326 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /., No.1, -,0 --+ (,**1) 14 ao EPA The Crystal Properties of Cyclic Nigerosyl-(+ 0)-nigerose (CNN) and P

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1 326 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /., No.1, -,0--+ (,**1) 14 ao EPA The Crystal Properties of Cyclic Nigerosyl-(+0)-nigerose (CNN) and Powdering of a-tocopherol, Cholecalciferol and EPA Using CNN Kazuyuki Oku, Naoki Kudou, Mayumi Kurose, Takashi Shibuya, Hiroto Chaen and Shigeharu Fukuda Glycoscience Institute, Research Center, Hayashibara Biochemical Laboratories, Inc., 01/+ Fujisaki, Okayama 1*,2**, Cyclic nigerosyl-(+0)-nigerose (CNN) has a unique structure consisting of four glucose residues connected by alternate a-(+-)- and a-(+0)-linkages. We investigated the crystal properties of CNN and the stability of powdered functional oils using CNN. As a result of thermal analysis, we found that CNN takes - crystal forms, /H,O, +H,O and anhydrous crystals. The alcohol retention capacity of variously cyclic saccharides, such as a-, b- andg-cyclodextrin (CD), was also examined. Ethanol and propanol retention capacities were observed in the order b-cdcnnb-cdg-cd. We then examined the stability of powdered fat-soluble vitamins, vitamin D -, vitamin E and eicosapentaenoic acid, by using anhydrous CNN ; CNNfunctional oil powders showed the highest residual values. These results indicate that CNN is useful for powdering easily oxidized fat-soluble substances. (Received Feb.,,,**1 ; Accepted Mar.,.,,**1) Keywords :cyclic nigerosyl-(+0)-nigerose, crystal properties, fat-soluble vitamins, EPA, powdering : EPA CNN ; cyclo 0-D- Glcp-+--a-D-Glcp-+0-a-D-Glcp-+--a-D-Glcp-+. a-+,- a-+,0 +, Bacillus globisporus, +,0oao +,-oao 0, CNN -/ CNN ph - +* 01 CNN CD 2 CD 1*,2**0 01/+ Corresponding author okukaz@hayashibara.co.jp D - V.D E V.E EPA EPA 3+, CNN CNN CNN CD CNN

2 15 : CNN / CNN +- a b g CD, : : CD : P CD 2* CD /* : SF, +/ no no no V.D, ao V.E, EPA, 3/ 33./ V.D - V.E +* EPA - ww, CNN / CNN / TGDTA / mg Al TG DTA TGDTA,,* SII -* -/* +*min -* mlmin - CNN CNN / +-* - 2* 0 CNN,* WV X RAD-B, Rigaku X ;Cu-Ka ; -/ kv, ;,/ ma. CNN CNN / -.CNN CNN *./ g RH --.* 31.-,/ + + X RH / CNN CNN Hashimoto 3 CNN,* wv - Ika, *../ m +0 CNN CD CD 0 *./ g +* ml GLC CNN +-+. TMS GLC CD CNN GLC :GLC ;GC- +.A ;TC-/ *./- mmid+/ m, df+./ mm, GL ;.*-** 1./min ; + mlmin, l +-* CNN :GLC ;GC-+.A ;, OV-+1 Chromosorb W AW-DMCS -.* mmid, m, GL ; +0*-,* 1./min ; -/ mlmin ; - l TMS 1 CNN, CD 2* 0 *./. g *.1/ g / + g,* ml V.D V.E 0* EPA.* + 2 V.D 1* vv /* ml - *** rpm, +* f*../ m V.D V.D UV-,.**PC

328 /. 1,**1 1 16 Abs.,0/ nm V.D V.D V.E EPA 0 ml +* ml V.E EPA V.E GLC EPA GLC +/ EPA - ml no + mgml + ml +. wv GL *./ ml 2* / EPA + ml no + ml EPA V.E EPA GLC V.E : GLC ;GC-+.A ;TC-/ *.

3 328 /. 1,** Abs.,0/ nm V.D V.D V.E EPA 0 ml +* ml V.E EPA V.E GLC EPA GLC +/ EPA - ml no + mgml + ml +. wv GL *./ ml 2* / EPA + ml no + ml EPA V.E EPA GLC V.E : GLC ;GC-+.A ;TC-/ *./- mmid+/ m, df*.,/ m, GL ;,**-,* 1./min ; + mlmin ;, l +-* EPA : GLC ; GC-+.B ; TC-FFAP *./- mmid-* m, df*.,/ m, GL ; +2*,.* 1./min ; + mlmin ;. l +-* + CNN CNN/ TGDTA Fig. + +** 3./ CNN / +.,+* -., + -** DTA CNN / +,, CNN CNN / +-* - 2* 0 X +-* -,.2 CNN + + 2* 0 *., CNN + : *.*1 CNN X CNN / Fig. + TG/DTA curve of CNN/H,O crystal Fig., X-ray di#raction patterns of dried CNN powders Fig., +-* - CNN + 2* 0 CNN CNN 3.1 Bradbrook X CNN CNN +. 2 Furihata CNN DMSO, NMR ROESY CNN CNN CNN + TGDTA / +** +,+* +,+* + CNN CNN / + -**,1+./

4 17 : 329 Fig. - Hygroscopicity of dried CNN powders placed at Various RH conditions at 1days for,/. A;CNN/H,O crystals, B ; CNNH,O crystals, C ; CNN anhydrous crystals, D ; amorphous CNN. ;RH--.*, ;RH/,.2, ;RH0*.*, ;RH1/.,, ;RH2..,, ;RH * CNN CNN CNN CNN - CNN CNN. CNN RH --.* 31.-,/ + X CNN Fig. - CNN / RH --.* 31.- CNN + RH 0*.* RH 2.., +. X / CNN + 3+* RH --.*0*.* +. RH 1/.,31.-, X / CNN 3+. RH --.*0*.* +. RH 1/.,31.- / CNN / CNN + CNN RH 0*.* RH 1/.- / CNN + CNN. CNN CD / CNN CNN CD Table + CNN CNN C- CNN + *./- *..* *.,. CNN a-cdcnnb-cdg-cd CNN / CNN CNN

5 330 /. 1,** Table + Alcohol content of the cyclic sugar-alcohol preparations Alcohol CNN a-cd b-cd g-cd ratio* ratio ratio ratio Methanol Ethanol n-propanol n-butanol n-pentanol / 1240 *4/, *42/ +4,, +4+1 *433 /4.,04,..4-, , *4++ *4.* *4/- *4,. *4*2, ,,4, *4*1 *4-0 *4.3 *4/+ *41, *4* 042 +*43, *4** *4,* *4,1 *4-/ *4., * Alcohol/Sugar. V.D CNN +/-* CNN 1 V.D /* V.E - CNN 3/ EPA CNN CNN 2/ 1 //.+ CD CNN MM- ab nito B-LYP0-+G**, EPA Oku cis CHO OHp NMR,*,+ CNN CNN CNN Fig.. E#ect of CNN on the stability of fat-soluble vitamins and fatty acid, as compared with the other saccharides A ; Vitamin D, B ; Vitamin E, C ; Eicosapentaenoic acid. ; CNN, ; trehalose, ; maltose, ; cellulose, ; branched CD. Fig.. CNN CNN CNN CD CNN CNN / CNN / +, CNN CNN

6 19 : 331 CNN / + CNN RH 1/ / CNN CD a-cd CNNb-CDg-CD CNN CNN CNN CNN + Cote, G.L. and Biely, P., Enzymically produced cyclic a- +,--linked and a-+,0-linked oligosaccharides of D-glucose. Eur. J. Biochem.,,,0, (+33.)., Biely, P., Cote, G.L. and Burgess-Cassler, A., Purification and properties of alternanase, a novel endo-a-+,--a-+,0 -D-glucanase. Eur. J. Biochem.,,,0, (+33.). - Aga, H., Higashiyama, T., Watanabe, H., Sonoda, T., Nishimoto, T., Kubota, M., Fukuda, S., Kurimoto, M. and Tsujisaka, Y., Production of cyclic tetrasaccharide from starch using a novel enzymes system from Bacillus globisporus C++. J. Biosci. Bioeng., 3., --0-., (,**,).. Aga, H., Nishimoto, T., Kuniyoshi, M., Maruta, K., Yamashita, H., Higashiyama, T., Nakada, T., Kubota, M., Fukuda, S., Kurimoto, M. and Tsujisaka, Y., 0-a- Glucosyltransferase and --a-isomaltosyltransferase from Bacillus globisporus N1/. J. Biosci. Bioeng., 3/,,+/,,. (,**-). / Nishimoto, T., Aga, H., Kubota, M., Fukuda, S., Kurimoto, M. and Tsujisaka, Y., Production of cyclic tetrasaccharide with 0-a-glucosyltransferase and a-isomaltosyltransferase. J. Appl. Glycosi., /+, +-/+.* (,**.). 0,.. /-3//*,**0 1 FFI,++ 2/.20,,**0 2 Bradbrook, G.M., Gessler, K., Cote, G.L., Momany, F. Biely, P., Bordet, P.,Perez, S. and Imberty, A., X-ray structure determination and modeling of the cyclic tetrasaccharide., Carbohydr. Res., -,3, 0//00/(,***). 3 Hashimoto, H., Preparation and application of cycrodextrins, Handbook of amylases and related enzymes,,--, Pergamon Press (+322). +* Minemoto, Y., Fang, X., Hakamata, K., Watanabe, Y., Adachi, S. Kometani, T. and Matsuno, R., Oxidation of linoleic acid encapsulated with soluble soybean polysaccharide by spray-drying., Biosci. Biotechnol. Biochem., 00, +2,3+2-. (,**,). ++ Watanabe, Y., Fang, X., Minemono, Y., Adachi, S. and Matsuno, R., Suppressive e#ect of saturated acyl L- ascorbate on the oxidation of linoleic acid encapsulated with maltodextrin or gum arabic by spray-drying., J. Agric. Food Chem., /*, (,**,). +, +3 +* / Watanabe, H., Nakano, M., Oku, K., Aga, H., Nishimoto, T., Kubota, M., Fukuda, S., Kurimoto, M. and Tsujisaka, Y., Cyclic tetrasaccharide in sake lees., J. Appl. Glycosci., /+, -./-.1 (,**.). +/ / Furihata, K., Fujimoto, T., Tsutsui, A., Machinami, T. and Tashiro, M., Identification of bond water molecules in the cyclic tetrasaccharide, cyclo 0)-D-Glcp-(+-)- a-d-glcp-(+0)-a-d-glcp-(+-)- a-d-glcp-(+)., Carbohydr. Res., -.*,,*0*,*0- (,**/). +1 Furihata, K., Fujimoto, T., Tsutsui, A., Machinami, T. and Tashiro, M., Practical aspects of ROESY experiments for indentification of bound waters in the cyclic tetrasaccharide., Magn. Reson. Chem.,.-, +*..+*.2 (,**/). +2 Yoshii, H., Furuta, T., Kawasaki, K., Hirano, H., Morita, Y., Shiina, C. and Nakayama, S., Quantitative analysis of a-cyclodextrin inclusion complexws with fatty acid methyl/ethyl esters by X-ray di#ractometry., Oyo Toshitsu Kagaku,.,,,.-,.3 (+33/) * ,* Oku, K., Watanabe, H., Kubota, M., Fukuda, S., Kurimoto, M., Tsujisaka, Y., Komori, M., Inoue, Y. and Sakurai, M., NMR and quantum chemical study on the OHp and CHO interactions between trehalose and unsaturated fatty acids : Implication for the mechanism of antioxidant function of trehalose., J. Am. Chem. Soc., +,/, +,1-3+,1.2 (,**-).,+ Oku, K., Kurose, M., Kubota, M., Fukuda, S., Kurimoto, M., Tsujisaka, Y., Okabe, A. and Sakurai, M., Combined NMR and quantum chemical studies on the interaction between trehalose and dienes relevant to the antioxidant function of trehalose., J. Phys. Chem. B, +*3, -*-, -*.* (,**/). +3,, +3 -,.

248 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /-, No./,,.2,/. (,**0) 12 * * * Microencapsulation of Glutamine with Zein by a Solvent Evaporation Metho

248 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /-, No./,,.2,/. (,**0) 12 * * * Microencapsulation of Glutamine with Zein by a Solvent Evaporation Method in Reverse Multiple Emulsion Masato Tanaka*, Yoshinari