JP6737481B2 - Secondary products derived from rare sugars - Google Patents
Secondary products derived from rare sugars Download PDFInfo
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- JP6737481B2 JP6737481B2 JP2019217915A JP2019217915A JP6737481B2 JP 6737481 B2 JP6737481 B2 JP 6737481B2 JP 2019217915 A JP2019217915 A JP 2019217915A JP 2019217915 A JP2019217915 A JP 2019217915A JP 6737481 B2 JP6737481 B2 JP 6737481B2
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- Prior art keywords
- sugar
- rare
- reaction
- raw material
- rare sugar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000000346 sugar Nutrition 0.000 title claims description 112
- 150000008163 sugars Chemical class 0.000 title description 27
- 239000002994 raw material Substances 0.000 claims description 34
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 28
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 24
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 20
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 19
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 18
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 18
- 229960002920 sorbitol Drugs 0.000 claims description 18
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 15
- 235000010356 sorbitol Nutrition 0.000 claims description 15
- 235000010355 mannitol Nutrition 0.000 claims description 14
- SRBFZHDQGSBBOR-OWMBCFKOSA-N L-ribopyranose Chemical compound O[C@H]1COC(O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-OWMBCFKOSA-N 0.000 claims description 12
- WQZGKKKJIJFFOK-QRXFDPRISA-N L-gulose Chemical compound OC[C@@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QRXFDPRISA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 5
- YTBSYETUWUMLBZ-IMJSIDKUSA-N L-threose Chemical compound OC[C@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IMJSIDKUSA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-WISUUJSJSA-N aldehydo-L-xylose Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WISUUJSJSA-N 0.000 claims description 4
- 229930195726 aldehydo-L-xylose Natural products 0.000 claims description 4
- 238000000034 method Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000000047 product Substances 0.000 description 30
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- 239000000203 mixture Substances 0.000 description 27
- 150000005846 sugar alcohols Chemical class 0.000 description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 21
- 239000011941 photocatalyst Substances 0.000 description 21
- 238000013032 photocatalytic reaction Methods 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
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- 238000007254 oxidation reaction Methods 0.000 description 13
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 235000003599 food sweetener Nutrition 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
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- 239000007787 solid Substances 0.000 description 7
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- 238000005261 decarburization Methods 0.000 description 5
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- -1 D-glucose Chemical class 0.000 description 4
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 239000000811 xylitol Substances 0.000 description 4
- 235000010447 xylitol Nutrition 0.000 description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 4
- 229960002675 xylitol Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004278 EU approved seasoning Substances 0.000 description 3
- 239000004386 Erythritol Substances 0.000 description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 235000019414 erythritol Nutrition 0.000 description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 3
- 229940009714 erythritol Drugs 0.000 description 3
- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000002972 pentoses Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-RSVSWTKNSA-N D-altro-hexose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-RSVSWTKNSA-N 0.000 description 2
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- GZCGUPFRVQAUEE-KAZBKCHUSA-N aldehydo-D-talose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-KAZBKCHUSA-N 0.000 description 2
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 230000001766 physiological effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
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- NVLRFXKSQQPKAD-UHFFFAOYSA-N tricarbon Chemical class [C]=C=[C] NVLRFXKSQQPKAD-UHFFFAOYSA-N 0.000 description 2
- OKDOWAAKOUUJPX-YFZIDVRXSA-N (2R,3S,4R,5Z)-5-hydroxyiminopentane-1,2,3,4-tetrol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)\C=N/O OKDOWAAKOUUJPX-YFZIDVRXSA-N 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001517013 Calidris pugnax Species 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 description 1
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- MNQZXJOMYWMBOU-GSVOUGTGSA-N L-(-)-glyceraldehyde Chemical compound OC[C@H](O)C=O MNQZXJOMYWMBOU-GSVOUGTGSA-N 0.000 description 1
- HEBKCHPVOIAQTA-IMJSIDKUSA-N L-arabinitol Chemical compound OC[C@H](O)C(O)[C@@H](O)CO HEBKCHPVOIAQTA-IMJSIDKUSA-N 0.000 description 1
- WQZGKKKJIJFFOK-ZZWDRFIYSA-N L-glucose Chemical compound OC[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-ZZWDRFIYSA-N 0.000 description 1
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- PYMYPHUHKUWMLA-VPENINKCSA-N aldehydo-D-xylose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-VPENINKCSA-N 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 150000001328 aldotetrose derivatives Chemical class 0.000 description 1
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- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ACKFDYCQCBEDNU-UHFFFAOYSA-J lead(2+);tetraacetate Chemical compound [Pb+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ACKFDYCQCBEDNU-UHFFFAOYSA-J 0.000 description 1
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- 235000013615 non-nutritive sweetener Nutrition 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- General Preparation And Processing Of Foods (AREA)
- Seasonings (AREA)
- Saccharide Compounds (AREA)
Description
本発明は、希少糖由来二次的生産物に係り、光触媒反応を用いて生成された希少糖を由来とする希少糖由来二次的生産物に関する。 The present invention relates to a rare sugar-derived secondary product, and relates to a rare sugar-derived secondary product derived from a rare sugar produced by a photocatalytic reaction.
希少糖は自然界に稀にしか存在しない単糖及びその誘導体と定義されている。天然に豊富に存在する単糖はＤ‐グルコースを始めとする数種類の限られた糖のみであり、その他の５０種類以上はすべて希少糖と呼ばれる。近年、希少糖は、生体への安全性が高い糖骨格の化学構造を持ちながら、グルコースとは異なり代謝されにくい性質があることから、低カロリー甘味料として期待されている。また、希少糖の中には有用な生理活性を有するものもあり、産業的利用価値は極めて高い。しかし、希少糖を工業的に製造する方法としては、高純度で安価で大量に製造可能な方法については、未だ有効な手段がないのが現状である。 Rare sugars are defined as monosaccharides and their derivatives which are rare in nature. Naturally abundant monosaccharides are only a few kinds of limited sugars including D-glucose, and other 50 kinds or more are all called rare sugars. In recent years, rare sugars have been expected as a low-calorie sweetener because they have a chemical structure of a sugar skeleton that is highly safe to the living body and have a property of being unlikely to be metabolized unlike glucose. In addition, some rare sugars have useful physiological activity, and thus have extremely high industrial utility value. However, as a method for industrially producing rare sugars, the present situation is that there is still no effective means for producing a high-purity, inexpensive and large-scale production.
希少糖を体系的に製造する方法としては、香川大学の何森教授らが発明した糖異性化酵素による画期的な方法が開示されている（特許文献１）。しかし、この方法は、製造過程において、工業製法としては高価である酵素触媒を用いて糖の変換を行なっており、安価な希少糖製造法という点において課題が残る。 As a method for systematically producing rare sugars, an epoch-making method using a glycoisomerase, which was invented by Professor Heimori and others of Kagawa University, is disclosed (Patent Document 1). However, this method uses an enzyme catalyst, which is expensive as an industrial production method, to convert sugars in the production process, and thus a problem remains in that it is an inexpensive rare sugar production method.
希少糖を化学合成する方法としては、現実的に入手できる安価な炭素原料を考慮すると、二炭素あるいは三炭素の化合物からの増炭反応か、六炭糖からの減炭反応が考えられる。しかし、増炭反応による方法は、糖が有する不斉炭素の多い構造上の特徴により、立体化学を制御するための有機合成化学の高度な技術が必要であり、工業的な大量合成法として確立することは非常に困難である。 As a method for chemically synthesizing a rare sugar, considering an inexpensive carbon raw material that is practically available, a carbon increase reaction from a dicarbon or tricarbon compound or a carbon decrease reaction from a hexose can be considered. However, the method based on the carbon-enrichment reaction requires advanced techniques of synthetic organic chemistry to control the stereochemistry due to the structural features of sugars containing many asymmetric carbons, and is established as an industrial mass-synthesis method. Very difficult to do.
減炭反応による方法のうち、一炭素減炭反応による方法では、Ｄ‐アラビノ酸カルシウムを過酸化水溶液で酸化する方法が開発されている（非特許文献１）。しかしこの方法は、酸化のために大量の過酸化水素を必要とする。他の方法ではＤ‐アラビノースオキシムを分解して製造する方法があるが、酢酸化アルドノニトリルを経由するため低収率である（非特許文献２）。四酢酸鉛を用いたＤ‐グルコースの酸化による方法も知られている（非特許文献３）。しかし、この方法は多段階の複雑な処理を必要とし、工業的製造法としては不適である。 Among the methods based on the carbon reduction reaction, among the methods based on the one carbon reduction reaction, a method of oxidizing calcium D-arabinate with an aqueous peroxide solution has been developed (Non-Patent Document 1). However, this method requires large amounts of hydrogen peroxide for oxidation. Another method is a method of producing D-arabinose oxime by decomposing it, but the yield is low because it passes through acetic acid aldononitrile (Non-Patent Document 2). A method by oxidation of D-glucose using lead tetraacetate is also known (Non-patent document 3). However, this method requires a multi-step complicated treatment and is unsuitable as an industrial manufacturing method.
六炭糖からの二炭素を減炭する方法では、コバルト、ニッケル及びルテニウムなどの金属塩の存在の下、グルコン酸塩の水溶液を過酸化水素で酸化する方法として、８７％の極めて高収率にＤ‐エリトロースを製造している（特許文献２）。しかしながらこの方法は、酸化のために大量の過酸化水素を必要とする。さらには食品添加物あるいは医薬品として応用する際に伴う健康被害や毒性による副作用の危険性を考慮すると、コバルト、ニッケル及びルテニウムなどの金属塩の存在は望ましくない。六炭糖からの二炭素を減炭する他の方法では、Ｄ‐グルコースを分解してＤ‐エリトロースを製造する方法として、超臨界状態あるいは亜臨界状態の水を溶媒として用い、Ｄ‐グルコースの希薄溶液（０．１〜１０％）を高温（２００〜８００℃）高圧下（２〜９０ＭＰａ）に処理する製造法が示されている（特許文献３）。この方法の収率と選択性は目覚ましいものではないが、大型の特殊設備が必要である。 As a method for reducing carbon dioxide from hexose sugar, an extremely high yield of 87% was obtained as a method for oxidizing an aqueous solution of gluconate with hydrogen peroxide in the presence of metal salts such as cobalt, nickel and ruthenium. Is producing D-erythrose (Patent Document 2). However, this method requires large amounts of hydrogen peroxide for oxidation. Further, considering the risk of adverse effects on health and toxicity associated with application as food additives or pharmaceuticals, the presence of metal salts such as cobalt, nickel and ruthenium is not desirable. Another method of decarbonizing dicarbons from hexoses is to decompose D-glucose to produce D-erythrose, using water in the supercritical or subcritical state as a solvent, A manufacturing method is disclosed in which a dilute solution (0.1 to 10%) is treated at high temperature (200 to 800° C.) and high pressure (2 to 90 MPa) (Patent Document 3). The yield and selectivity of this method are not remarkable, but large specialized equipment is required.
光触媒を用いた糖の変換では、一炭素減炭反応による方法があり、Ｄ‐グルコース（六炭糖）を光触媒により分解することでＤ‐アラビノース（五炭糖）及びＤ‐エリトロース（四炭糖）が生成することが報告されている（非特許文献４）。しかし、上記のようなアルドースに対する光触媒反応の分解速度は遅く、目的の生成物は低収量となり、実用化は困難である。さらには、二炭素減炭された四炭糖を得る場合にはＤ‐グルコースからＤ‐アラビノースを経てＤ‐エリトロースを生成するため、四炭糖の収量としては極微量である。 The conversion of sugars using a photocatalyst can be performed by a one-carbon decarburization reaction, in which D-arabinose (pentose) and D-erythrose (tetracarbonose) are decomposed by photocatalytic decomposition of D-glucose (hexose). ) Is generated (Non-Patent Document 4). However, the decomposition rate of the photocatalytic reaction for aldose as described above is slow, the target product has a low yield, and practical application is difficult. Furthermore, when a dicarbon-depleted tetracarbon sugar is obtained, since D-erythrose is produced from D-glucose through D-arabinose, the yield of the tetracarbon sugar is extremely small.
以上のように、希少糖を含む単糖の有効な工業的製造法は確立しておらず、市販価格も非常に高価なものとなっている。そのため、キシリトールやエリスリトールなどの一部の例外を除いて、市場への供給量は非常に少なく、現在、甘味料や食品添加物、機能性食品として市場へ流通するには至っていない。近年、希少糖を含む単糖の生物学的意義が見直され、応用研究も盛んに行われるようになり、様々な生理活性も見つかりつつある（非特許文献５）。今後、さらに産業的に重要な特性が見つかる可能性も高く、希少糖を安価に大量生産する技術の確立は急務である。 As described above, an effective industrial production method of monosaccharides containing rare sugars has not been established, and the commercial price is very expensive. Therefore, with some exceptions such as xylitol and erythritol, the market supply is very small, and at present, it has not reached the market as a sweetener, a food additive, or a functional food. In recent years, the biological significance of monosaccharides containing rare sugars has been reexamined, application researches have been actively conducted, and various physiological activities are being found (Non-Patent Document 5). It is highly likely that industrially important characteristics will be found in the future, and it is an urgent task to establish a technology for mass-producing rare sugars at low cost.
これまでに知られている希少糖を含む単糖の製造法は、二炭素あるいは三炭素の化合物からの増炭反応経路では立体化学の制御と有機合成化学の高度な技術が必要であること、減炭反応経路では収率が低いこと、大量の酸化剤（過酸化水素など）や有害金属を必要とすること、精製が困難である、などの欠点がある。希少糖に期待される食品、化粧品、および医療品への用途を考慮した場合、安全性や大量合成の観点から工業的製造法には不適である。事実として、広く商業的に流通している高純度の希少糖は、キシリトールやエリスリトールなどの例外を除いて存在しておらず、一部で流通している研究試薬としての価格も非常に高価なものとなっている。 The known methods for producing monosaccharides containing rare sugars require that advanced control of stereochemistry and synthetic organic chemistry are required in the carbon-increasing reaction pathway from di- or tri-carbon compounds. The carbon reduction reaction route has drawbacks such as a low yield, a large amount of oxidizing agents (such as hydrogen peroxide) and harmful metals, and difficulty in purification. Considering the applications of rare sugars to foods, cosmetics, and medical products, they are not suitable for industrial production from the viewpoint of safety and large-scale synthesis. In fact, rare high-purity rare sugars that are widely distributed commercially do not exist, with the exception of xylitol and erythritol, and the price as a research reagent distributed in some areas is also very expensive. It has become a thing.
希少糖に期待される用途は、医薬品、食品、化粧品、有機合成のビルディングブロック等、多岐に渡るものの、安全で高純度の希少糖が入手困難である点が、市場流通における大きな障害となっている。したがって本発明は、高純度で安全性の高い希少糖を工業的に製造する方法を提供するとともに得られた希少糖を由来とする安全性の高い希少糖由来二次的生産物を提供することを目的とする。 Expected uses for rare sugars are diverse, including pharmaceuticals, foods, cosmetics, and building blocks for organic synthesis, but the difficulty in obtaining safe and high-purity rare sugars is a major obstacle to market distribution. There is. Therefore, the present invention provides a method for industrially producing a rare sugar having high purity and high safety, and a highly safe rare sugar-derived secondary product derived from the obtained rare sugar. With the goal.
本発明は、上記のような従来技術に伴う商業的困難を解消するために創案されたものである。酸化チタンに代表される光触媒を利用した光触媒反応は、強力な酸化力を有することが知られている。しかし、光触媒反応を糖分解に応用した例であるグルコース（六炭糖）を光触媒反応で分解する方法では、アラビノース（五炭糖）を経て、エリトロース（四炭糖）が生成される一炭素ずつの減炭反応となるため、希少糖の一つであるエリトロース生成量は微量であり、実用に値しないものであった。本出願人らは、光触媒反応による糖分解の研究を進めていく中で、光触媒反応の原料に糖アルコールを用いると、二炭素の減炭反応を優先的に引き起こすことができ、六炭糖の糖アルコールから希少な四炭糖を効率良く製造できることを見出した。さらには、光触媒である酸化チタンに対し、糖の酸化反応に適当な金属を担持させることにより、触媒反応速度を飛躍的に向上させることができることを見出した。この方法により、従来法であるグルコースを原料として光触媒反応を用いた場合に比較して、エリトロースを始めとする四炭糖の生成量を飛躍的に向上させることに成功した。また、この糖アルコールを原料とした光触媒反応では、副産物として別の六炭糖への変換や光学異性体への変換が一部起きることもわかり、これを利用した新たな糖変換方法としても有用な技術であることを見出した。また、本発明方法によって得られた希少糖含有組成物は安全性が高いので、当該希少糖を由来とする希少糖由来二次的生産物が有用であることを見出した。
本発明の第１の態様の希少糖由来二次的生産物は、Ｄ‐エリトロース３５．５％、Ｌ‐トレオース６．９％、Ｌ‐グロース３．８％、Ｄ‐グルコース４．０％、Ｄ‐アラビノース４．３％、Ｌ‐キシロース７．５％（百分率は原料のＤ‐グルシトールに対する生成率）を含むことを特徴とする。
本発明の第２の態様の希少糖由来二次的生産物は、Ｄ‐エリトロース３８．５％、Ｄ‐マンノース４．９％、Ｄ‐アラビノース９．８％（百分率は原料のＤ‐マンニトールに対する生成率）を含むことを特徴とする。
The present invention was created in order to solve the above-mentioned commercial difficulties associated with the prior art. It is known that a photocatalytic reaction using a photocatalyst represented by titanium oxide has a strong oxidizing power. However, in the method of degrading glucose (hexose) by photocatalysis, which is an example of applying a photocatalytic reaction to saccharide decomposition, erythrose (tetracarbon sugar) is produced through arabinose (pentose). Therefore, the amount of erythrose, which is one of the rare sugars, was very small, which was not practical. In the course of research on sugar decomposition by photocatalytic reaction, the present applicants can preferentially induce a carbon reduction reaction of dicarbon by using sugar alcohol as a raw material for photocatalytic reaction. It was found that rare tetracarbon sugar can be efficiently produced from sugar alcohol. Furthermore, it has been found that the catalytic reaction rate can be dramatically improved by supporting titanium oxide, which is a photocatalyst, with a metal suitable for the oxidation reaction of sugar. By this method, we succeeded in dramatically improving the production amount of tetracarbon sugars such as erythrose, as compared with the case of using a photocatalytic reaction using glucose as a raw material, which is a conventional method. It was also found that in the photocatalytic reaction using this sugar alcohol as a by-product, some conversion to another hexose sugar and conversion to optical isomers occur, which is also useful as a new sugar conversion method utilizing this. It was found to be a new technology. Further, since the rare sugar-containing composition obtained by the method of the present invention is highly safe, it was found that a rare sugar-derived secondary product derived from the rare sugar is useful.
The rare sugar-derived secondary product of the first aspect of the present invention is: D-erythrose 35.5%, L-threose 6.9%, L-gulose 3.8%, D-glucose 4.0%, It is characterized by containing 4.3% of D-arabinose and 7.5% of L-xylose (percentage is a production rate with respect to D-glucitol as a raw material) .
The rare sugar-derived secondary product of the second aspect of the present invention is: D-erythrose 38.5%, D-mannose 4.9%, D-arabinose 9.8% (percentage relative to the raw material D-mannitol. Generation rate) .
光触媒技術を用いた本発明によって、従来入手困難であった四炭糖の希少糖であるエリトロースおよびトレオース、及びその他の希少糖を、高純度で安全性の高い形で提供できることとなる。光触媒反応で用いる酸化チタンは低価格で入手が容易である上、繰り返し利用が可能であり、工業生産に適した触媒である。さらに、光触媒反応は光触媒と光があれば進む反応であるため、工業的に汎用される簡易な装置構成で実現できる点も工業生産に適している。また、酸化チタン自体の安全性も高いが、光触媒反応は光照射と光触媒（酸化チタン）のみがあれば、水溶液中で進む反応であり、有機溶媒等、毒性の高い物質を全く使わない点でも安全性が高い。したがって、本発明によって提供されるエリトロースおよびトレオース、及びその他の希少糖は、大量生産が可能で、特に食品、化粧品、医薬品の用途に適応させやすい点で大きな産業的意義がある。具体的には、本発明方法によって得られた希少糖含有組成物は安全性が高いので、当該希少糖を由来とする安全性の高い希少糖由来二次的生産物を安価にしかも大量に提供することができる。 According to the present invention using the photocatalytic technique, it is possible to provide erythrose and threose, which are rare sugars of tetracarbon sugar, which have been difficult to obtain conventionally, and other rare sugars in a highly pure and highly safe form. Titanium oxide used in the photocatalytic reaction is a catalyst suitable for industrial production because it is inexpensive and easily available and can be repeatedly used. Furthermore, since the photocatalytic reaction is a reaction that proceeds if there is light with the photocatalyst, it is also suitable for industrial production in that it can be realized with a simple apparatus configuration that is used industrially. In addition, titanium oxide itself is highly safe, but the photocatalytic reaction is a reaction that proceeds in an aqueous solution if there is only light irradiation and a photocatalyst (titanium oxide), and it does not use highly toxic substances such as organic solvents at all. High safety. Therefore, the erythrose and threose and other rare sugars provided by the present invention have great industrial significance in that they can be mass-produced and can be easily adapted to the use of foods, cosmetics and pharmaceuticals. Specifically, since the rare sugar-containing composition obtained by the method of the present invention is highly safe, a highly safe rare sugar-derived secondary product derived from the rare sugar is provided inexpensively and in large quantities. can do.
本発明において糖アルコールとは、単糖のカルボニル基が還元されてヒドロキシ基になった構造の物質を包括的に指すものであり、炭素数は問わず、全ての糖アルコールに適用される。また、糖アルコール原料として、単糖を常法により還元し水素化したものを用いてもよい。単糖の水素化による糖アルコールへの変換については、一般的な化学還元剤を用いて収率良く還元できる方法が汎用されているのでそれを利用することができる。 In the present invention, the sugar alcohol comprehensively refers to substances having a structure in which a carbonyl group of a monosaccharide is reduced to a hydroxy group, and is applied to all sugar alcohols regardless of carbon number. As the sugar alcohol raw material, monosaccharides reduced and hydrogenated by a conventional method may be used. Regarding the conversion of monosaccharides into sugar alcohols by hydrogenation, a method that can be reduced in a good yield using a general chemical reducing agent is widely used and can be used.
本発明の光触媒による糖アルコール水溶液の酸化反応は、光触媒の有する強力な酸化力により、優先的に二炭素減炭反応を引き起こすことができる。化１に示したように、この二炭素減炭反応は、糖アルコールの両側の末端から進行する。このとき、減炭された側の末端の炭素のヒドロキシ基はアルデヒド基となり、残りの炭素のヒドロキシ基は立体構造を維持する。この反応の立体化学特性を利用すれば、糖アルコールの種類を変えることにより、任意の四炭糖（アルドテトロース）あるいは三炭糖（グリセルアルデヒド）を製造することができる。例えば、Ｄ‐グルシトール（一般名Ｄ‐ソルビトール）を原料として用いた場合、Ｃ１位とＣ２位の炭素が減炭されたＤ‐エリトロースと、Ｃ６位とＣ５位の炭素が減炭されたＬ−トレオースの２種類の四炭糖が生成される。同様に、Ｄ‐マンニトールを原料とすれば、両方の二炭素減炭反応においてＤ‐エリトロースが生成され、Ｄ‐イジトールを原料とすれば、両方の二炭素減炭反応においてＤ‐トレオースが生成される。さらに例を挙げれば、メソ体のキシリトールからはＤＬ‐グリセルアルデヒドが生成され、Ｄ‐アラビニトールからはＤ‐グリセルアルデヒド、Ｌ‐アラビニトールからはＬ‐グリセルアルデヒドが生成される。なお、この二炭素減炭反応は上に例示した糖アルコールに限定されるものではなく、他の糖アルコールにも適用できる。 The oxidation reaction of the sugar alcohol aqueous solution by the photocatalyst of the present invention can preferentially cause a dicarbon reduction reaction due to the strong oxidizing power of the photocatalyst. As shown in Chemical formula 1, this two-carbon decarburization reaction proceeds from both ends of the sugar alcohol. At this time, the hydroxy group of the terminal carbon on the decarburized side becomes an aldehyde group, and the hydroxy group of the remaining carbon maintains the three-dimensional structure. By utilizing the stereochemical characteristics of this reaction, an arbitrary tetracarbon sugar (aldotetrose) or tricarbon sugar (glyceraldehyde) can be produced by changing the type of sugar alcohol. For example, when D-glucitol (generic name D-sorbitol) is used as a raw material, carbon atoms at C1 and C2 are decarbonized, and carbon at carbon atoms C6 and C5 is L-. Two types of four-carbon sugars of threose are produced. Similarly, D-mannitol as a raw material produces D-erythrose in both dicarbon decarburization reactions, and D-iditol as a raw material produces D-threose in both dicarbon decarburization reactions. It For example, meso-form xylitol produces DL-glyceraldehyde, D-arabinitol produces D-glyceraldehyde, and L-arabinitol produces L-glyceraldehyde. The dicarbon reduction reaction is not limited to the sugar alcohols exemplified above, but can be applied to other sugar alcohols.
本発明の光触媒による糖アルコールの酸化反応は、上記の二炭素減炭反応の他に、収量は低いものの、副産物として別の糖も生成する。化２に示したように、単糖ではアルデヒド基であるＣ１位とは逆の末端、すなわち六炭糖の糖アルコールのＣ６位（五炭糖ならＣ５位、四炭糖ならＣ４位）のヒドロキシ基を酸化することによりアルデヒド基が生じ、その結果、光触媒酸化を受けにくいアルドースの構造となり、副産物として残存する。このとき他の立体構造の変化は起きず、そのまま維持される。この反応の立体化学特性を利用すれば、単糖を還元し糖アルコールとした後、光触媒酸化反応を行うことによって、糖を同じ炭素数の別の糖に変換、あるいは、別の立体異性（Ｄ体またはＬ体）への変換ができる。例えば、Ｄ‐グルコースを還元し、Ｄ‐グルシトール（一般名Ｄ‐ソルビトール）を光触媒により酸化すれば、一部をＬ‐グロース（別の六炭糖）に変換することができる。同様に、Ｄ‐グロースからはＬ‐グルコース、Ｄ‐アルトロースからはＤ‐タロース、Ｄ‐タロースからはＤ‐アルトロース、Ｄ‐アラビノースからはＤ‐リキソース、Ｄ‐リキソースからはＤ‐アラビノースがそれぞれ生成される。さらに例を挙げれば、メソ体のキシリトール、及びメソ体のエリスリトールからはＤＬ‐キシロース、及びＤＬ‐エリトロースがそれぞれ生成される。なお、この糖アルコールを介した糖変換反応は、上に例示した糖に限定されるものではなく、他の単糖及び糖アルコールにも適用できる。 The oxidation reaction of the sugar alcohol by the photocatalyst of the present invention produces a different sugar as a by-product, although the yield is low, in addition to the above-mentioned dicarbon reduction reaction. As shown in Chemical formula 2, in the monosaccharide, the aldehyde group has a terminal opposite to the C1 position, that is, a hydroxy group at the C6 position of the sugar alcohol of a hexose (the C5 position for a pentose and the C4 position for a tetrasaccharide). An aldehyde group is generated by oxidizing the group, and as a result, an aldose structure which is less susceptible to photocatalytic oxidation is formed and remains as a by-product. At this time, the other three-dimensional structure is not changed and is maintained as it is. Utilizing the stereochemical characteristics of this reaction, a monosaccharide is reduced to a sugar alcohol, and then a photocatalytic oxidation reaction is performed to convert the sugar into another sugar having the same carbon number, or to change another stereoisomerism (D Body or L-body). For example, if D-glucose is reduced and D-glucitol (generic name D-sorbitol) is oxidized by a photocatalyst, a part can be converted into L-gulose (another hexose). Similarly, L-glucose from D-gulose, D-talose from D-altrose, D-altrose from D-talose, D-lyxose from D-arabinose, and D-arabinose from D-lyxose. Generated respectively. As a further example, DL-xylose and DL-erythrose are produced from meso-form xylitol and meso-form erythritol, respectively. The sugar conversion reaction via this sugar alcohol is not limited to the sugars exemplified above, but can be applied to other monosaccharides and sugar alcohols.
本発明における光触媒反応とは、原料と光触媒に対し、その光触媒の光吸収特性および光反応活性に対応した紫外光から可視光領域の波長の光照射することによって行われる化学反応である。本発明における光触媒とは、基本原理として半導体性物質であれば、光触媒として光触媒反応を実施する事ができる。代表的な光触媒の例としては、酸化チタン、酸化タングステン、酸化スズ、チタン酸ストロンチウム、酸化ニオブ、タンタル酸カリウム、酸化ジルコニウム等がある。本発明における反応容器および光照射装置については、既存の光化学反応で常用される設備を適宜用いることができる。 The photocatalytic reaction in the present invention is a chemical reaction that is carried out by irradiating a raw material and a photocatalyst with light having a wavelength in the range from ultraviolet light to visible light corresponding to the photoabsorption characteristics and photoreactive activity of the photocatalyst. The photocatalyst in the present invention can carry out a photocatalytic reaction as a photocatalyst as long as it is a semiconductor substance as a basic principle. Examples of typical photocatalysts include titanium oxide, tungsten oxide, tin oxide, strontium titanate, niobium oxide, potassium tantalate, zirconium oxide and the like. Regarding the reaction container and the light irradiation device in the present invention, the equipment commonly used in the existing photochemical reaction can be appropriately used.
本発明の好ましい光触媒反応では、糖アルコール１種類あるいは複数の糖アルコールを含有する水溶液に対し、酸化チタン、好ましくは金属担持した酸化チタン存在下において、紫外光から可視光領域の波長を光照射することで実施される。 In a preferred photocatalytic reaction of the present invention, an aqueous solution containing one or more sugar alcohols is irradiated with light having a wavelength in the ultraviolet to visible light region in the presence of titanium oxide, preferably titanium oxide supported on metal. It will be implemented.
本発明の好ましい金属担持酸化チタンの金属種については、貴金属であれば、酸化チタンに担持して用いることで、光触媒の二炭素減炭反応効率を上昇させることができる。貴金属とは、具体的には白金（Ｐｔ）、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、イリジウム（Ｉｒ）、パラジウム（Ｐｄ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、オスミウム（Ｏｓ）である。好ましくは、糖の化学変換に対して高い光触媒活性を示す白金（Ｐｔ）、銅（Ｃｕ）を担持した酸化チタンによって、本発明は実施される。酸化チタンへの担持形態としては、上記の例示した金属の単体、化合物、錯体の形を用いることができる。本発明の方法は、上記に例示した金属のいずれか一つ、あるいは複数の金属を担持した酸化チ
タンによっても実施可能である。
As for the preferred metal species of the metal-supported titanium oxide of the present invention, if a noble metal is used by supporting it on titanium oxide, the efficiency of the dicarbon carbon reduction reaction of the photocatalyst can be increased. Specifically, the noble metal is platinum (Pt), copper (Cu), silver (Ag), gold (Au), iridium (Ir), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium ( Os). The present invention is preferably practiced by titanium oxide carrying platinum (Pt) and copper (Cu), which show high photocatalytic activity for chemical conversion of sugar. As the supporting form on the titanium oxide, a simple substance, a compound, or a complex of the above-exemplified metals can be used. The method of the present invention can be carried out by using any one of the above-exemplified metals or titanium oxide carrying a plurality of metals.
本発明の光触媒反応により得られた特定の希少糖を含む溶液は、原料の構造に由来する類縁の糖誘導体で構成される希少糖含有組成物である。したがって、反応粗精製物の形態としても食品、化粧品の用途に用いることができる。また、上記反応粗精製物を活性炭処理やイオン交換カラムクロマトグラフィーなどの工業的に汎用される精製を行うことで、容易に高純度希少糖液とすることができる。得られた高純度希少糖液は、食品、化粧品、医薬品、医薬品や化成品の原料中間体等の用途に用いることができる。
即ち、本発明方法によって得られた希少糖含有組成物は安全性が高いので、当該希少糖を由来とする安全性の高い希少糖由来二次的生産物を安価にしかも大量に提供することができる。この希少糖由来二次的生産物としては、反応粗精製物や高純度希少糖液からなる希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって、食品、機能性食品、甘味料、食品添加物、化粧品、医薬品および医薬品または化成品の原料中間体のいずれかを生産して得られたものである。
The solution containing a specific rare sugar obtained by the photocatalytic reaction of the present invention is a rare sugar-containing composition composed of a sugar derivative having an analog derived from the structure of the raw material. Therefore, it can be used for food and cosmetics even in the form of a reaction crude product. Further, the above-mentioned reaction crudely purified product is subjected to industrially commonly used purification such as treatment with activated carbon or ion exchange column chromatography to easily obtain a highly pure rare sugar solution. The obtained high-purity rare sugar liquid can be used for foods, cosmetics, pharmaceuticals, raw materials intermediates for pharmaceuticals and chemical products, and the like.
That is, since the rare sugar-containing composition obtained by the method of the present invention is highly safe, it is possible to provide a highly safe rare sugar-derived secondary product derived from the rare sugar at a low cost and in a large amount. it can. As the rare sugar-derived secondary product, a rare sugar-containing composition consisting of a reaction crudely purified product or a high-purity rare sugar liquid is added, contained, or chemically reacted to give a food or a functional product. It is obtained by producing any of foods, sweeteners, food additives, cosmetics, pharmaceuticals and raw material intermediates for pharmaceuticals or chemical products.
以下に、本発明である光触媒を用いた糖アルコールからの希少糖製造方法の具体的な実施例並びに希少糖由来二次的生産物の実施例を説明する。 Hereinafter, specific examples of the method for producing a rare sugar from a sugar alcohol using a photocatalyst according to the present invention and examples of a secondary product derived from a rare sugar will be described.
＜光触媒による六炭糖の糖アルコールから四炭糖の生成（二炭素減炭反応）＞
従来技術である六炭糖を原料とした場合と、本発明である六炭糖の糖アルコールを原料とした場合との、光触媒反応によるＤ‐エリトロース（四炭糖）の生成率の比較をおこなった。単糖原料にはＤ‐グルコース、糖アルコール原料にはＤ‐グルシトール（六炭糖Ｄ‐グルコースの糖アルコール：一般名Ｄ‐ソルビトール）、及びＤ‐マンニトールを使用した。Ｄ‐グルシトール、及びＤ‐マンニトール各０．１３６ｇに対し、純水５０ｍｌを添加し、それぞれ１５ｍＭのＤ‐グルシトール水溶液、及びＤ‐マンニトール水溶液とした。同様に、Ｄ‐グルコース０．１３５ｇに対し、純水５０ｍｌを添加し、１５ｍＭのＤ‐グルコース水溶液とした。それぞれの水溶液へ酸化チタン（アナターゼ／ルチル形）２５ｍｇを添加し、低圧水銀ランプを用いて２ｍＷ／ｃｍ２の強度で光照射をし、撹拌しながら室温（約２５℃）で光触媒反応を行った。光触媒反応後の溶液から、遠心分離により酸化チタンを除去し、その上清に対して高速液体クロマトグラフィーによる定量分析を行うことで、生成されたＤ‐エリトロースを定量した。その結果、図１に示したように、従来技術であるＤ‐グルコースを原料とした場合に比較して、本発明であるＤ‐グルシトール、及びＤ‐マンニトールを原料とした場合では、Ｄ‐エリトロースの生成率が約４倍〜約５倍に向上した。
<Production of tetracarbon sugar from sugar alcohol of hexacarbon sugar by photocatalyst (dicarbon carbon reduction reaction)>
A comparison was made of the production rate of D-erythrose (tetracarbon sugar) by the photocatalytic reaction between the case of using the conventional hexose sugar as a raw material and the case of using the hexose sugar alcohol according to the present invention as a raw material. It was D-Glucose was used as a raw material of a monosaccharide, D-glucitol (sugar alcohol of hexose D-glucose: common name D-sorbitol), and D-mannitol were used as a raw material of sugar alcohol. 50 ml of pure water was added to 0.136 g each of D-glucitol and D-mannitol to obtain a 15 mM aqueous D-glucitol solution and a D-mannitol aqueous solution, respectively. Similarly, 50 ml of pure water was added to 0.135 g of D-glucose to prepare a 15 mM D-glucose aqueous solution. Titanium oxide (anatase/rutile type) 25 mg was added to each aqueous solution, and light irradiation was performed with a low pressure mercury lamp at an intensity of 2 mW/cm 2, and a photocatalytic reaction was performed at room temperature (about 25° C.) with stirring. .. The titanium oxide was removed from the solution after the photocatalytic reaction by centrifugation, and the supernatant was subjected to quantitative analysis by high performance liquid chromatography to quantify the produced D-erythrose. As a result, as shown in FIG. 1, in the case of using D-glucitol and D-mannitol of the present invention as raw materials, D-erythrose was compared to the case of using D-glucose as a raw material of the related art. The production rate of was improved about 4 times to about 5 times.
＜光触媒への金属担持による二炭素減炭反応の促進効果＞
光触媒である酸化チタンに白金を担持したことによる二炭素減炭反応の促進効果について検証した。Ｄ‐グルシトール、及びＤ‐マンニトール各０．１３６ｇに対し、純水５０ｍｌを添加し、それぞれ１５ｍＭのＤ‐グルシトール水溶液、及びＤ‐マンニトール水溶液とした。そこへＰｔ担持酸化チタン、及び酸化チタン（アナターゼ／ルチル形）各２５ｍｇを添加し、低圧水銀ランプを用いて２ｍＷ／ｃｍ２の強度で光照射をし、撹拌しながら室温（約２５℃）で光触媒反応を行った。光触媒反応後の溶液から、遠心分離により酸化チタンを除去し、その上清に対して高速液体クロマトグラフィーによる定量分析を行うことで、生成されたＤ‐エリトロースを定量した。その結果、図２に示したように、金属担持した酸化チタンを用いた方が、Ｄ‐グルシトールとＤ‐マンニトールの両方において、Ｄ‐エリトロースの生成率が約４倍に向上した。
<Promoting effect of dicarbon reduction reaction by supporting metal on photocatalyst>
The promotion effect of the dicarbon reduction reaction by supporting platinum on titanium oxide which is a photocatalyst was verified. 50 ml of pure water was added to 0.136 g each of D-glucitol and D-mannitol to obtain a 15 mM aqueous D-glucitol solution and a D-mannitol aqueous solution, respectively. 25 mg of each of Pt-supported titanium oxide and titanium oxide (anatase/rutile type) was added thereto, and light was irradiated with an intensity of 2 mW/cm 2 using a low pressure mercury lamp, and at room temperature (about 25° C.) with stirring. A photocatalytic reaction was performed. The titanium oxide was removed from the solution after the photocatalytic reaction by centrifugation, and the supernatant was subjected to quantitative analysis by high performance liquid chromatography to quantify the produced D-erythrose. As a result, as shown in FIG. 2, the use of metal-supported titanium oxide improved the production rate of D-erythrose by about 4 times in both D-glucitol and D-mannitol.
＜光触媒による糖アルコールの酸化による副生成物の分析＞
実施例２と同様の方法で、Ｄ‐グルシトール及びＤ‐マンニトール水溶液に対し光触媒反応を行うことで得られる原料由来糖生成物を、適宜複数の分析カラムを用いて、高速液体クロマトグラフィーによって分析した。図３に示したように、Ｄ‐グルシトールからは、Ｄ‐エリトロース３５．５％、Ｌ‐トレオース６．９％、Ｌ‐グロース３．８％、Ｄ‐グルコース４．０％、Ｄ‐アラビノース４．３％、Ｌ‐キシロース７．５％が検出された（百分率は原料に対する生成率を示す）。したがって、原料のＤ‐グルシトールの立体構造に準じて、二炭素減炭反応による主生成物であるＤ‐エリトロース及びＬ‐トレオースが確認され、糖アルコール末端の酸化による副生成物であるＬ‐グロース及びＤ‐グルコースが確認された。反応過程で生成したＬ‐グロース及びＤ‐グルコースの光触媒酸化（一炭素減炭反応）と思われるＬ‐キシロース及びＤ‐アラビノースの生成も確認された。
一方、Ｄ‐マンニトールからはＤ‐エリトロース３８．５％、Ｄ‐マンノース４．９％、Ｄ‐アラビノース９８％が検出された（百分率は原料に対する生成率を示す）。したがって、原料のＤ‐マンニトールの立体構造に準じて、二炭素減炭反応による主生成物であるＤ‐エリトロース、糖アルコール末端の酸化による副生成物であるＤ‐マンノースが確認された。反応過程で生成したＤ‐マンノースの光触媒酸化（一炭素減炭反応）と思われるＤ‐アラビノースの生成も一部あることが確認された。
また、Ｄ‐グルシトールとＤ‐マンニトールからの主生成物である二炭素減炭反応による四炭糖の総量を比較すると、想定された反応機構通り、同程度の総量となることを確認した。
<Analysis of by-products due to oxidation of sugar alcohol by photocatalyst>
In the same manner as in Example 2, a sugar product derived from a raw material obtained by performing a photocatalytic reaction on an aqueous D-glucitol and D-mannitol solution was analyzed by high performance liquid chromatography by appropriately using a plurality of analytical columns. .. As shown in FIG. 3, from D-glucitol, D-erythrose 35.5%, L-threose 6.9%, L-gulose 3.8%, D-glucose 4.0%, D-arabinose 4 were used. 0.3% and L-xylose 7.5% were detected (percentages indicate the production rate with respect to the raw material). Therefore, according to the three-dimensional structure of the starting material D-glucitol, D-erythrose and L-threose, which are the main products of the dicarbon decarburization reaction, were confirmed, and L-gulose, a by-product of the oxidation of the sugar alcohol terminal, was confirmed. And D-glucose was confirmed. The production of L-xylose and D-arabinose, which is considered to be the photocatalytic oxidation of L-gulose and D-glucose (one carbon decarbonization reaction) produced in the reaction process, was also confirmed.
On the other hand, from D-mannitol, 38.5% of D-erythrose, 4.9% of D-mannose, and 98% of D-arabinose were detected (percentage shows the production rate with respect to the raw material). Therefore, according to the three-dimensional structure of the starting material D-mannitol, D-erythrose, which is the main product of the dicarbon carbon reduction reaction, and D-mannose, which is the by-product of the oxidation of the sugar alcohol terminal, were confirmed. It was confirmed that the photocatalytic oxidation of D-mannose produced in the reaction process (one-carbon decarbonization reaction) also produces some D-arabinose.
Further, when the total amount of tetracarbon sugars produced by the dicarbon reduction reaction, which is a main product from D-glucitol and D-mannitol, was compared, it was confirmed that the total amount was about the same as the expected reaction mechanism.
＜希少糖由来二次的生産物の種類＞
反応粗精製物や高純度希少糖液からなる希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって、食品、機能性食品、甘味料、食品添加物、化粧品、医薬品および医薬品または化成品の原料中間体が生産される。
食品には、全ての公知の固体状、液体状、気体状の食品に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。他の生物用としては飼料が含まれる。
機能性食品には、栄養と味のほかに、食品の第三の機能として食品の成分のもつ生体防御、体調リズム調節、疾病の防止と回復などの機能を重視し工夫された食品を意味しており、公知の機能性食品に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。
甘味料には、全ての公知の固体状、液体状、気体状の甘味料に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。
食品添加物には、全ての公知の固体状、液体状、気体状の食品添加物に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。
化粧品には、全ての公知の固体状、液体状、気体状の化粧品に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。
医薬品には、全ての公知の固体状、液体状、気体状の医薬品に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。勿論、人用のみならず、他の生物用のものも含まれている。
医薬品の原料中間体には、全ての公知の固体状、液体状、気体状の医薬品の原料中間体に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。
化成品の原料中間体には、全ての公知の固体状、液体状、気体状の医薬品の原料中間体に希少糖含有組成物を添加したり、含有させたり、化学反応させたりすることによって利用して形成されたり、新規な組成として形成されるものが含まれている。
<Types of secondary products derived from rare sugars>
By adding, containing, or chemically reacting a rare sugar-containing composition consisting of a reaction crudely purified product or a high-purity rare sugar liquid, a food, a functional food, a sweetener, a food additive, a cosmetic, a pharmaceutical product. And a raw material intermediate of a drug or a chemical product is produced.
Foods can be formed by adding, containing, or chemically reacting a rare sugar-containing composition with all known solid, liquid, or gaseous foods, or forming a novel composition. What is formed as. Of course, not only for humans but also for other living things are included. For other organisms, feed is included.
In addition to nutrition and taste, functional foods mean foods that are devised with an emphasis on functions such as biological defense, physical condition rhythm control, and disease prevention and recovery of food ingredients as the third function of food. It is formed by adding, containing, or chemically reacting a rare sugar-containing composition with a known functional food, or includes a composition formed as a novel composition. .. Of course, not only for humans but also for other living things are included.
The sweetener may be formed by adding, containing or chemically reacting a rare sugar-containing composition with all known solid, liquid and gaseous sweeteners, What is formed as a different composition is included. Of course, not only for humans but also for other living things are included.
For food additives, all known solid, liquid, and gaseous food additives may be formed by adding, containing, or chemically reacting a rare sugar-containing composition with the composition. , Those formed as a novel composition are included. Of course, not only for humans but also for other living things are included.
For cosmetics, all known solid, liquid, and gaseous cosmetics can be formed by adding, containing, or chemically reacting a rare sugar-containing composition with a novel composition. What is formed as. Of course, not only for humans but also for other living things are included.
Drugs can be formed by adding, containing, or chemically reacting a rare sugar-containing composition with all known solid, liquid, or gaseous drugs, or forming a novel composition. What is formed as. Of course, not only for humans but also for other living things are included.
For the raw material intermediates of pharmaceuticals, use by adding, containing, or chemically reacting a rare sugar-containing composition to all known solid, liquid, or gaseous pharmaceutical raw material intermediates. And those formed as a novel composition are included.
Used as a raw material intermediate for chemical products by adding, containing, or chemically reacting a rare sugar-containing composition to all known solid, liquid, or gaseous pharmaceutical raw material intermediates. And those formed as new compositions.
＜反応粗精製物由来の希少糖由来二次的生産物＞
反応粗精製物由来の希少糖由来二次的生産物には、精製していない希少糖含有組成物である反応粗精製物の特性を利用した二次的生産物が含まれる。例えば、食品、機能性食品、甘味料、食品添加物、化粧品等が挙げられる。
食品としては次のものが挙げられる。通常の食品類の他に、和菓子、氷菓子、洋菓子、糖菓等の菓子類等である。素材で分類すると穀類加工食品、漬物類、畜産製品類、魚肉製品類、総菜食品類等である。形態で分類すると、固体状の食品、ペースト状の食品、佃煮類、プレミックス粉類、清涼飲料水類、日本酒や洋酒等の酒類、各種飲食物類、瓶詰め缶詰類である。人用以外の食品となる飼料としては、家畜用、動物用、養蜂用、蚕用、魚類用、昆虫用等が挙げられる。
機能性食品としては次のものが挙げられる。人用や人以外の生物の体力活性化剤が挙げられる。近年においては、草木用や水耕栽培用の植物活性化剤が挙げられる。
甘味料としては次のものが挙げられる。成分素材で分類すると、希少糖単体や一般糖類と希少糖を複合させた甘味料や食品添加物である。用途で分類すると、複合調味料、各種の調味料等の調味料類、食品への添加物類である。
食品添加物としては、反応粗精製物を利用した素材であって、主として食品衛生法第４条第２項の規定「添加物とは、食品の製造の過程において又は食品の加工若しくは保存の目的で、食品に添加、混和、浸潤その他の方法によって使用するものをいう。」に分類されるものが挙げられる。
化粧品としては次のものが挙げられる。主として人体の美容用、医療用等の各種の化粧品に反応粗精製物を添加した素材が挙げられる。
<Secondary product derived from rare sugar derived from crude reaction product>
The rare sugar-derived secondary product derived from the crude reaction product includes a secondary product that utilizes the characteristics of the crude reaction product that is an unpurified rare sugar-containing composition. Examples include foods, functional foods, sweeteners, food additives, cosmetics and the like.
Examples of food include the following. In addition to ordinary foods, confectionery such as Japanese confectionery, ice confectionery, Western confectionery, confectionery and the like. When classified by material, they are processed grain foods, pickles, livestock products, fish meat products, side dishes, etc. When classified by form, they are solid foods, paste foods, boiled foods, premixed powders, soft drinks, alcoholic beverages such as sake and western liquor, various foods and drinks, and bottled canned foods. Examples of feeds other than human foods include livestock, animals, beekeeping, silkworms, fish, insects and the like.
The following may be mentioned as functional foods. Examples include physical strength activators for humans and non-human organisms. In recent years, a plant activator for plants and plants and hydroponic culture can be mentioned.
Examples of the sweetener include the following. When classified by ingredient material, it is a sweetener or a food additive in which rare sugar simple substance or general sugar and rare sugar are combined. When classified by use, they are complex seasonings, seasonings such as various seasonings, and additives to foods.
As a food additive, a raw material that uses a reaction crudely purified product, and mainly the provisions of Article 4, Paragraph 2 of the Food Sanitation Act “Additives are used in the process of food production or for the purpose of processing or preservation of food. And those used by adding, mixing, infiltrating or other methods to foods."
The following are examples of cosmetics. Mainly used are various cosmetics such as cosmetics for human body and medical use, which are obtained by adding a reaction crude product.
＜高純度希少糖液由来の希少糖由来二次的生産物＞
高純度希少糖液由来の希少糖由来二次的生産物には、精製を施して得られる希少糖含有組成物である高純度希少糖液の特性を利用した二次的生産物が含まれる。例えば、食品、化粧品、医薬品、医薬品や化成品の原料中間体等が挙げられる。
食品および化粧品としては、反応粗精製物よりもきめ細かな希少糖としての特性を備えている高純度希少糖液を利用した食品および化粧品であって、より付加価値の高い食品および化粧品が挙げられる。
医薬品、医薬品や化成品の原料中間体としては、技術的、医学的、関連法的に要請されている高い基準を満たすために高純度希少糖液を利用して生産したものが挙げられる。
<Secondary product derived from rare sugar derived from high-purity rare sugar liquid>
The rare sugar-derived secondary product derived from the high-purity rare sugar liquid includes a secondary product utilizing the characteristics of the high-purity rare sugar liquid, which is a rare sugar-containing composition obtained by performing purification. Examples thereof include foods, cosmetics, pharmaceuticals, and raw material intermediates for pharmaceuticals and chemical products.
Examples of foods and cosmetics include foods and cosmetics using a high-purity rare sugar liquid that has a finer characteristic as a rare sugar than the reaction crude product, and foods and cosmetics with a higher added value.
Examples of pharmaceuticals, raw materials intermediates for pharmaceuticals and chemical products include those produced by using a high-purity rare sugar solution in order to meet the high standards required in technical, medical and related laws.
なお、本発明は前記実施形態および実施例に限定されるものではなく、必要に応じて適宜に変更することができる。 The present invention is not limited to the above-described embodiments and examples, and can be appropriately modified as necessary.
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