Accepted Manuscript
Title: Tea aroma formation
Author: Chi-Tang Ho Xin Zheng Shiming Li
PII: S2213-4530(15)00018-X DOI: http://dx.doi.org/doi:10.1016/j.fshw.2015.04.001 Reference: FSHW 54
To appear in:
Received date: 15-2-2015 Accepted date: 23-3-2015
Please cite this article as: C.-T. Ho, X. Zheng, S. Li, Tea aroma formation, Food Science and Human Wellness (2015), http://dx.doi.org/10.1016/j.fshw.2015.04.001
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Tea aroma formation
Chi-Tang Ho1*, Xin Zheng1, Shiming Li2*
1Department of Food Science, Rutgers University, New Brunswick, NJ 08901, USA
2College of Life Sciences, Huanggang Normal University, Hubei 438000, China
Corresponding author:
Chi-Tang Ho, Ph.D
Department of Food Science, Rutgers University, New Brunswick, NJ 08901, USA
Email: [email protected]; Telephone: (01)848-932-5553 or
Shiming Li, Ph.D
College of Life Sciences, Huanggang Normal University, Hubei, 438000, China
Email: [email protected]; Telephone: (86)713-883-3611
Received 15 February 2015; Accepted 23 March 2015
Accepted Manuscript
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Page 1 of 36 Abstract
Besides water, tea is one of the most popular beverages around the world. The chemical ingredients and biological activities of tea have been summarized recently. The current review summarizes tea aroma compounds and their formation in green, black, and oolong tea. The flavor of tea can be divided into two categories: taste (non-volatile compounds) and aroma (volatile compounds). All of these aroma molecules are generated from carotenoids, lipids, glycosides etc. precursors, and also from Maillard reaction. In the current review, we focus on the formation mechanism of main aromas during the tea manufacturing process.
Keywords: Tea, Aroma, Formation, Volatile, Taste
Accepted Manuscript
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Page 2 of 36 1. Background
Tea is the second most widely consumed beverage around the world after water [1]. The
popularity of tea as a global beverage rests on its pleasant flavor, mildly stimulating effects, and
nutritional properties, which people find appealing and attractive. According to the
manufacturing process, tea can be divided into at least three basic types: non-fermented green tea,
fully fermented black tea, and semi-fermented oolong tea [2,3]. The flavor of tea can be divided into two categories: aroma, which consists mainly of volatile compounds; and taste, which consists mainly of non-volatile compounds. The volatile aromas are important criterion in the evaluation of tea quality.
Nowadays, more than 600 volatile compounds have been reported during the tea manufacturing process, and these compounds can be divided into 11 classes [4-6]. All of these aromas are generated from four main pathways: carotenoids as precursors, lipids as precursors, glycosides as precursors, and Maillard reaction pathway. To the best of our knowledge, no previous study has provided the details of formation mechanisms for tea aromas. Therefore, in the present study, we review main aromas starting from the manufacturing process, with biological and chemical mechanisms.
Accepted Manuscript
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Page 3 of 36 2. Carotenoids as precursors
Carotenoids include β-carotene, lutein, zeaxanthin, neoxanthin, xanthophyll, and
lycopene, and more have been identified as precursors for many tea flavors. Many of them play
key roles in deciding the quality of tea. Fig. 1 lists the most common aroma compounds derived
from carotenoids. There are mainly thirteen carbon cyclic compounds, such as β-ionone (1,
woody), β-damascenone (2, floral, flowery, cooked apple), C13-spiroether theaspirone (3, sweet
floral, tea-like), and theaspirone (4) as well as oxygenated theaspirone derivatives (5 and 6, fruity)
[7].
O O O O O O O 3 4 O OH 1 2 C13-Spiroether 6 β-Ionone β-Damascenone Theaspirone 5 theaspirone
Fig. 1. Carotenoid-derived aroma compounds
There are two main mechanisms of carotenoid degradation. One is enzymatic oxidative
degradation (Table 1) and the other is non-enzymatic oxidation. The enzymatic pathway is
catalyzed by dioxygenases during fermentation (Fig. 2a) [7]. First, carotenoids are cleaved by
dioxygenases, forming primary oxidation products. Subsequently, the enzymatic transformation
of oxidation products gives rise to aroma precursors, followed by acid hydrolysis to liberate
volatile aroma compounds. The order of carotenoid enzymatic oxidation is β-carotene > zeaxanthin > lutein.Accepted It should be pointed out that aromas Manuscript originating from carotenoid degradation must be assisted with the oxidative tea flavonols during fermentation. The oxidized tea flavonols–quinones are oxidizing reagents for the degradation of carotenoids. This suggests that the oxidation of tea flavonols by catechol oxidase remarkably affects the formation of tea aromas during the manufacturing process (Fig. 2b) [8]. Without the oxidation of non-volatile compounds, no aroma could be detected during the manufacturing process. Therefore, it is evident that there
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Page 4 of 36 is a relationship between non-volatile and volatile compounds.
acid catalyzed oxidative Primary Cleavage enzymatic Aroma Carotenoids Non-volatile Metabolites Products compounds (Aroma Precursors) conversions cleavage transformation
Fig. 2a. Enzymatic degradation of carotenoids [7]
OH O OH O
HO O Catechol Oxidase HO O R1 R1
R2 O R2 R 2 R3 OH 3 OH
Flavanols o-Quinone
Carotenoids Degradation products
Fig. 2b. Flavonol oxidation participates in carotenoid degradation (red arced arrow indicates the driving force of flavonol oxidation in carotenoid degradation) [8]
β-Damascenone (Fig. 3) and β-ionone (Fig. 4a) are two representative aromas formed
from carotenoid degradation. β-damascenone has an apple-like flavor and has an extremely low
threshold in water (0.002 ppb). It was first identified in Bulgarian rose oil in 1970 [9] and is an
essential odor in black tea infusion [10-12]. It comes from the enzymatic oxidation of neoxanthin
(Figure 3). The first step is the cleavage of neoxanthin by dioxygenases between the C-9 and C-
10 double bond, yielding grasshopper ketone. Next, this ketone is enzymatically reduced to
allenic triol, which is known as a progenitor of β-damascenone. The last step is acid-catalyzed dehydration to odoriferousAccepted β-damascenone [13]. In addition,Manuscript it can directly originate from neoxanthin in non-enzymatic reactions, such as thermal degradation or oxidation, under acidic conditions during the tea manufacturing process [14].
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Page 5 of 36 HO OH
HO OH H O Oxidative O Cleavage Neoxanthin Grasshopper ketone OH
HO OH O Enzymatic -2H O 2 Black tea, Green tea transformation HO Fruity, apple-like
Allenic triol β-Damascenone
Fig. 3. Formation mechanism of β-damascenone [13]
β-Ionone (Fig. 4a) is a significant contributor to the flavor of green and black tea and has
a low odor threshold (0.007 ppb). It can be produced either by enzymatic reactions during
fermentation or thermal degradation during the green tea manufacturing process (Fig. 4a) [15]. It
comes from the primary oxidation of β-carotene. Fermentation and heat-drying steps are both
needed to generate the final product β-ionone. β-ionone can be further oxidized to 5,6-epoxy-β- ionone. After two reduction steps, it is converted to a saturated triol that undergoes an intramolecular cyclization followed by an oxidation reaction generating dihydroactinidiolide and theaspirone, which are viewed as critical aromas in determining the characters of black tea (Fig.
4b) [8,16,17]. Table 1 lists tea aromas generated by primary and secondary enzymatic oxidations from their carotenoid precursors [8,18]. Accepted Manuscript
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Page 6 of 36 β -Carotene oxidative cleavage by dioxygenase
O Green tea, Black tea O O + Woody, violet
C14-Dialdehyde β-Ionone
Fig. 4a. Primary oxidation of β-carotene [16]
O HO HO HO HO O oxidation +H2O reduction O O O
β-Ionone 5,6-Epoxy-β-ionone
HO reduction Black tea HO -2H 2O oxidation O Fruity HO O O Dihydroactini diolide
oxidation Black tea O Flowery, nutty -H2O O Theaspirone
Fig. 4b. Secondary oxidation of β-ionone [8,16]
Non-enzymatic degradation of carotenoids includes photo-oxidation (solar withering and
solar drying), auto-oxidation, and thermal degradation (steaming, pan-firing, rolling, and drying).
As an example, photo-oxidation of β-carotene under UV light results in 5,6-epoxy- β-ionone, 3,3-dimethyl-2,7-octanedione,Accepted 2,6,6-trimethyl-2-hydroxycyclohexanoe, Manuscript dihydroactinidiolide, and β-ionone. The first step is the epoxidation of the double β-ionone bond on cyclohexene, followed by the cleavage of epoxides, C-9 and C-10 double bond, or C-7 and C-8 double bond, producing cyclic and straight chain aromas (Fig. 5a). Another example is the formation of oolong tea aromas nerolidol, α-farnesene, and geranylacetone from photo-oxidation of phytofluene (Fig. 5b)
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Page 7 of 36 [18].
Table 1. Carotenoid-derived aromas produced by primary and secondary enzymatic oxidation [8]
Carotenoids in tea leaves Primary oxidation products Secondary oxidation products Dihydroactinidiolide; 5,6-Epoxyionone β-Carotene β-Ionone 2,2,6-Trimethylcyclohexanone; Theaspirone 2,2,6-Trimethyl-6-hydroxycyclohexanone α-Carotene β-Ionone; α-Ionone Theaspirone Phytoene Linalool -- Phytofluene Linalool -- Lycopene Linalool 6,10-Dimethyl-3,5,9-undecatriene-2-one γ-Carotene β-Ionone Theaspirone Cryptoxanthin β-Ionone Theaspirone Terpenoid-like Lutein Theaspirone aldehydes/ketones Neoxanthin β-Damascenone --
β-Carotene
UV, O2
O O O O O OH O O O 5,6-Epoxy- Dihydroactinidiolideβ-Ionone 2,6,6-Trimethyl-2- 3,3-Dimethyl-2,7- β-ionone octanedione hydroxycyclohexanone
Fig. 5a. Photo-oxidation of β-carotene
Accepted Manuscript
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Page 8 of 36 Phytofluene
Epoxidation/ Photo-oxidation
O
O
OH O
Nerolidol Geranylacetone (Oolong tea, flowery) (Green, Oolong, black tea, Floral) dehydration
-Farnesene (Oolong tea, Fruity)
Fig. 5b. Photo-oxidation of phytofluene [18]
Table 2 lists the main carotenoid-derived tea aromas in three types of tea. Aromas yield
higher concentrations during the fermentation step due to enzymatic oxidation. Indoor withering is another essential enzymatic oxidation that generates substantial aroma in oolong tea. Solar drying and thermal degradation are non-enzymatic ways for the formation of green tea aromas.
β-ionone, 5,6-epoxy-β-ionone, nerolidol, and dihydroactinidiolide account for the high concentration of flavors in green tea. Dihydroactinidiolide, theaspirone, nerolidol, and safranal are highly concentrated flavors in black tea. Oolong tea combines both aromas in green and black tea with different concentrations depending on its fermentation degree [8,18,19].
Accepted Manuscript Table 2. Contribution of carotenoid-derived aroma compounds in tea [18]
Compound Green Tea Oolong Tea Black Tea β-Damascenone √ √ √ β-Ionone √ √ √ α-Ionone √ 6-Methyl-5-hepten-2-one √ √ 6-Methyl-E-3,5-heptadien-2-one √ √ 2,6,6-Trimethyl-2-hydroxycyclohexanone √ √ √
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Page 9 of 36 β-Cyclocitral √ √ √ Safranal √ √ √ 2,6,6-Trimethylcyclohex-2-en-1,4-dione √ √ α-Farnesene √ √ α-Damascone √ Geranylacetone √ √ √ 3,3-Dimethyl-2,7-octanedione √ √ 5,6-Epoxy-β-ionone √ √ √ Nerolidol √ √ √ Theaspirone √ √ √ Dihydroactinidiolide √ √ √
3. Lipids as precursors
Unsaturated fatty acids, such as α-linolenic acid, linoleic acid, oleic acid, and palmitoleic
acid, are precursors for six to ten carbon aroma compounds, such as (E)-2-hexanal (leafy), (E)-2-
hexanol, and (Z)-3-hexanol (leafy), which contribute fresh and greenish odors in tea infusion
(Fig. 6) [20]. Formation of these volatile aromas from the oxidation of tea lipids is usually
associated with two main pathways. The first pathway is an oxidation reaction initiated by free
radicals, such as autoxidation, photo-oxidation, and thermal oxidation. The rate of lipid oxidation
increases with the unsaturation degree of lipids. The second pathway is called lipoxygenase-
mediated lipid oxidation, which is also the main pathway contributing to the flavor of tea.
O OH O O 1-Octen-3-one 1-Octen-3-ol 1-Penten-3-one n-Nonanal
OH O O OH cisAccepted-3-Penten-1-one n-Heptanal cisManuscript-3-Penten-1-ol 1-Penten-3-ol
OH HO OHC n-Heptanol n-Nonanol (E,E)-2,4-Heptadienal
Fig. 6. Volatile compounds generated from lipid degradation [21]
A good example of lipoxygenase-assisted oxidation is the formation of six carbon
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Page 10 of 36 aldehydes and alcohols from α-linolenic acid and linoleic acid (Fig. 7) [22-24]. In the primary
step, lipids are oxygenated by lipoxygenase (LOX) to form lipid hydroperoxides, which are then
cleaved by hydroperoxide lyases (HPLs) to six carbon aliphatic aroma compounds, such as (Z)-
3-hexenal and n-hexanal. Subsequently, these aldehydes can be further reduced to their
corresponding alcohols by alcohol dehydrogenases (ADHs) or isomerized to trans isomers and then reduced to alcohols (Fig. 7). LOX is the key enzyme in this mechanism and located in the tea leaf chloroplast and activated seasonally. LOX reaches its maximum level in the summer and drops to its lowest level in the winter [25].
In addition, it has been reported that 1-octen-3-one and 1-octen-3-ol are formed from linoleic acid and 1-penten-3-one, 1-penten-3-ol, cis-3-penten-1-one, and cis-3-penten-1-ol are formed from α-linolenic acid. Oleic acid and palmitoleic acid are the precursors of n-nonanal, n-
nonanol, n-heptanal, and n-heptanol. The amount of 1-octen-3-one, geranial, hexanal, and other
related carbonyl compounds in aged green tea are dramatically low because tea catechins are
great scavengers that trap carbonyl compounds [26]. Lipid degradation can also produce cyclic
aromas, such as methyl jasmonate, cis-jasmone, and jasmine lactones. They are fragrant volatiles
initially identified from flowers of Jasminum grandiflorum, with high concentrations in oolong
and some green tea [27,28].
Accepted Manuscript
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Page 11 of 36 O O OH OH -Linolenic acid Linoleic acid LOX LOX
OOH O OOH O OH OH
HPL HPL
O ADH n-Hexanal O HO
(Z)-3-Hexenal (Z)-3-Hexenol ADH Leafy alcohol isomerization HO
n-Hexanol O ADH HO (E)-3-Hexenal (E)-3-Hexenol Green isomerization Odour
O ADH HO (E)-2-Hexenal (E)-2-Hexenol Leafy aldehyde
Green Odour
Fig. 7. Biosynthetic pathway of six carbon aromas in tea leaves [23-25]
Methyl jasmonate is a representative aroma in oolong tea derived from α-linolenic acid. It represents two isomers (1R, 2R) and (1R, 2S) in natural oolong tea. (1R, 2R) has quite a low threshold value compared with (1R, 2S) but can be converted to (1R, 2S) by heating. This is the reason why oolongAccepted tea has intense floral and sweet odorsManuscript after the manufacturing process. The mechanism of methyl jasmonate formation is predicated from the biosynthetic pathway in
Arabidopsis (Fig. 8) [25]. α-Linolenic acid is first oxygenated by lipoxygenase, forming 13S-
hydroxylinolenic acid, which subsequently undergoes oxidation catalyzed by allene oxide
synthase (AOS) and then allene oxide cyclase (AOC) yielding 12-oxo-phytodienoic acid
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Page 12 of 36 (OPDA). After reduction and three consecutive steps of β-oxidation from OPDA, jasmonic acid
is produced, which is a substantial intermediate to be converted into various jasmonic derivatives
by hydroxylation, O-glycosylation, or conjugation with amino acids [29]. It can also be further transformed into either cis-jasmone, a key aroma in oolong tea and green tea or methyl jasmonate by jasmonic acid carboxyl methyl transferase (JMT). Table 3 lists representative volatile aromas derived from lipid oxidation during the tea manufacturing process.
O OOH O 13-LOX AOS OH OH
-Linolenic acid 13S-Hydroperoxylinolenic acid
O O O O AOC OH COOH COOH
12,13S-Epoxylinolenic acid OPDA
O O O [O] Green tea, Oolong tea -oxidation -CO2 Floral, jasmin-like COOH -H 2O COOH
Jasmonic acid cis-Jasmone
O Green tea, Oolong tea
COOMe Floral, sweet
Methyl jasmonate
Fig. 8. Methyl jasmonate biosynthetic pathway [25,29]
Table 3. Lipid oxidation derived aroma compounds [20] Accepted Manuscript Compound Green Tea Oolong Tea Black Tea Hexanal √ √ √ Pentanal √ Jasmine √ Nonanal √ cis-Jasmone √ √ √ Heptanal √ 1-Penten-3-ol √ (E)-2-Hexenal √ √ √
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Page 13 of 36 (Z)-3-Hexen-1-ol √ √ (E,E)-2,4-Hexadienal √ (E)-2-Hexen-1-ol √ Methyl jasmonate √ √ Nerolidol √ √
4. Glycosides as precursors
Glycoside is a molecule in which a sugar moiety is bound to a functional group via a
glycosidic bond. Glycosides are flavorless compounds in fresh tea leaves. During the
manufacturing process, injured tea leaf tissues release enzymes into cell walls or cavities to
hydrolyze glycosidic bonds liberating volatile aromas, such as monoterpene alcohols (linalool,
linalool oxides, and geraniol) or aromatic alcohols (benzyl alcohol and phenylethanol) [25,30-
32]. The concentration of glycosidic enzymes seasonally change in tea leaves, expressed from
high to low as spring > summer > autumn [25,33]. Sugar moieties of glycosides are typically
monosaccharides or disaccharides (Table 4) [6,25]. The structure of glycoside-derived tea aromas
are summarized in Table 5. Some volatile aromas are present in all types of tea; however, some unique flavors exist in specific tea.
Table 4. Different types of sugar moieties in tea leaves [6,25]
R O Glycoside HO HO O Aglycone OH Glycoside glucoside primeveroside acuminoside vicianoside
residue O OH O HO O HO- HO O O HO O R group OH HO Accepted ManuscriptOH OH OH hydroxyl β-D-xylopyranosyl β-D-apiofuranosyl α-L-arabinopyranosyl
Table 5. Glycoside-derived aromas in three types of tea
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Page 14 of 36 Green Tea Black Tea Oolong Tea
HO HO HO
(Z)-3-hexenol (Z)-3-hexenol (Z)-3-hexenol Greenish Greenish Greenish OH OH OH OH OH OH
Linalool Hotrienol Linalool Geraniol Linalool Geraniol Floral Fruity Floral Sweet, Honey-like Floral Sweet, Honey-like HO HO HO HO O O HO O HO O O O Linalool oxide I II Linalool oxide I II Linalool oxide III IV Linalool oxide III IV Linalool oxide I II Linalool oxide III IV (furanoid) (furanoid) (pyranoid) (pyranoid) (furanoid) (pyranoid) Sweet, Floral, Creamy Earthy Sweet, Floral, Creamy Earthy Sweet, Floral, Creamy Earthy
OH O OH OH OH O OH OH HO OH HO benzyl alcohol benzyl alcohol 3-hydroxy-7,8-dihydro- -ionol benzyl alcohol methylsalicylate 2-phenylethanol 3-hydroxy-7,8-dihydro- -ionol Sweet, Honey-like Fruity Sweet, Honey-like Fruity Sweet, Honey-like Fresh, Sweet Honey-like O O HO O
O -damascenone -damascenone DMHF Sweet, Rose-like Sweet, Rose-like Caramel-like, Sweet
OH OH O H HO O O H HO HO HO O OH HO OH (Z)-3-Hexenol (Z)-3-Hexenyl-(tetra-O-acetyl)- β-D-glucopyranoside
O HO O HO HO Green, Oolong, Black tea OH O H HO O HO (Z)-3-Hexenol Green OH (Z)-3-Hexenyl- -D-xylopyranosyl- β-D-glucopyranoside(β-primeveroside)
Fig. 9. (Z)-3-Hexenol released from its glycoside precursor
Accepted Manuscript The following illustrates are examples of aroma compounds that are important to tea
flavors. One popular example in tea flavor is (Z)-3-hexenol, named leafy alcohol, and it is
present in all three types of tea, but higher concentration is present in green tea. It can be
obtained either by lipid degradation (Fig. 7) or by hydrolysis of its glycoside precursors during
the withering stage (Fig. 9) [6,34,35]. Linalool (threshold value: 6 ppb in water), geraniol
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Page 15 of 36 (threshold value: 7.5 ppb in water), benzyl alcohol, and 2-phenylethanol are mainly volatile
compounds in black tea released from their corresponding glycosides [6,36,37]. Geraniol and
linalool are liberated by geraniol synthase and linalool synthase, respectively, from the geranyl
pyrophosphate (geranyl-PP) precursor (Fig. 10). The sweet and floral aroma of four linalool
oxides are not from oxidization of linalool, instead, they come from the glycoside forms of
linalool oxides in fresh tea leaves [38,39]. Linalool oxide I and II are cleaved from glycation
bonds with the sugar moieties of β-D-glucoside and β-primeveroside. Except β-D-glucoside and
β-primeveroside, linalool oxide III and IV also bond with β-acuminoside moiety as glycoside
forms in oolong tea. (Fig. 11) [6,40,41].
OPP OH OH OPP geraniol synthase Linalool synthase
Geraniol Geranyl-PP Linaloyl-PP Linalool
Fig. 10. Formation of geraniol and linalool [25]
2,5-Dimethyl-4-hydroxy-3(2H)-furanone (DMHF), also called furaneol, (threshold value: 60
ppb in water) is a caramel and pineapple-like aroma that exists in many berries. It was first
isolated from pineapples in 1967. β-D-glucopyranoside of DMHF has been reported as the major metabolite for DMHFAccepted [38-40,42]. In addition, it has Manuscriptbeen reported that sugars with D configuration, such as D-glucose and D-fructose, were first transformed into D-fructose-1,6-
bisphosphate, which can be hydrolyzed into DMHF (Fig. 12) [42]. However, L-configuration
sugars cannot covert to DMHF.
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Page 16 of 36 O O HO O HO O HO H HO H O O OH HO O HO O OH HO O O HO HO OH Sweet, Floral, Creamy OH H O Linalool oxide I trans-Linalool 3,6-oxide-6- O-β-D-xylopyranosyl- cis-Linalool-3,6-oxide-6- O-β-D-xylopyranosyl- (trans, furanoid) β-D-glucopyranoside (β-primeveroside) β-D-glucopyranoside (β-primeveroside)
HO H HO O O HO HO O HO O HO O HO OH O OH H O H Sweet, Floral, Creamy trans -Linalool 3,6-oxide-6- O- Linalool oxide II cis-Linalool-3,6-oxide-6- O-β-D-glucopyranoside β-D-glucopyranoside (cis, furanoid)
O O O O HO O O O HO O HO HO OH HO HO OH O OHOH OHOH O HO cis-Linalool 3,7-oxide 6-O-β-D-apiofuranosyl- trans -Linalool 3,7-oxide 6-O-β-D-apiofuranosyl- β-D-glucopyranoside β-acuminoside) β-D-glucopyranoside (β-acuminoside) O Earthy O HO O O HO Linalool oxide III HO O O HO OH HO O (trans, pyranoid) O HO OH HO O HO OH OH O O cis-Linalool-3,7-oxide-6- O-β-D-xylopyranosyl- trans-Linalool 3,7-oxide-6- O-β-D-xylopyranosyl- β-D-glucopyranoside (β-primeveroside) HO β D-glucopyranoside (β-primeveroside) HO Earthy O O HO HO O O HO HO O OH Linalool oxide IV HO (cis, pyranoid) OH O O cis-Linalool-3,7-oxide-6- O-β D-glucopyranoside trans -Linalool 3,7-oxide-6- O-β-D-glucopyranoside
Fig. 11. Linalool oxides and their glycoside precursors [38,39]
Some non-alcoholic volatile aromas such as benzaldehyde, coumarin, and β-
damascenone also occur as their glycosidically-bound form, and these glycosidically-bound
volatile aromas take more steps than glycosidically-bound alcoholic volatiles to release free volatile aromas [43].Accepted For instance, benzaldehyde is liberatedManuscript from prunasin to mandelonitrile as an intermediate, which isomerizes from acid to aldehyde (Fig. 13) [25]. Coumarin has been
characterized as a sweet-herbaceous and cherry flower-like aroma in green tea. The steaming
time and drying temperature both influence the final concentration of coumarin. It has been
reported that most coumarin occurs in its free form in fresh green tea leaves but small amounts of
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Page 17 of 36 it bond with its primeveroside precursor. It is formed by the intramolecular esterification of
hydroxycinnamic acid after hydrolysis from 2-coumaric acid primeveroside (Fig. 13) [25,44].
D-glucose D-glucose 6-phosphate
D-fructose-6-phosphate D-fructose
D-fructose 1,6-bisphosphate
HO O Black tea L-Rhamnose
caramel-like sweet O L-fucose DMHF OR O O DMHF ß-D-glucopyranoside R=H HO OH O OH DMHF 6-O-malonyl ß-D-glucopyranoside O R=COCH2CO2H
Fig. 12. DMHF and its glycoside precursors [42]
HO O H H HO O CN HO CN HO CHO OH
Prunasin Benzaldehyde
COOH COOH O HOOC O O HO O H HO O hv Green tea OH HO O HO HO HO OH OH sweet-herbaceous Coumarin cherry flower-like 2-Coumaric acid primeveroside trans-O-Hydroxycinnamic acid
Fig. 13. Formation of benzaldehyde and coumarin [25,44]
Four β-damascenoneAccepted glycosidic precursors (7aManuscript, 7b, 8a, and 8b) have been isolated and identified from black and green tea leaves. The pH and processing temperature significantly
affect the hydrolysis of these glycosidic precursors. It has been demonstrated that a strong acidic
condition (pH 2.0) with a high temperature (90°C) favors the hydrolysis of glycosidic bonds.
Compounds 7a and 7b are first dehydrated to form the glycoconjugates of 8a and 8b via 9 and
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Page 18 of 36 10 intermediates, which leads to β-damascenone (Fig. 14) [12]. Table 6 illustrates aromas derived from glycosidic bonds with different sugar moieties in three types of tea.
OH OH OH OH HO OH OH O HO HO OH O O OH O OH O O
HO OH HO HO 8a 7a
OH OH OH OH HO HO O OH O O OH O O
HO -damasceonoe 9a 10a
OH
OH OH OH OH OH O O O HO HO HO O OH O O HO OH HO OH HO OH 7b 8b
OH OH O OH O HO O HO OH -damasceonoe 9b 10b
Fig. 14. Formation of β-damascenone from glycoside precursors [12]
TableAccepted 6. Glycoside-derived aromas and their Manuscript sugar residues in three types of tea Sugar residues Aglycone Green Tea Black Tea Oolong Tea Reference β-Primeveroside geraniol √ √ √ [31,45-47] linalool √ √ √ [31,45-47] benzyl alcohol √ √ √ [45,46,48] 2-phenylethanol √ √ √ [45,46] methyl salicylate √ √ √ [46,49,50] linalool oxide I √ √ √ [46,49] linalool oxide II √ √ √ [25,46,49]
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Page 19 of 36 linalool oxide III √ √ [25,38,39] linalool oxide IV √ √ [38,39] (Z)-3-hexenol √ √ √ [35] 8-hydroxygeraniol √ [46,49] 1-phenylethanol √ √ √ [43] benzyl alcohol √ √ √ [38,46,49] (Z)-3-hexenol √ √ √ [38,45,46,49] 2-phenylethanol √ √ [25,38] methyl salicylate √ √ [25,34] geraniol √ √ [25,38] β-D- linalool oxide I √ √ [25,38] Glucopyranoside linalool oxide II √ √ [25,38] linalool oxide III √ [25,38] linalool oxide IV √ [25,38] β-damascenone √ [9] DMHF √ [42] 1-phenylethanol √ √ √ [43] linalool oxide III √ [46,49] linalool oxide IV √ [46,49] β-Acuminoside 3-hydroxy-7,8- √ √ √ [25,51] dihydro-β-ionol β-Vicianoside geraniol √ √ [38,52]
5. Maillard reaction products
The Maillard reaction is universal in food processing. Large amounts of heterocyclic compounds such as furan, pyrrole, thiophene, and their derivatives have also been generated by the Maillard reaction during the tea manufacturing process, and some of these compounds are summarized in Table 7 [53-55].
AcceptedTable 7. Heterocyclic compounds Manuscript in tea fusion [53].
20
Page 20 of 36 Compound Structure Flavor
Furan spicy, smoky, cinnammon-like N H
Pyrrole sweet ether-like, slightly smoky O
Thiophene weak sulfurous S
N Oxazole pyridine-like, sweet in a diluted solution O
N Thiazole slightly smoky, coffee-like S
N Imidazole odorless N H
5.1 Strecker degradation products
Amino acids in tea leaves react with carbonyl compounds via the Strecker degradation
during fermentation forming distinctive aroma aldehydes, called Strecker aldehydes. It can also
occur in steaming or pan-firing steps [56]. The general mechanism is the nucleophilic addition of
the amine group to the carbonyl group forming an unstable hemiaminal. This hemiaminal readily undergoes removalAccepted of one molecule of water forming Manuscript a Schiff base followed by irreversible decarboxylation yielding an imine zwitterion. The addition of another molecule of water results
in an unstable amino alcohol. Finally, it decomposes into a α-ketoamine and an aldehyde, called
Strecker aldehyde, which is one carbon atom less than its amino acid precursor (Fig. 15) [57-59].
21
Page 21 of 36 H2O OH HO COOH CO2 H O O R2 N R3 NH O R2 N R3 + COOH R2 R R3 R3 H R2 1 NH2 R O R1 O 1 R1 O -Dicarbonyl Amino acid
O H H O OH 2 O NH2 R2 N R3 R2 NH H + H R3 R3 H R2 R1 R1 O R1 O Strecker aldehyde
Fig. 15. Mechanism of the Strecker degradation
R2 OH OH COOH OH OH OH COOH COOH H O CO O 2 2 HO OH + NH2 N R NH R 1 + 1 H H R2 OH OH O Amino acid OH OH N R 2 O NH Amino acid 2 Strecker aldehyde Amadori compounds COOH
O2 metal ion H2O
OH O OH R H O OH R OH OH COOH OH 1 2 1 HO HO HO H O NH2 H R N COOH N 2 + 1 N R1 O O O HO Strecker aldehyde OH OH O HO HO CO2
Fig. 16. Amadori compounds generate Strecker aldehydes
Amadori compounds are viewed as another type of carbonyl compounds and can either
react with amino acids via the Strecker degradation or can be oxidized by oxygen catalyzed by metal ions giving rise to Strecker aldehydes (Fig. 16) [57,59-61]. Fig. 17a lists reported amino
acids and their corresponding Strecker aldehydes produced during the tea manufacturing process
[8]. In addition, the Strecker degradation of amino acids in tea leaves must be present in oxidizing tea flavonols,Accepted which is the same as carot enoidManuscript degradation. It is the driving force for Strecker degradation (Fig. 17b).
22
Page 22 of 36 O COOH O H2N COOH H H H NH2 Glycine Formaldehyde Phenylalanine Phenylacetaldehyde COOH O
NH2 H Alanine Acetaldehyde O COOH H O NH2 2-Methylbutanal H Isoleucine H2N COOH Valine Isobutyraldehyde
O S COOH S O
H NH2 H H2N COOH Methional Leucine Isovaleraldehyde Methionine
Fig. 17a. Amino acids and their corresponding Strecker aldehydes [8]
O OH O R R R OH 1 2 3 Catechol HO O (-)-Epicatechin (EC) H OH H HO O Oxidase R1 R1 (-)-Epicatechin-3-gallate (ECG) H Gallate H (-)-Epigallocatechin (EGC) OH OH H R2 R2 O2 R3 (-)-Epigallocatechin-3-gallate (EGCG) OH Gallate H R3 OH OH (+)-Catechin (C) H H OH (+)-Catechin-3-gallate (CG) H H Gallate Flavanols o-Quinone
Amino Acids Strecker Aldehydes and other degreadtion products
Fig. 17b. The red arced arrow indicates that oxidation of tea flavonols is the driving force of the Strecker degradation [8]
In principle, all free amino acids should have their corresponding Strecker aldehydes.
However, only amino acids listed in Fig. 17a have their Strecker aldehydes. One reason is that non-volatile productsAccepted are generated instead of volatile Manuscript aldehydes. Glutamic acid degradation into succinimide is a good example. The other possibility is some Strecker aldehydes are so unstable
that they readily decompose into other volatiles by cyclization, coupling, or dehydration. The
representative example is the degradation of theanine, an abundant free amino acid in tea leaves.
When theanine is heated to 180°C, a large amount of N-ethyl formamide, ethyl amine, propyl
amine, 2-pyrrolidone, N-ethyl succinimide, and 1-ethyl-3,4-dehydropyrrolidone can be detected
23
Page 23 of 36 (Fig. 18a) [62]. If it is heated with D-glucose or other monosaccharides above 150°C, they can
condense to a large amount of 1-ethyl-3,4-dehydropyrrolidone with some pyrazines and furan
derivatives, such as 1-ethyl-5-methyl-pyrrole-2-aldehyde, 1-ethylpyrrole, ethylmethylpyrrole, 1-
ethyl-2-acetylpyrrole, 2-acetylpyrrole (threshold value: 170 ppm in water), 2,5-dimethylpyrazine, trimethylpyrazine, 2-ethylpyrazine, 5-methyl-2-furfuryl alcohol, 2-acetylfuran, 5-methyl-2-
furaldehyde, and 2-furaldehyde (Fig. 18b) [63-65].
It should be pointed out that the longer the storage of oolong tea, the deeper is the
oxidation with stronger flavors [66]. Thus, volatile constituents in aging oolong tea include many
nitrogen-containing heterocycles, such as pyridine and pyrrole derivatives, which are assumed to
be the consequence of Strecker degradation. Figure 19 shows the mechanism of furfural and 5-
methylfurfuryl alcohol (5-HMF) originated from the Maillard reaction between hexose/pentose
and theanine [67].
. O O N O N NH H2N H 2 N O N-Ethyl formamide Ethyl amine Propyl amine 1-Ethyl-3,4-dehydropyrrolidone N-Ethyl succinimide
Fig. 18a. Products of theanine thermal degradation
Accepted Manuscript
24
Page 24 of 36 O O N O N N
1-Ethyl-5-methylpyrrole-2-al 1-Ethyl-3,4-dehydropyrrolidone 1-Ethyl-2-acetylpyrrole
O O O N OH H NH2 N N NH H Theanine 2-Acetylpyrrole 1-Ethylpyrrole n-Propylpyrrole 150-160° + N N N OH OH N O N N HO 2-Ethylpyrazine Trimethylpyrazine 2,5-Dimethyl-pyrazine OH OH O D-Glucose O OH CHO O O O O 2-Acetylfuran 5-Methyl-2-furaldehyde 2-Furaldehyde 5-Methylfurfuryl alcohol Fig. 18b. Theanine reacts with D-glucose via the Strecker degradation [65]
NR NHR CHO HC NR HC NHR H OH CHO H OH HC OH HC RNH2 H O H+ H O H OH H OH 2 H OH H OH H OH OH 2 or or or H OH H OH H OH H OH H OH H OH H OH H OH H OH H OH H OH H OH pH<5 CH OH CH OH CH2OH CH2OH CH2OH 2 CH2OH 2
Hexose Pentose Schiff base 1,2-Enaminol
O O HC HC O O OH OH OHC O H2O OHC O CH2 CH NHR H OH CH HO HC NHR H OH H OH HC H2ORNH2 5-HMF OH CH2OH CH2OH CH OH or 3,4-DDH H OH CH H OH H OH H O O HC CH2OH CH2OH HC O O OHC O H2O OHC O H OH CH HO H OH CH CH OH AcceptedCH2OH Manuscript2 Furfuraldehyde 3,4-DDP
Fig.19. Formation of furfural and 5-HMF via the Maillard reaction between theanine and reducing sugars [67]
5.2 Sulfide compounds
Methionine plays a major role in the formation of odorous sulfur-containing compounds.
25
Page 25 of 36 Its Strecker aldehyde is methional (threshold value: 0.2 ppb in water), which is usually
considered to be the main precursor of methanethiol (threshold value: 0.02 ppb in water, Fig. 20)
[68]. Methanethiol is the direct precursor of numerous sulfide compounds with very low
perception thresholds.
O O R S 2 S S O OH -CO2 OH + O N OH N O NH2 R1 R R R R 1 2 Methionine 1 2
[O], H2O
NH3, R1-(CO)2-R2 S OH S O O CH3SH +
Methional Acrolein (Strecker aldehyde) Methanethiol
Strecker degradation of methionine [O]
O O S S CH3 S S S S OH R-SH S O HO-S
Dimethyl sulfide Dimethyl trisulfide
Fig. 20. Formation mechanism of sulfide compounds
Dimethyl trisulfide has a putrid flavor in black tea. It comes from further oxidation of
methional to sulfone, which then decomposes into dimethyl trisulfide (Fig. 20). Dimethyl disulfide (threshold value: 7.6 ppb) has a garlic-like flavor in black tea and green tea. Its formation mechanism is the same as dimethyl trisulfide (Fig. 20). Methyl methionine sulfonium salt has also been reported as the precursor of dimethyl sulfide in green tea [8,69].
5.3 Pyrrole derivatives
Pyrrole derivativesAccepted are primarily responsible Manuscriptfor the roasted, nutty, and popcorn-like flavors in tea infusion [62]. Pyrazines are important constituents in black tea and oolong tea (Fig.
21). A myriad of factors affect the production of pyrazines, such as storage time, pH, temperature, water activity, and enzymes.
26
Page 26 of 36 N N
N N
R4 N R1 nutty nutty
N R3 N R2 N COCH3
Pyrazine N OMe N roasted, nutty earthy, musty roasted
Fig. 21. Basic structure of pyrazines
2-Acetyl-2-thiazoline (AT, threshold value: 1.3 ppb in water) has an intense roasted aroma. 2-(1-Hydroxyethyl)-4,5-dihydrothiazole (HDT) was identified as the key intermediate for the formation of AT [70], which is the reaction between cysteamine and 2-oxoprpanal. The first step is the formation of the aminoacetal (a). Isomerization of (a) into intermediate (b) enables a nucleophilic attack of the thiol group with formation of the thioacetal (c). Elimination of water would yield intermediate HDT. Its tautomeric formation (d) further reacts with excess 2- oxopropanal giving rise to AT (Fig. 22).
SH SH SH S OH CHO SH O H O + OH O NH N OH NH2 NH NH H OH OH MGO a O b c Cysteamine (2-Oxopropanal) CHO S S S -H O O Loss of 2 S N OH N OH N OH +H2O MGO H O N HDT d HO O AT Accepted Manuscript Fig. 22. Formation mechanism of 2-acetyl-2-thiazoline (AT) [70]
2-Acetyl-1-pyrroline (AP), a popcorn-like flavor in black tea, has a threshold value of 0.1 ppb in water. AP and 2-acetyltetrahydropyridine (ATHP) have been established as crucial contributors in many processed foods. 1-Pyrroline was recognized as a key intermediate. It has
27
Page 27 of 36 been reported that 1-pyrroline and hydroxyl-2-propanone generated from the reaction of proline
and 2-oxopropanal via the Strecker degradation (Fig. 23a) [71]. Hydroxyl-2-propanone then
attached to the carbon-2 of 1-pyrroline, forming 2-(1-hydroxy-2-oxopropyl) pyrrolidine
intermediate. Next, it undergoes a ring opening reaction leading to 5, 6-dioxoheptylamine. Then,
the amine group nucleophilic attached to the first carbonyl group forming a six member ring and
finally isomerizing to ATHP [72]. If there is a high concentration of 2-oxopropanal in the initial step (Fig. 23a), it reacts with 1-pyrroline much faster than hydroxyl-2-propanone forming AP as the final product (Fig. 23b) [72].
O O OH HO N -H2O OH -CO2 N -H O + HO 2 N O HO H O HO O OH HO OH HO OH Proline 1-Deoxyglucosone OH
O H HO H O O -H2O HO HO H N OH OH MGO
O HO
OH N N H2O N N H OH OH 1-Pyrroline
O H HO
HO O Hydroxy-2-propanone
Accepted Manuscript Fig. 23a. Formation of 1-pyrroline, 2-oxopropanal, and hydroxyl-2-propanone [72]
28
Page 28 of 36 O HO O
N + N OH N OH OH H H 1-Pyrroline Hydroxy-2-propanone
O O Black tea O NH N N Roasty 2 OH H NH2 O O ATHP
O O O HO HO OH O HO OH H O +H2O H2O OH N N N N NH H MGO -H2O N H 1-Pyrroline O H
HO O -HCOOH O +H2O 2 N O N N OH N O OH H -H2O H AP NH2
Fig. 23b. Mechanism of ATHP and AP formation [72]
Indole is an essential volatile aroma in black tea and green tea. One possible precursor is
tryptophan that can be oxidized by tryptophan indole-lyase (Fig. 24) [73]. An alternative
mechanism is that it is released from L-tryptophan, an Amadori compound under pyrolysis
conditions [74,75].
COOH COOH NH 2 NH H O Black tea, Green tea tryptophan-indol HO H N N N H H OH H H lyase animal-like H OH Indole Tryptophan OH Amadori Compound AcceptedFig. 24. Indole and itsManuscript precursors
Only a small amount of Maillard reaction products are found in green tea. It is presumed
that a large amount of tea polyphenols, particularly catechins, are characterized as superior
carbonyl compound scavengers to effectively inhibit the glyoxal formation from D-glucose,
which may be useful for cutting an advanced Maillard reaction pathway [76]. This observation
29
Page 29 of 36 demonstrates that different manufacturing processes highly influence the final aromas in tea [77].
6. Summary
Aroma compounds differ largely depending on the manufacturing process, even from the same categories of different origins. Black tea volatiles are mainly dependent on the oxidation of tea flavonols during fermentation. Virtually, most alcohols, aliphatic acids, phenols, and carbonyls occur in this stage. The degree of partial fermentation determines the constitution and concentration of major aromas in oolong tea, such as jasmine lactones, nerolidol, and methyl jasmonate. Non-fermented green tea contains abundant tea catechins that give it its unique greenish aroma. Major volatile aroma compounds identified in different types of tea with their precursors are summarized in Table 8, which lists aroma compounds, their flavor notes, precursors of formation, odor threshold, and existing tea category.
Table 8. Main tea aromas and their precursors of formation
Odor Threshold Reference Compounds Precursors Type of tea identified Aroma quality (ppb in water) β-Ionone Carotenoids Green, Oolong, Black tea Woody, violet 0.007 [7,22] Nerolidiol Carotenoids Green, Oolong, Black tea flowery [7,50] Theaspirone Carotenoids Black tea flowery [8] α-Ionone Carotenoids Black tea Woody, hay-like [78,79] sweet [78] β-Damascone Carotenoids Green tea hay-like Sarfranal Carotenoids Green, Oolong, Black tea herbal [79] Geranylacetone Carotenoids Green, Oolong, Black tea Floral, hay-like [78,79] Carotenoids [12,14] β-Damascenone Green, Black tea fruity, apple-like 0.002 Glycosides Lipids, [6,34] (Z)-3-hexenol Green, Oolong, Black tea green 13 AcceptedGlycosides Manuscript Green tea, Oolong tea, [22,50] Hexanal Lipids grassy, green 10 Black tea pungent, malt, [50] Pentanal Lipids Green tea almond (Z)-1,5-octadien- [78] Lipids Green tea geranium-like 3-one Jasmine Lipids Green tea jasmine-like [50] (E,Z)-2,6- [50] Lipids Green tea cucumber-like 0.03 nonadienal 1-octen-3-one Lipids Green tea mushroom-like [78]
30
Page 30 of 36 floral, jasmine- [22,34,50] cis-Jasmone Lipids Green, Oolong, Black tea like (Z)-4-heptanal Lipids Green, Oolong, Black tea hay-like 0.06 [50] 1-penten-3-ol Lipids Oolong tea butter, green [22] (E)-2-hexenal Lipids Green tea, Black tea green 190 [22] (E,E)-2,4- [22] Lipids Black tea fatty hexadienal (E,E)-2,4- [78] Lipids Green tea, Black tea fatty, fried 0.16 decadienal (Z)-3-hexenal Lipids Green tea, Black tea green [22] Methyl [34] Lipids Green, Oolong, Black tea floral jasmonate Hexanoic acid Lipids Black tea Sweaty, green 890 [78,79] 2,3-butanedione Lipids Green tea butter 10 [78.79] (E)-geraniol Glycosides Green, Oolong, Black tea rose-like 3.2 [22,50] Carotenoids Green, Oolong, Black tea [22,50] Linalool floral 6 Glycosides Linalool Oxide I Green, Oolong, Black tea earthy, floral, [38] Glycosides II III IV creamy Hotrienol Glycosides Oolong tea flowery 110 [25] Methyl salicylate Glycosides Green, Oolong, Black tea minty [22,50] Green, Oolong, Black tea burning taste, [22,50] Benzyl alcohol Glycosides faint aromatic 2-Phenyl ethanol Glycosides Oolong tea, Black tea honey-like 1000 [22] 4-hydroxy-2,5- [42] dimethyl-3(2H)- Glycosides Black tea caramel-like 60 furanone dimethyl Maillard [22.50] Green tea, Oolong tea garlic-like 7.6 disulfide reaction Maillard Black tea [78] trimethylsulfide putrid 0.01 reaction 2-acetyl-3- Maillard Black tea [78] roasty methylpyrazine reaction 2-ethyl-3,5- Maillard Black tea [78] nutty 0.04 dimethylpyrazine reaction 5-ethyl-2,3- Maillard Black tea [78] nutty 0.09 dimethylpyrazine reaction Maillard [22,33] Indole Green tea, Oolong tea animal-like reaction 2-acetyl-2- Maillard [22] Black tea popcorn-like 1.3 thiazoline reaction 2-acetyl-1- Maillard [22] AcceptedBlack tea Manuscript popcorn-like 0.1 pyrroline reaction Phenyl- Maillard [22] Oolong tea, Black tea honey-like 4 acetaldehyde reaction 4-methyl-2- Maillard [78] methyl-2- Green tea meaty 0.00002 reaction butanethiol 4-mercapto-4- Maillard [78] methyl-2- Green tea meaty 0.0001 reaction pentanone Methional Maillard Green, Black tea potato-like 0.2 [78]
31
Page 31 of 36 reaction
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