K., Yamamoto, S., Matsuno, R. and Kamiubo, T., Analysis of dispersion mechanism in gel chromatography. Agric. Biol. Chem., -+, +.0/ +.1- ( +311). +, - pp. /-12,/ +- Adachi, S., Mizuno, T. and Matsuno, R., Thermogravimetric measurement of the distribution coe$ cients of maltooligosaccharides upon a cation-exchange resin. Food Sci. Technol., Int., +, -. -1 ( +33/ ). +. Hashimoto, K., Adachi, S., Shirai, Y. and Horie, M., E# ect of the content of divinylbenzene of ion-exchange resin on the chromatographic separation of a-cyclodextrin and glucose. J. Chromatogr.,..2,,.+,.2 ( +322). +/ Adachi, S., Watanabe, T. and Kohashi, M., E# ects of the divinylbenzene content and ionic form of cationexchange resin on the chromatographic separation of maltooligosaccharides. Agric. Biol. Chem., /-, -+3--,+ ( +323). +0 Maeda, A., Adachi, S. and Matsuno, R., Chromatographic separation of --etoglucose and glucose or --etocello- biose and cellobiose using a cation-exchange resin in potassium-ion form. Biochem. Eng. J. +-, +/, (,-). +1 Adachi, S., Watanabe, T. and Hashimoto, K., Distribution and dispersion properties in gel chromatographic
286 /1 1,+ 1 12 separation of maltooligosaccharides with hydrophilic --. vinyl polymer gel. Denpun Kagau, -0,,+,. ( +323 ). pp. /-12,/ +2 Adachi, S., Panintrarux, C., Arai, Y., Kimura, Y. and -. Hashimoto, K., Adachi, S., Noujima, H. and Ueda, Y., A Matsuno, R., Separation of alyl-b-d-glucosides and n- new process combining adsorption and enzyme reacalcohols by using a porous trimethylolpropane tri- tion for producing higher-fructose syrup. Biotechnol. methacrylate homopolymer gel. Biosci. Biotech. Biochem., Bioeng.,,/,,-1+,-3- ( +32-). /2, +//2 +/0- ( +33. ). -/ Hashimoto, K., Adachi, S. and Shirai, Y., Development of +3 Adachi, S., Panintrarux, C. and Matsuno, R., Methods for new bioreactors of a simulated moving-bed type. Preestimating the parameters of nonlinear adsorption iso- parative and Production Scale Chromatography, Chaptherms of Langmuir- and Freundlich-types from a re- ter +1, ed. by G. Ganetsos and P.E. Barer, Marcel sponse curve of pulse input of an adsorbate. Biosci. Deer, New Yor, pp. -3/.+3 ( +33-). Biotech. Biochem., 0+, +0,0 +0-- ( +331). -0 /, Broughton, D.B., Continuous sorption process employ- pp. +-, +/,,/ ing fixed bed of sorbent and moving inlets and outlets. -1 Adachi, S., Watanabe, T. and Kohashi, M., An enzyme US Patent,32//23 ( +30+ ). reactor based on the di# erence in migration rate in gel,+ Hashimoto, K., Morishita, M., Adachi, S., Shindo, K., chromatographic columns between enzyme and sub- Shirai, Y. and Tanigai, M., Continuous separation of strate. Agric. Biol. Chem., /-, +/31 +0, ( +323). bio-components by rotating annular chromatography. -2 Adachi, S., Hashimoto, K., Matsuno, R., Naanishi, K. Prep. Chromatogr., +, +0- +11 ( +323). and Kamiubo, T., Pulse response in an immobilized-,, Hashimoto, K., Adachi, S., Noujima, H. and Maruyama, enzyme column : theoretical method for predicting elu- H., Models for the separation of glucose/fructose mix- tion curves. Biotechnol. Bioeng.,,,, 113131 ( +32 ). ture using a simulated moving-bed adsorber. J. Chem. -3 Adachi, S., Hashimoto, K., Miyai, K., Kurome, H., Matsuno, Eng. Japan, +0,..0 ( +32-). [ 0] R. and Kamiubo, T., Pulse response in an immobilizedenzyme,- column : elution profiles in reversible and con- +0 +3- +30 secutive reactions. Biotechnol. Bioeng.,,-, +30+ +310 ( +32+ ). +33. Adachi, S., Tanabe, S. and Hashimoto, K., Determination,. of pyruvate, L-lactate, and glutamic pyruvic transcolumn. aminase by using an immobilized-lactate dehydrogenase +1 Biotechnol. Bioeng.,,0, 0-/ 0-3 ( +32. ). 0,-0,0 +33+.+ Wanger, W. and Pruß, A., The IAPWS formulation +33/,/ Hashimoto, K., Adachi, S., Shirai, Y. and Horie, M., Con- for the thermodynamic properties of ordinary water tinuous separation of a-cyclodextrin and glucose using substance for general and scientific use. J. Phys. Chem. a simulated moving-bed adsorber. J. Food Eng., 2, +21 Ref. Data, -+, -21 /-/ (,,)., ( +322 ).., Wiboonsiriul, J., Hata, S., Kimura, K., Tsuno, T. and,0 Hashimoto, K., Adachi, S. and Shirai, Y., Continuous Adachi, S., Production of functional substances from desalting of protein by a simulated moving-bed adsorber. Agric. Biol. Chem., /,,,+0+,+01 ( +322). blac rice bran by its treatment in subcritical water. LWT-Food Sci. Technol.,., +1-, +1. (,1).,1 Hashimoto, K., Yamada, M., Shirai, Y. and Adachi, S..- Wiboonsiriul, J., Kimura, K., Kadota, M., Morita, H., Continuous separation of glucose-salts mixture with non-linear and linear adsorption isotherms by using a simulated moving-bed adsorber. J. Chem. Eng. Japan,,,./.+ ( +321)... Tsuno, T. and Adachi, S., Properties of extracts from defatted rice bran by its subcritical water treatment. J. Agric. Food Chem., //, 21/3210/ (,1). Hata, S., Wiboonsiriul, J., Maeda, A., Kimura, Y. and,2 Hashimoto, K., Yamada, M., Adachi, S. and Shirai, Y., A Adachi, S., Extraction of defatted rice bran by subcritical simulated moving-bed adsorber with three zones for continuous separation of L-phenylalanine and NaCl. J. Chem. Eng. Japan,,,,.-,.-. ( +323)../ water treatment. Biochem. Eng. J.,.,.. /- (,2). Wiboonsiriul, J., Kimura, Y., Kanaya, Y., Tsuno, T. and Adachi, S., Production and characterization of functional,3 Hashimoto, K., Shrai, Y., Morishita, M. and Adachi, S., substances from a by-product of rice bran oil and Continuous separation of glycerol and NaCl with linear and unfavorable adsorption isotherms by use of a simulated moving-bed adsorber. J. Chem. Eng. Japan,,/,./-.// ( +33, )..0 protein production by a compressed hot water treatment. Biosci. Biotechnol. Biochem., 1,, -2. -3, (,2). Jeyashoe, N., Chiou, T.Y., Neoh, T.L., Murayama, Y. Kobayashi, T. and S. Adachi, S. E# ect of temperaturerising - Hashimoto, K., Shirai, Y. and Adachi, S., A simulated rate on the antioxidative ability of the defatted moving-bed adsorber for the separation of tricompo- rice bran extract obtained by subcritical water treatment. nents. J. Chem. Eng. Japan,,0, /, /0 ( +33-). Food Sci. Technol. Res., +0, +31, (,+). -+ Adachi, S., Simulated moving-bed chromatography for.1 Murayama, Y., Neoh, T.L., Kobayashi, T. and Adachi, S., continuous separation of two components and its lication Production of emulsifying and antioxidative sub- to bioreactors. J. Chromatogr. A, 0/2,,1+,2, stances from defatted rice bran by two-step subcritical ( +33. ). water treatment. Japan J. Food Eng., +, +1 ++. (,3). -, Hashimoto, K., Adachi, S., Shirai, Y. and Morishita, M.,.2 Wiboonsiriul, J., Saai, Y., Hosoda, A., Morita, H., Operation and design of simulated moving-bed adsorbers, Preparative and Production Scale Chromatography, Chapter +-, ed. by G. Ganetsos and P. E. Barer, Marcel Deer, New Yor, +33-, pp.,1--. Kimura, Y., Taniguchi, H., Tsuno, T. and Adachi, S., Mutagenicity of the extract from defatted rice bran by subcritical water treatment. Japan J. Food Eng., 3, 1/ 12 (,2).
13 : 287.3 Wiboonsiriul, J., Khuwijitjaru, P., Kimura, Y., Morita, R. and Adachi, S., Degradation inetics of monosac- H. Tsuno, T. and Adachi, S., Production optimization of charides in subcritical water. J. Food Eng., 02, -3-+- the extract with high phenolic content and radical (,/). scavenging activity from defatted rice bran by subcrit- 0/ Usui, C., Kimura, Y. and Adachi, S., Degradation of ical water treatment. Japan J. Food. Eng., 2, -++ -+/ pentaoses and hexauronic acids in subcritical water. (,1). Chem. Eng. Technol., -+, +-- +-1 (,2). / Khuwijitjaru, P., Nualchan, P. and Adachi, S., Foaming 00 Wang, R., Kobayashi, T. and Adachi, S., Degradation and emulsifying properties of rice bran extracts ob- inetics of D-glacturonic aid and sdium D-glacturonate tained by subcritical water treatment. Silpaorn U. Sci. in sbcritical wter. J. Appl. Glycosci., /0, +2+ +2. (,3). Technol. J., +, 1 +, (,1). 01 Wang, R., Neoh, T.L., Kobayashi, T., Miyae, Y., Hosoda, /+ Wiboonsiriul, J., Naazawa, R., Kobayashi, T., Morita, A., Taniguchi, H. and Adachi, S., Degradation inetics of H., Tsuno, T. and Adachi, S., Suppression of the oxida- glucuronic acid in subcritical water. Biosci. Biotechnol. tion of methyl linoleate encapsulated with the extract Biochem., 1., 0+ 0/ (,+). from defatted rice bran by a compressed hot water 02 Ohshima, J., Haghighat Khajavi, S., Kimura, Y. and treatment. Eur. Food Res. Technol.,,,2, +3 ++. (,2). Adachi, S., E# ects of sodium chloride on the degradation /, Habeych, E., van der Goot, A. J. and Boom, R., Comdependences of hexoses and the hydrolysis of sucrose in subcrit- patibilization of starch-zein blends under shear flow. ical water. Eur. Food Res. Technol.,,,1, 1332- (,2). Abstract of / th International Symposium on Food Rhe- 03 Oomori, T., Haghighat Khajavi, S., Kimura, Y., Adachi, ology and Structure, Zurich,,3. S. and Matsuno, R., Hydrolysis of disaccharides contain- /- Wiboonsiriul, J. and Adachi, S., Extraction of function- ing glucose residue in subcritical water. Biochem. Eng. al substances from agricultural products or by-products J., +2, +.- +.1 (,.). by subcritical water treatment. Food Sci. Technol. Res., 1 Haghighat Khajavi, S., Kimura, Y., Oomori, T., Matsuno, +., -+3-,2 (,2). R. and Adachi, S., Decomposition inetics of maltose in /. Kataoa, M., Wiboonsiriul, J., Kimura, K. and Adachi, subcritical water. Biosci. Biotechnol. Biochem., 02, 3+ 3/ S., Properties of extracts from wheat bran by its subcrit- (,.). ical water treatment. Food Sci. Technol. Res., +., //- //0 1+ Haghighat Khjavi, S., Kimura, Y., Oomori, T., Matsuno, (,2). R. and Adachi, S., Kinetics on sucrose decomposition in // Murayama, Y., Kobayashi, T. and Adachi, S., Properties subcritical water. Lebensm.- Wissens. u. Technol., -2,,31 of extracts from soy sauce cae using subcritical water -, (,/). treatment. Japan J. Food Eng., ++, 011+ (,+). 1, Haghighat Khajavi, S., Ota, S., Naazawa, R., Kimura, Y. /0 Khuwijitjaru, P., Chalooddong, K. and Adachi, S., Phenolic and S. Adachi, S., Hydrolysis inetics of trisaccharides content and radical scavenging capacity of a$ r lime fruit peel extracts obtained by pressurized hot water extraction. Food Sci. Technol. Res., +., +. (,2). 1- consisting of glucose, galactose and fructose residues in subcritical water. Biotechnol. Prog.,,,, +-,+ +-,0 (,0). Haghighat Khajavi, S., Ota, S., Kimura, Y. and Adachi, /1 Khuwijitjaru, P., Adachi, S. and Matsuno, R., Solubility S., Kinetics of maltooligosaccharide hydrolysis in subcritical of saturated fatty acids in water at elevated temperatures. Biosci. Biotechnol. Biochem., 00, +1,- +1,0 (,,). 1. water. J. Agric. Food Chem., /., -00--001 (,0). Kobayashi, T., Taase, K. and Adachi, S., Degradation /2 Khuwijitjaru, P., Kimura, Y., Matsuno, R. and Adachi, S., Solubility of oleic and linoleic acids in subcritical water. inetics of branched-chain amino acids in subcritical water. Biosci. Biotechnol. Biochem., 1., 0.30/+ (,+). Food Sci. Technol. Res., +,,0+,0- (,.). 1/ /3 Khuwijitjaru, P., Kimura, Y., Matsuno, R. and Adachi, S., Preparation of finely dispersed O/W emulsion from + p. 31,3 fatty acid solubilized in subcritical water. J. Colloid 10 Khuwijitjaru, P., Fujii, T., Adachi, S., Kimura, Y. and Interface Sci.,,12, +3, +31 (,.). Matsuno, R., Kinetics on the hydrolysis of fatty acid 0 Katagi, S., Kimura, Y. and Adachi, S., Continuous preparation esters in subcritical water. Chem. Eng. J., 33, +. (,.). of O/W nano-emulsion by the treatment of a coarse emulsion under subcritical water conditions. LWT Food Sci. Technol.,., +-10 +-2 (,1). 11 Fujii, T., Khuwijitjaru, P., Kimura, Y. and Adachi, S., Decomposition inetics of monoacyl glycerol and fatty acid in subcritical water under temperature-program- 0+ Mori, M. and Adachi, S., Temperature dependence of med heating conditions. Food Chem., 3., -.+ -.1 (,0). distribution coe$ cients of ca# eine and vanillin on hydrophobic resin in an aqueous system. Japan J. Food Eng., 1, +.+ +./ (,0). 12 Asano, T., Maeda, A., Kimura, Y., Taahashi, T., Naa- mura, A., Maeda, H. and Adachi, S., Condensation reaction between angiotensin II and dicarboxylic acid in 0, Kiuchi, S., Kobayashi, T. and Adachi, S., Dependences water at high temperature without any catalytic agent of the distribution coe$ cients of hydrophobic solutes additive. Biotechnol. Progr.,,+, ++03 ++1. (,/). on porous methyl methacrylate resin on the temperature 13 Usui, C., Kimura, Y. and Adachi, S., Conversion of and methanol content of the eluent. Food Sci. linoleic acid to its conjugated isomers in subcritical Technol. Res., +., +.. +.1 (,2). water. Japan J. Food Eng., 1, +.1 +/ (,0). 0- Kiuchi, S., Kobayashi, T. and Adachi, S., Temperature 2 Usui, C., Kimura, K. and Adachi, S., Isomerization of of the distribution coe$ cients of hydro- hexoses in subcritical water. Food Sci. Technol. Res., +-, phobic solutes onto porous styrene divinylbenzene resin for the eluent with a low methanol content. J. Biosci. Bioeng., +0,,2,+ (,2).,/,3 (,1).,,., 0. Haghighat Khajavi, S., Kimura, Y., Oomori, T., Matsuno,