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研究生:柳煌
研究生(外文):Liu, Hwang
論文名稱:橘皮精油之區分及Limonene之轉化
論文名稱(外文):Fractionation of Orange Peem Essential Oil and Conversions of
指導教授:李敏雄李敏雄引用關係
指導教授(外文):Min-Hsiung Lee
學位類別:博士
校院名稱:國立臺灣大學
系所名稱:農業化學系
學門:農業科學學門
學類:農業化學類
論文種類:學術論文
論文出版年:1997
畢業學年度:85
語文別:中文
論文頁數:165
中文關鍵詞:烯類精油區分轉化
外文關鍵詞:Pseudomonas aeruginosaTerpeneLimoneneEssential oilFractionationConversionPseudomonas aeruginosa
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柑橘類水果味美香甜,營養豐富,為國人深愛之季節性水果,台灣於
民國80年柑橘類水果之總產量約為45萬公噸,除用於生食外,也大量用於
果汁加工業,製造過程會產生大量的果皮廢棄物。因此,若能有效而簡易
地分離其中之精油成分,則可應用於食品(果汁、飲料、糖果等)及化粧
品工業上,因而提高廢棄物之利用價值。 一般精油萃取法所得之柑橘
精油約含95%以上的單帖烯類(monoterpenes)及倍半帖烯類(
sesquiterpenes)化合物,其中90%以上為d-Limonene。而d-Limonene香氣
較平弱,對柑橘類水果香氣的貢獻很少,且易於儲存過程中劣化,造成精
油的變味、不安定。柑橘類主要的香氣成分為精油中含量只佔4-7%的含
氧帖烯類化合物(oxygenated terpenes),因此,為了提高柑橘精油之利
用價值,有關碳氫帖烯類的去除與轉化研究一直深受重視。 本研究首
先探討以柑橘皮自體酵素將d-Limonene轉換成含氧之帖烯類,以降低精油
中碳氫帖烯類含量,相對提高含氧帖烯類之含量,實驗發現柑橘皮經打碎
後,放置於室溫30℃,14天後,其自體酵素會將橘皮中部分d-Limonene催
化轉換成含氧化合物a-Terpineol,Linalool,Linalool oxide等。新鮮
椪柑皮乙酸乙酯萃出精油之d-Limonene含量為876.5mg/g精油,經自體酵
素作用後,可減為609.7mg/g精油,d-Limonene 的轉換率達30.4%,精油
成分中之碳氫化合物組成也由原來的95.6%減至79.3%,相對的含氧化合
物則由4.4%增至20.7%,對精油之香味品質改進許多。 本研究也以
液/液相萃取法,探討不同含水量之極性溶劑,對椪柑皮自體酵素作用後
以乙酸乙酯萃出之精油區分出d-Limonene 之效果。研究結果顯示,橘皮
精油中d-Limonene在含水10-30%極性溶劑/正己烷兩相系統之正己烷層中
,有很高之分配比例,達90%以上。先將橘皮萃出之精油配製成5%(w/v)
之正己烷溶液,再以不同含水量之極性溶劑(甲醇、乙醇及乙睛)萃取,結
果顯示: 80%甲醇、70%乙醇及90%乙睛對d-Limonene 之區分效果最佳
,可萃出d-Limonene均達98% 以上。精油回收率則分別為18.7、18.8
及8.4%。三種含水極性溶劑萃出之精油成分中,以含氧化合物(oxyated
compounds)為主,佔65%以上,而d-Limonene含量僅佔2-10 mg/g精油左
右,含氧化合物之主要組成為Linalool,a-Terpineol,Linalool oxide
,cis-Carveol及b-Sinensal等,碳氫化合物僅殘留5-7%。 本研究也
探討了以矽膠管柱區分椪柑皮經自體酵素作用後乙酸乙酯萃取精油中之非
極性碳氫帖烯類(Hydrocarbon terpenes)及極性之含氧化合物(
Oxygenated compounds)。實驗結果顯示,以溼式充填之矽膠管柱區分效
果良好,能有效的吸附精油中極性之含氧化合物,而未吸附之非極性碳氫
化合物,能輕易的以正己烷溶洗出來,而後再以極性溶劑(丙酮及乙醇)將
極性含氧化合物洗出。溼式充填之矽膠管柱之吸附力飽合量為0.22-0.24g
精油/g矽膠,10 %(w/v) 之精油正己烷溶液倒入溼式充填之矽膠(50g)管
柱以正己烷、丙酮及乙醇依序溶洗,各區分部分之精油成分為:正己烷部
分(回收率為76.3 %)以碳氫化合物為主(佔99.61 %),其中d-Limonene
佔85 %左右;丙酮區分部分(回收率為7.4 %)以含氧化合物為主(佔99.22
%),其中醇類(48.68 %)、醛類(11.15 %)及其它極性化合物(37.05 %),
此部分具有柑橘水果之濃香和甜味;乙醇區分部分(回收率3.8 %)以醇
類(36.34 %)、醛類(1.22 %)與其他(62.44 %)極性化合物為主,此部分亦
具柑橘香味。 本研究還探討了微生物轉化d-Limonene的可行性。本研
究室自台灣大學校園內土壤篩選得之NTU-FC-8菌株 (經鑑定為
Pseudomonas aeruginosa),以d-Limonene為培養基唯一碳源馴養後,進
行對d-Limonene轉化發酵之實驗。結果發現培養基之d-Limonene 濃度
在0.2-5.0%(v/v)時,該菌均可生長,且以d-Limonene 濃度1.5%生長情
況最為良好。無機氮源硝酸銨(濃度0.75% w/v)可幫助菌體生長,0.6
ppm的硫酸錳及鉬酸鈉對菌體的生長有促進的作用。Pseudomonas
aeruginosa NTU-FC-8對d-Limonene之主要轉化產物經氣相層析/質譜儀鑑
定為perillyl alcohol,該菌株於37℃,120rpm下培養60小時,可使轉化
率達到2.9%。於菌體生長至恆常期(stationary phase),再額外加添d-
Limonene做為生物轉化基質,轉化率可提高至3.8%。也嘗試以靜止細胞
轉化d-Limonene,即待菌體生長至對數生長期(exponential phase)末段
後,製成靜止細胞,再加入d-Limonene,於37℃,120 rpm下培養24小時
,可得perillyl alcohol的轉化率達5.5%。 本論文研究,最後還探
討了使用化學轉化方法,希望在不破壞d-Limonene碳結構情況下,將d-
Limonene氧化成相關的具有濃郁香氣味的醛類(aldehyde),酮類(ketone)
,或是具有較淡花香味的醇類(alcohol)。經實驗發現有一過氧化氫/硫
酸/d-Limonene反應系統,於攪拌均勻少時即可產生激烈反應,其生成物
為具有濃郁香味及抑菌效果成分之物質,並將其訂名為*Limox反應*。反
應生成物經液/液相(methanol / n-hexane)萃取,區分為極性的P-1部分
及非極性的NP-1部分。經實驗發現P-1部分,具有香氣及強烈抑菌性質,
經氣相層析/質譜分析,發現無法自Wiley138資料庫現有檔案中,比對穫
得相似性較高之已知化合物,有可能為不常見之化合物或新化合物。NP-1
部分之香氣較弱,且不具明顯的抑菌性,氣相層析/質譜分析,發現主要
成分為異構化反應(Isomerization reaction)的生成物,及一群為數眾多
的二分子聚合物(Dimers)。
Citrus fruits are a family of popular seasonal fruits with
tasty, nutrition and full of water. According to the
government statistic, the annual productionof Citrus fruit in
Taiwan is about 450,000 metric tons. Except eating as fruit,
it''''s also used for fruit juice processing tremandously, so, the
recovery of orangeessential oil as a by-product prevent from
becoming an environmental pollutant andprovides an excellent
flavoring material for juices and beverages industry. Cold-
pressed or solvent extracted orange oil contains about 95%
terpene hydrocarbon (mostly d-Limonene), 1.6 %aldehydes
(largely Octanal and Decanal),0.8 %alcohols (mostly Linalool),
0.3 %esters (largely Octyl and Neryl acetates)... etc.
Oxygenated compounds, especially the aldehydes, are most
important to the flavor of orange oil. Terpene hydrocarbons
oxidize readily inthe presence of air, leads to the development
of undesirable flavors. The technology of concentrating of
orange oil or removal of a portion of terpenes from orange oil
becomes an interesting topic. This research try to find out
the possibility of converting the terpene hydrocarbons into
oxygenated compounds by the self-enzyme of the orange peel. We
found that after reacted under room temperature (30℃) for 14
days by self-enzyme of the orange peel, part of d-Limonene did
convert to a-Terpineol,Linalool, Linalool oxide..etc, Oxygenated
compounds. The d-Limonene contents changed from 876.5 mg/g
essential oil to 609.7 mg/g essential oil and changed from
95.6%to 79.3%, the conversion rate is 30.4 %. And the
Oxyzenated compounds contents changed from 4.4% to 20.7%. It
did improve the flavor quality of orange essential oil.
This research also try to develope some Liquid/Liquid extraction
solvent system, in order to fractionate the d-Limonene from
orange essential oil ethyl acetate extract, and we hope by these
system, we can get better quality terpeneless orange essential
oil. We found that 80%methanol, 70%ethanol, 90% acetonitrile
/Water solution system can remove almost 98%of d-Limonene,
andcan get the best quality terpeneless orange essential oil.
The recovery rate ofthe essential oil can be 18.7%, 18.8%and
8.4%. The terpeneless orange essential oils made by this
process contain about 65%oxygenated compounds, themajor are
Linalool, a-Terpineol, Linalool oxide, cis-Carveol and b-
Sinensal..etc.and only about 5-7%remains. This research also
spend some effort try to use silica gel column chromato-graphy
to fractionate d-Limonene from the self-enzyme reacted orange
essential oil. We found the wet column have better turn out
than the dry one. It can adsorb oxygenated compound more
effectively, and the terpene hydrocarbon can be easily eluted by
n-hexane, and the oxygenated compounds can be eluted by
acetoneand ethanol afterward. The adsorption capacity is
0.22-0.24 g essential oil/g silica gel. If we try 10g essential
oil/100L n-hexane (10%) to 50 g Silica gelwet column, and then
wash by n-hexane, acetone and ethanol sequentially, we found the
recovery rate will be 76.3 % in n-hexane portion (99.61%
terpene hydro-carbon), 7.4%in acetone portion (99.22%
oxygenated compounds, among them 48.68%alcohol, 11.15%ketone
and 37.05%others), Acetone portion is the most flavour come
from, and 3.8%in ethanol portion (36.34%alcohol, 1.22%ketone
and 62.44%others), ethanol portion have orange flavour, too.
This research also try to develope a microorganism system to use
d-Limonene as sole carbon source to fermentate and produce some
oxygenated compound. We found a bacterium(named Pseudomonas
aeruginosa NTU-FC-8) can have good growth situation under d-
Limonene concentration 0.2~5.0 %(v/v)。We found the bacterium
fermentate with 1.5%(v/v)d-Limonene & 0.75%(w/v)ammonium
nitrate, 37℃ 120 rpm for 60 hrs, the conversion rate of
perillyl alcohol to d-Limonene can be 2.9 %.0.6 ppm MnSO4、Na2
MoO4 will be the conversion. If we add extra d-Limonene during
the fermention reach stationary phase can elevate the conversion
rate to 3.5%. And we try the bioconversion of resting cell,
the conversion rate can even elevate to 5.5%. Finally,
this reseach also tried several chemical system to convert d-
Limonene into some other chemicals with better or stronger
flavour or fragrancecharacter. We found a system of Hydrogen
peroxide/Sulfuric acid/d-Limonene(1:1:1), after stirring under
water cooling system for few minutes, can produce a strong
reaction and turn out to be a group of compounds. After liquid/
liquid (methanol / n-hexane)extraction, we can get P-1 and NP-1
fractions. With GC and GC/MSD analysis result, we found P-1
fraction mainly a mixture of several polar compounds, search
from Wiley 138 MS library, we can not identify most of the
compounds in this stage. But we found P-1 fraction have strong
flavour and very strong anti-bacteria character. And NP-1
fraction is mainly isomerization products such as
1-Phellandrene, a-Terpinolene, g-Terpinene, a-Terpinene..etc
and a group of dimerization products of d-Limonene.
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