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ウメ(Prunus mume Sieb. et Zucc.)果実の加工副産物から工業的に調製したフェノール性化合物の化学的性質
誌名誌名 日本食品工学会誌 = Japan journal of food engineering
ISSNISSN 13457942
著者著者
三谷, 隆彦味村, 妃紗堀西, 朝子多中, 良栄森, めぐみ稲葉, 伸也山西, 妃早子赤木, 知裕大江, 孝明小山, 一林, 行則尾崎, 嘉彦
巻/号巻/号 18巻3号
掲載ページ掲載ページ p. 147-153
発行年月発行年月 2017年9月
農林水産省 農林水産技術会議事務局筑波産学連携支援センターTsukuba Business-Academia Cooperation Support Center, Agriculture, Forestry and Fisheries Research CouncilSecretariat
Japan Journal of Food Engineering, Vol. 18, No. 3, pp. 147-152, Sep. 2017 DOI: 10.11301/jsfe.17492
000 Original Paper 000
Chemical Features of Phenolic Extracts Prepared on an Industrial Scale from a Processing Byproduct of the Japanese Apricot, Mume Fruit
(Prunus mume Sieb.et Zucc.)
Takahiko MITANI1't, Hisa MIMURA1, Asako HORINISHI2, Yoshie TANAKA3
,
Megumi MORI4, Nobuya INABA5, Hisako YAMANISHI4, Tomohiro AKAGI4, Takaaki OE6
, Hajime KOYAMA3, Yukinori HAYASHI7
, Yoshihiko OZAKI2
1 Center of Regional Revitalization, Research Center for Food and Agriculture, Wakayama University, Wakayama, Wakayama 640-8510, japan
2 Faculty of Biology-oriented Science and Technology, Kindai University, Kinokawa, Wakayama 649-6493, japan 3 School of Medicine, Wakayama Medical University, Wakayama, Wakayama 641-0011, japan
4 Industrial Technology Center of Wakayama Prefecture, Wakayama, Wakayama 649-6261, japan 5 Wakayama Agricultural Processing Research Corporation, Wakayama, Wakayama 649-6212, japan
6 Fruit Tree Experimental Station, Wakayama Research Center of Agriculture and Fisheries, Minabe, Hidaka, Wakayama 645-0021, japan
7 jA (Japan Agricultural Cooperatives) Kinan, Tanabe, Wakayama 646-0027, japan
Mume fruit, Japanese apricots (Prunus mume Sieb. et Zucc.), have traditionally been used for pickles, juice, and liqueur in Japan. During the pickling of mume fruit, an exudate fluid from the fruit called umesu (or umezu) is produced as a byproduct. We developed laboratory-scale and factoryscale methods using synthetic absorbents HP-20 column chromatography to prepare phenolic fractions from umesu (umesu phenolics or umezu phenolics, hereafter referred to as UPs). In this study, we obtained six batches of UPs using a factory-scale method, and their chemical features were examined. The phenolic contents were 13.1±0.8% and 19.2±2.1%, respectively, with gallic acid and p-coumaric acid as standards. The total sugar content was 57.7±4.7%. Very close similarity was observed in the high-performance liquid chromatograms and compositions of the phenolics in the six batches of UPs. The four major phenolic compounds found in the alkaline hydrolysate of UPs were caffeic acid, cis-p-coumaric acid, trans-p-coumaric acid, and ferulic acid. Some batches showed high amounts of cis-p-coumaric acid / total p-coumaric acid. Since this isomerization did not occur during the UP preparation process, it seems likely that isomerization of trans-p-coumaric acid into cis-pcoumaric acid occurred due to sunlight irradiation during umesu storage. Keywords: Prunus mume; umeboshi; byproduct; phenolics
1. Introduction
Mume fruit, the Japanese apricot (Prunus mume Sieb.
et Zucc.), belongs to the Rosaceae family and is one of
the most popular fruits in Japan, with an annual produc
tion of -100,000 tons. In Japan, mume fruit is processed
into umeboshi (pickled mume fruit), umeshu Oiqueur),
juices, etc. Processed mume fruit products have tradi
tionally also been used as a folk remedy in Japan and
eastern Asian countries [1]. Several investigations have
been conducted into the constituents of mume fruit that
might provide health benefits. Chlorogenic acids, flavo-
(Received 22 Apr. 2017: accepted 20 Aug. 2017)
t Fax: +81-73-457-7550, E-mail: [email protected]
nol oligoglycosides, prunoses I, II, and III, and mumeose
K-O, all found in the fruit or flowers of mume trees, were
reported to show several physiological activities [2-8].
We have already found that the flesh of fully mature
mume fruit contains up to 1% of phenolic compounds on a
dry-weight basis and demonstrated that the phenolics in
the methanol-extractable fraction were hydroxycinnamic
acid (mainly p-coumaric acid, caffeic acid, and ferulic
acid) derivatives. Among these, 3 compounds have been
identified as chlorogenic acid (5-O-caffeoylquinic acid),
3-O-caffeoylquinic acid, and Prunose II [9].
During the umeboshi production process, the har
vested fruit is first salted and pressed for a few weeks. In
the process of pickling, the salted fruit gradually exudes
its juice, called umesu or umezu (often translated as
© 2017 Japan Society for Food Engineering
148 Takahiko MITANI, Hisa MIMURA, Asako HORINISHI, Yoshie TANAKA, Megumi MORI, Nobuya INABA,
Hisako YAMANISHI, Tomohiro AKAGI, Takaaki Oe, Hajime KOYAMA Yukinori HAYASHI, Yoshihiko OZAKI
"mume vinegar," although it is not true vinegar), one of
the major byproducts of umeboshi making. Since umesu
contains high concentrations of Na Cl (20%) and citric
acid (5%), it is difficult to find a proper use or application
for this byproduct. However, umesu is expected to con
tain aqueous phenolic compounds because it is exuded
from mume fruit.
We have already prepared phenolic fractions in the lab
oratory from umesu (umesu phenolics, UP) derived from
the 2006-2008 harvest seasons by using synthetic adsor
bents HP-20 (Mitsubishi Chemical Corporation) and
found that the three batches of UP demonstrated very
close similarity in their high-performance liquid chroma
tography (HPLC) results and compositions of phenolic
compounds [10]. In laboratory studies, several
approaches were used in order to scale-up the produc
tion of UP. These included increasing the following: (1)
amount of phenolic compounds that adhere to HP-20 col
umn, (2) efficacy of water washing for elimination of
sodium chloride and citric acid in the column, (3) recov
ered amount of phenolic compounds in 60% aqueous eth
anol eluate and (4) regeneration of HP-20 resin after
chromatography. These experiments were useful for the
establishment and validation of a scaled-up production.
However, the majority of umesu is obtained at umeboshi
manufacturing farms in Wakayama Prefecture.
Therefore, it was important to characterize the bulk UP,
considering that there could be large variations in the
quality of umesu from different orchards.
Recently, we have been able to obtain UPs in bulk from
various batches of umesu. In this paper, we report analyt
ical data for the mass-produced UPs and discuss the cis
p-coumaric acid that exists in the UPs.
2. Materials and Methods
2.1 Chemicals
Caffeic acid, trans-p-coumaric acid, and ferulic acid
were purchased from Sigma-Aldrich (St Louis, MO,
USA) or Wako Pure Chemical Industries Ltd. (Osaka,
Japan). Diaion HP-20 resin was obtained from
Mitsubishi Chemical Co. Ltd. (Tokyo, Japan). Folin
Ciocalteu reagent was purchased from Nacalai Tesque
Inc. (Kyoto, Japan). All chemicals were of analytical- or
HPLC-grade purity.
Phytochemical Co. Ltd., Chiba, Japan, and UP#2 and
UP#3 were donated by SUNACTIS Co. Ltd., Osaka,
Japan. UP#4, UP#5, and UP#6 were gifts from Kinan
Agricultural Cooperatives (Tanabe, Wakayama).
2.3 Determination of total phenolics and
sugar
The total phenolic content was determined by the
Folin-Ciocalteu method with gallic acid as a standard
[11]. p-Coumaric acid was also used as a standard. The
total sugar content was assayed by the phenol-sulfuric
acid method with glucose as a standard [12].
The moisture was expressed as weight loss upon dry
ing at 90°C for 24 h under atmospheric conditions.
2.4 HPLC analyses
A Shimazu LC-2010 instrument was used for HPLC.
All samples were injected into a Hydrosphere C18 col
umn (04.6 mmx250 mm; YMC, Kyoto, Japan). The col
umn was eluted with mixed solvents A (0.1% trifluoroace
tic acid in water): B (methanol) at a flow rate of 1.0 mL/
min. The eluent was A: B=80:20 for 10 min, then a linear
gradient system was applied that reached A: B=25:75
after 80 min. All analyses were carried out at 30°C and
monitored by UV absorption at 280 nm.
2.5 Method for UP preparation in bulk
In the preparation of UPs, Diaion HP-20 resin, which
is often used to prepare phenolic extracts, was used
[13,14]. An example of the column method on the indus
trial scale was as follows: 3000 L of umesu were applied
to a Diaion HP-20 column (030 cmx2 m) at a flow rate of
300 L/h, and the column was washed with 500 L water to
remove sodium chloride and citric acid for 1 h. The phe
nolic compounds were eluted with 500 L of 60% aqueous
ethanol containing 0.05% acetic acid over 1 h. The eluate
was then concentrated under vacuum at 50°C , freeze
dried, and stored at - 30°C until analysis.
2.6 Alkaline hydrolysis
Ester linkages were hydrolyzed by alkali as described
by Krygier et al. [15]. Samples of 100 mg of UP or 250 mg
of freeze-dried fruit flesh were suspended in 4 mL of 1 N
NaOH that were deoxidized in advance by nitrogen gas
bubbling. After 4 h of incubation at 37°C , the suspension
was acidified by adding phosphoric acid and was
2.2 Samples extracted three times with ethyl acetate. The combined
Six UP batches (#1, #2, #3, #4, #5, and #6), produced in ethyl acetate layers were evaporated to dryness, and the
bulk, were obtained. UP#l was a product of TOKIWA residue obtained was dissolved in a minimal volume of
© 2017 Japan Society for Food Engineering
Preparation of Mume Phenolics 149
HPLC mobile phase. The contents of caffeic acid, p-cou
maric acid, and ferulic acid in the UP hydrolysate were
quantified by comparison with the HPLC peak areas of
authentic compounds.
2. 7 Preparative HPLC
An AKTA Explorer l0S System (GE Healthcare
Bioscience) was used for preparative HPLC. A portion of
UPs was loaded into a Hydrosphere C18 column (010
mmx250 mm, 5 µm; YMC, Kyoto, Japan). Separation
was performed by elution with a series of linear gradi
ents of C (0.5% formic acid in water) and D (methanol) in
a cold room at 4°C with a flow rate of 1.5 mL/min as fol
lows: 15% D in C; 15-35% D in C, 0-20 min; 35-100% D in
C, 220-260 min. Aliquots of elute corresponding to each
peak were collected, evaporated to dryness, and dis
solved in methanol.
2.8 Determination of NMR spectra
The isolated sample was dissolved in methanol-d4 or
deuterated dimethylsulfoxide. The 1H NMR and 13C
NMR spectra were recorded on a Bruker Avance 400
MHz (100 MHz 13C) spectrometer. Chemical shifts are
reported as 8 values (in ppm) relative to internal tetra
methylsilane and coupling constants (]) are given in
Hertz.
2.9 Spectral data of isolated compounds
from UP
Compound A, caffeic acid: 1H NMR (400 MHz, metha
nol-d4): 8=6.21 (lH, d, ]=16 Hz), 6.76 (lH, d, ]=8 Hz),
6.92 (lH, dd,]=2, 4 Hz), 7.02 (lH, d,]=4 Hz), 7.52 (lH,
d,]=16 Hz).
Compound B, cis-p-coumaric acid: 1H NMR (400 MHz,
methanol-d4): 8=5.77 (lH, d,]=16 Hz), 6.73 (lH, d,]=8
Hz), 6.77 (lH, d,]=8 Hz), 7.59 (lH, d,]=8 Hz).
Compound C, trans-p-coumaric acid [9]: 1H NMR (400
MHz, methanol-d4): 8 =6.28 (lH, d, ]= 16 Hz), 6.80 (2H,
d,]=8 Hz), 7.44 (lH, d,]=8 Hz), 7.59 (lH, d,]=16 Hz).
Compound D, ferulic acid: 1H NMR (400 MHz, metha
nol-d4): 8=3.89 (3H, s), 6.31 (lH, d,]=16 Hz), 6.81 (lH,
d, ]=8 Hz), 7.06 (lH, dd, ]=4, 8 Hz), 7.17 (lH, d, ]=4
Hz), 7.59 (lH, d,]=16 Hz).
3. Results and Discussion
3.1 Chemical analysis of DPs on an
industrial scale
The moisture, phenolics, and total sugar contents of
six batches of UPs produced on an industrial scale are
shown in Table 1. There was not much of difference in
the contents of moisture, phenolics, and total sugars
among the six batches. It was assumed that the 20%
sodium chloride and 5% citric acid contained in umesu
provided a favorable environment to stabilize the pheno
lic compounds. Oe et al. reported that phenolic contents
in mume fruits are relatively stable annually under differ
ent weather conditions [16].
Gallic acid, which has three hydroxide groups, is usu
ally commonly used as a standard in the Folin-Ciocalteu
method. The phenolics of mume fruit consist of p-cou
maric acid, caffeic acid, and ferulic acid, which have one
or two hydroxide hydroxyl groups in each molecule [9].
Therefore, if gallic acid is used as the standard, the total
phenolic content of the UPs should be underestimated.
Hirawan et.al. reported the Folin-Ciocalteau method for
assessment of phenolic acids in wheat by using ferulic
acid as the standard [17]. As shown in Table 1, shows
that the total phenolic content of UPs with p-coumaric
acid as the standard was about -48% higher than that
with gallic acid as the standard.
HPLC chromatograms of the UPs are shown in Fig.
lA. Each HPLC chromatogram was broadly similar to the
others, but there were some peaks in a different portion
of the chromatogram. These variations reflect small
structural modifications of the phenolics due to the
orchard location and picking season of the mume fruit or
the storage conditions for the umesu.
Table 1 The content of moisture, phenolics, and sugar in UPs prepared in bulk.
UP #1 #2 #3 #4 #5 #6 Mean±SD
Umesu, season 2012 2013 2013 2014 2015 2016
Moisture (%) 3.25 2.49 3.56 4.52 3.46 2.22 3.25±0.12
Phenolics GA (%) 14.4 12.0 12.8 12.8 13.3 14.5 13.1±0.8
Phenolics PC (%) 17.4 20.8 16.7 19.4 22.4 18.7 19.2±2.1
Total sugar (%) 52.1 56.6 53.7 63.7 62.6 56.0 57.7±4.7
© 2017 Japan Society for Food Engineering
150
mV
Takahiko MITANI, Hisa MIMURA, Asako HORINISHI, Yoshie TANAKA, Megumi MORI, Nobuya INABA,
Hisako YAMANISHI, Tomohiro AKAGI, Takaaki Oe, Hajime KOYAMA Yukinori HAYASHI, Yoshihiko OZAKI
A B
f 2 3
UP#l
"4 \~4 J1l M~~.t~.t-~ I i i I . I': 1' I I:._ _____ ,:_=--~
UP#2 I
_,iYtW~.LikL~L~-- JJL_,,~------, r
UP#3
I ,! 1}l l111 I I 11 l ,. H \ _j~\11'.\JmJJ~11t-!\~~'::J!~~~~A!_~-~-===i .,\ 1'i! I\ ,i.
I I
I r
UP#4
1~)i\ivlJ.,tl~1. ____ 1 l .). U . ..~ . I UP#5
~k\t4k-Jt~JL__ I . t JI, . '!: I UP#6
Jti:.jJ~\i,JLJ.L,, I I '.""': ' ·~~: :·::: I 20 40 60 min 20 40 60 min
Fig. 1 HPLC analysis of UPs and their alkali hydrolysates. (A) Chromatogram of UP dissolved. (B)
UPs were suspended in 4 mL of lN NaOH and incubates for 4 h. After extraction with ethyl acetate,
the ethyl acetate fractions were evaporated to dryness, and the residue was subsequently dissolved
in HPLC mobile phase. The hydrolysates were analysed by HPLC. The peaks shown by an arrow
correspond to (1) caffeic acid, (2) cis-p-coumaric acid, (3) trans-p-coumaric acid, and (4) ferulic acid.
3.2 Alkaline hydrolysis of UPs and
characterization of isolated compounds
from alkaline hydrolysate of UPs
matogram of the hydrolysate for each batch of UPs con
sisted commonly of four major peaks and several minor
peaks.
Many peaks were observed in the chromatograms of
the UP as shown in Fig. lA. We have already reported
that alkaline hydrolysis simplified the complex phenolic
profile of mume fruit [9]. As shown in Fig. lB, the chro-
© 2017 Japan Society for Food Engineering
The four major peaks (Peaks 1, 2, 3, and 4) were puri
fied using preparative HPLC, and the chemical structure
corresponding to each peak was confirmed by comparing
the HPLC retention time and 1H NMR spectrum with
Preparation of Mume Phenolics 151
those of standard compounds. When a standard com
pound was not commercially available, the 1H NMR spec
trum was compared with those in the literature. Peaks 1,
2, 3, and 4 were assigned to caffeic acid, cis-p-coumaric
acid, trans-p-coumaric acid, and ferulic acid, respec
tively [9] .
These results showed that the UPs consisted of
hydroxycinnamic acid derivatives and that these four
compounds were identical to those in the phenolics of
mume fruit. As the ethanol-extractable fraction of the
kernel and albumen did not contain caffeic acid, cis-p
coumaric acid, trans-p-coumaric acid and ferulic acid
(data not shown), it was concluded that the UPs were
derived from the mume fruit flesh.
3.3 Occurrence of cis-p-coumaric acid in Ups
We have already reported the presence of cis-p-cou
maric acid in mume flesh phenolics [9]. Table 2 indicates
the ratio of cis-p-coumaric acid to total p-coumaric acids
(cis-p-coumaric acid +trans-p-coumaric acid) in the six
Table 2 Ratio of cis-p-coumaric acid to total p-coumaric acid (cisp-coumaric acid +trans-p-coumaric acid) in six UP batches
UP#
1
2
3
4
5
6
mV
cis-p-coumaric acid
cis-and trans-p-coumaric acid (%)
18.7
39.6
34.6
37.4
22.8
25.5
A
trans-p-coumaric acid
cis-p-coumaric acid
10 20 50 60 JO BO ..,
mV
UP batches and shows that there was a large variation in
the ratio. We have tried to resolve the cause of this varia
tion. Among the six UP batches, it was clarified that the
umesu for UP#2, UP#3, and UP#4 had been kept in trans
lucent containers out of doors for several months. On the
other hand, the umesu for UP#l, UP#5, and UP#6 had
been stored in containers inside buildings. Since it is
known that ultraviolet light induces isomerization of
trans-p-coumaric acid to cis-p-coumaric acid, we
attempted to determine whether such isomerization was
induced in umesu kept in translucent containers out of
doors. An aliquot of umesu from UP#5 in a clear plastic
container was left under sunlight irradiation for two
months. The phenolic fraction was prepared from the
umesu by using HP-20 column chromatography and was
hydrolyzed by alkali. As shown in Fig. 2, the peak
assigned to cis-p-coumaric acid had increased in height
after sunlight irradiation. It is thought that the high per
centage of cis-p-coumaric acid in UP#2, UP#3, and UP#4
resulted from their storage outdoors. The ratios of cis-p
coumaric acid to total p-coumaric acids in the umesu for
UP#5 and UP#6 were 22.8% and 25.5%, respectively.
Therefore, we believe that the isomerization occurred
due to the quality of umesu, not by the UP-preparation
process. Since we have obtained preliminary data in
which there seems to be a difference in the bioavailabil
ity of p-coumaric acid between the cis and trans forms, it
is important to store the umesu out of sunlight. Makila et
al., reported that trans-p-coumaric acid is more easily
converted into the corresponding cis isomer under UV or
sunlight than caffeic and ferulic acid [18]. Therefore,
cis-p-coumaric acid was detected in the UPs.
These chemical analyses will contribute to the produc-
trans-p-coumaric acid
cis-p-coumaric acid /
10 50 ;o
B
70 80
""' Fig. 2. Isomerization of p-coumaric acid in umesu after sun irradiation for two months. An aliquot of umesu was kept in
translucent containers outdoors for two months. The phenolic fraction was prepared from the umesu by using HP-20
column chromatography and was hydrolyzed by alkali. The hydrolysates were analysed by HPLC. (A) 0 months. (B) 2
months.
© 2017 Japan Society for Food Engineering
152 Takahiko MITANI, Hisa MIMURA, Asako HORINISHI, Yoshie TANAKA, Megumi MORI, Nobuya INABA,
Hisako YAMANISHI, Tomohiro AKAGI, Takaaki Oe, Hajime KOYAMA Yukinori HAYASHI, Yoshihiko OZAKI
tion of Ups, which that may be useful as a food ingredi
ents in health-promoting foods.
Acknowledgements
This work was supported by research grants from the
Regional Innovation Strategy Support Program
(Wakayama Kihokukichu Area) of the Ministry of
Education, Culture, Sports, Science and Technology of
Japan and also by research grants (Heisei 27,28 nendo)
from the Kishu-Tanabe Ume Promotion Committee.
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「日本食品工学会誌」，Vol.18, No. 3, p. 153, Sep. 2017
◇◇◇和文要約◇◇◇
ウメ (Prunusmume Sieb.et Zucc.)果実の加工副産物から
工業的に調製したフェノール性化合物の化学的性質
三谷隆彦庄味村妃紗＼堀西朝子 2, 多中良栄 3, 森めぐみ 4,稲菓伸也凡
山西妃早子4,赤木知裕4,大江孝明円小山 一叫林行則 7, 尾崎嘉彦 2
1和歌山大学 地域活性化総合センター 食農総合研究所， 2近畿大学生物理工学部，
3和歌山県立医科大学， 4和歌山県工業技術センター， 5一般社団法人和歌山県農産物加工研究所，
6和歌山県果樹試験場 うめ研究所， 7紀南農業協同組合
ウメ (Prunusmume Sieb. et Zucc.)果実は梅干し，
ジュース，梅酒などに加工されている．和歌山県はウメ
果実の生産鼠は約 6万トンで，全国の生産量の 6割に達
し，その 70%が県内で梅干し製造に用いられる．梅干
し製造過程では推定 1.6万トンの梅酢が副産物として生
じるが，梅酢は 20%の食塩と 5%のクエン酸を含有して
いることから，その利用，もしくは廃棄法が大きな課題
となっている．われわれは梅酢には果実由来のフェノー
ル化合物が存在し，その調製法を実験室レベルで明らか
にしてきたその後，梅酢由来のフェノール化合物 (UP
と省略）を工業的に製造する開発に繋がった．その方法
の 1つの事例を示すと，化学吸着樹脂 DiaionHPー20を
充填したステンレスカラム（直径 30cmx長さ 2m) に
梅酢 3トンを流速 300L/hで通過させ，フェノール性
化合物を吸着させる．その後脱イオン水 500Lを通過さ
せてカラム内に残存している食塩およびクエン酸を除去
する．その後 500Lの0.05%の酢酸を含む 60%エタノー
ルをカラムに流し，フェノール化合物を回収する．この
液を凍結乾燥して UP原末を得る．
UPの工業的製造が開始されたので，工業的に製造し
た6ロットの化学的特性を調べたまずフェノール性化
合物の平均含量をフォーリン・チオカルト法で調べた．
この場合，通常没食子酸を検量用の標準物質として用い
るが，没食子酸はフェノール環に水酸基が 3個ついてい
る．ところでウメのフェノール性物質はヒドロキシ桂皮
酸の誘導体で，フェノール環に水酸基は 1個もしくは 2
個であることがすでに明らかになっており，没食子酸を
標準物質にすると，フェノール性物質の含量が低く見積
もられることになる．そのため，フェノール環に水酸基
（受付 2017年 4月22日，受理 2017年 8月20日）
1〒640-8510 和歌山県租歌山市栄谷 930
2〒649-6493 和歌山県紀の川市西三谷930
3〒641-0011 和歌山県和歌山市三葛 580番地
4〒649-6261 和歌山県和歌山市小倉 60
5〒640-8331 和歌山市美園町五丁目 1番地の 1
6〒645-0021 和歌山県日高郡みなべ町東本庄 1416-7
7〒646-0027 和歌山県田辺市朝日ヶ丘24番 17号
t Fax: 073-457-7550, E-mail: [email protected]
が 1個のpークマル酸も，別途標準物質として用いた．
その結果， UPのフェノール性化合物の平均含量は，没
食子酸換算で 13.1土0.79%,pークマル酸換算で 19.2土2.11%
であることが判明した全糖量はフェノール硫酸法で求
め，その平均含量は 57.7土4.7%であった．これらの 6ロッ
トの HPLCプロファイルおよびフェノール性化合物の組
成はピークの高さは多少の違いはあるものの，全体とし
て類似していた. UPのアルカリ加水分解によりカフェ
酸， trans-pークマル酸， cis-pークマル酸， およびフェル
ラ酸が見いだされた． これらは実験室レベルで製造した
UPと，同じ分子種であったこれまで，実験室レベル
で製造した UPは，梅酢製造の年が違っても，またウメ
果実の収穫場所が異なっても，品質に大きな差異は見い
だされなかったことから，工業的なレベルでもこの事が
確認できた．恐らく梅酢中では塩分磯度が高く，酸性条
件であるためフェノール性化合物は長期間安定に保たれ
ると考えられた．以上，これらの検査項目は UPの品質
規格として利用される予定である．
しかし工業的に製造した UPの幾つかのロットでは，
pークマル酸総量に占める cis-pークマル酸星の割合が高い
ものが見いだされた梅干し製造後に生じた梅酢は，個々
の梅干し製造業者や農家で保管されているが，その保管
方法はバラバラで，屋外や屋内で，半透明もしくは光を
通さない容器で保管されており，温度条件も当然異なっ
てくる. cis-pークマル酸量は trans-pークマル酸が紫外線
の作用を受けることで異性化されるので，ウメ果実でも
一定量が生成していると考えられるが， UPの中で極端
にその割合が高いロットは，原料梅酢が太陽光に当たる
場所で半透明の容器に保管されていたことが追跡調査で
明らかになったこの事を再現するため，実験室レベル
で梅酢を太陽光に 2か月間照射した場合， p-クマル酸総
量に占める cis-pークマル酸最の割合が著しく増加したこ
とから，確認することができた. cis-pークマル酸量は UP
の機能性に影響を及ぼすことが判明してきており（未発
表データ），今後工業的に UPを製造する場合，原料梅
酢の保管方法などを十分考慮する必要がある．
c2017 Japan Society for Food Engineering
