Attokaran M. Natural Food Flavors and Colorants

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126 Individual Flavors and Colorants

Chemistry

The composition of the bark will vary from species to species. On average, the bark

contains 7 – 32% carbohydrate, 3 – 3.5% protein, about 2% ﬁ xed oil, 12 – 28% crude

ﬁ ber, and 0.5 – 5% essential oil.

The volatile oil is the most important constituent because of its aroma and ﬂ avor.

The major component is cinnamic aldehyde or cinnamaldehyde (Fig. 31.1 ).

Cinnamaldehyde was ﬁ rst isolated in 1834 by Dumas and Peligot. Naturally occurring

cinnamaldehyde is trans isomer.

Essential Oil

On prolonged steam distillation, ground cassia gives cassia oil. The oil consists of a

high boiling fraction like cinnamaldehyde and has a speciﬁ c gravity higher than 1.0.

Photo 6. Cassia. See color insert.

Figure 31.1. Cinnamaldehyde.

CH = CH – CHO

31 Cassia 127

To facilitate steam distillation, it is better to use a side arm connected to the water

condenser above the packed material, instead of an upward gooseneck. The collected

oil tends to diffuse, making its separation from water very difﬁ cult. Salting may not

help, as the oil is heavier than water and so will sink. Separation requires the solution

to stand for some time. The commercial yield will be about 2%. The cinnamaldehyde

content will be around 75%. Other compounds present are α - pinene 1.2%, limonene

2%, coumarin 2.5%, benzaldehyde, cinnamic acetate, and chavicol.

Cassia oil is extremely difﬁ cult to produce. Cassia leaf oil is used as the essential

oil.

According to the FCC, cassia leaf oil is a yellow to brown liquid with the charac-

teristic odor and taste of cassia cinnamon. On aging or exposure to air it darkens and

thickens. It is soluble in glacial acetic acid and in alcohol.

Physical characteristics as deﬁ ned by the FCC are as follows.

Optical rotation − 1 ° to + 1 °

Refractive index 1.602 – 1.614 at 20 ° C

Speciﬁ c gravity 1.045 – 1.063

Solubility 1 mL dissolves in 2 mL of 70% alcohol

Cassia bark is found to have signiﬁ cant quantities of cinnamaldehyde. The highest

level is noticed in the debarked cortex (He et al. 2005 ). By establishing markers based

on major components and coumarin, scientists are able to distinguish genuine cassia

bark from adulterants. In another study, trans cinnamaldehyde is determined by

1 H - NMR spectrometry. The amount of cinnamaldehyde extracted is highest with

ethyl acetate, followed by chloroform and n - hexane (Song et al. 2005 ). By extracting

with supercritical carbon dioxide, 3.75% cinnamon bark oil is obtained with a pressure

of 120 bar (Cai et al. 2008 ). Compounds identiﬁ ed in the tender stem of cassia include

2 - methoxy cinnamic acid, 1,4 - diphenylbutanedione, ergosterol - 5a - , 8a - peroxide,

2 - methoxybenzoic acid, and syringaldehyde, which have not been reported earlier (Liu

et al. 2002 ).

Oleoresin

Because of the long duration of distillation and for separation of oil, cassia bark is

generally extracted directly to make oleoresin. For this, the raw material is pulverized

coarsely in a hammer mill, followed by passing through a roller mill. It is then

extracted using solvents such as ethylene dichloride or acetone – hexane mixture.

The yield of oleoresin in the case of ethylene dichloride is around 5% with a volatile

oil content of 60 – 70% v/w. If the solvent is an acetone – hexane mixture, the yield is

slightly lower, with about 4.8% with oil content of 60 – 70% v/w. The oleoresin so

obtained with either solvent will be a thick reddish - brown liquid with a sharp, medici-

nal aroma and a spicy burning taste. Suitable diluents can give a relatively free - ﬂ owing

product. Generally, acetone extraction gives a reddish tint and ethylene dichloride a

brownish tint. This will be reﬂ ected in the extraction using the acetone – hexane

mixture.

128 Individual Flavors and Colorants

Uses

Cassia is a spice that gives a strong ﬂ avor generally referred to as “ cinnamon ﬂ avor. ”

Sri Lankan cinnamon ( Cinnamomum verum ) is generally regarded as tree cinnamon,

but it is very mild. In the United States, cassia is a popular ﬂ avor in meat, vegetable,

and bakery products. The well - known cinnamon rolls are ﬂ avored using cassia. For

such processed food products, oleoresin is very convenient to use. Oil is rarely used.

The cassia leaf oil is used in cleaning lotions and other cheaper toiletries where the

phenolic constituents of the oil serve as a mild antiseptic.

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Cassia oil 2258 8007 - 80 - 5 182.20 –

84961 - 46 - 6

Cassia oleoresin/extract 2257 84961 - 46 - 6 – –

Cassia absolute ( Acacia farnesiana ) 2260 8023 - 82 - 3 172.510 –

89958 - 31 - 6

References

Baruah , Akhil . 2010 . Essential oils of Cinnamomum tamala Nees and Eberm from Northeast India — an

overview . Indian Perfumer 54 ( 1 ), 54 – 55 .

Cai , Ding - jian ; Zhou , Yu - qin ; and Mao , Lin - chun . 2008 . GC - MS analysis on the composition of the essential

oil from Chinese cinnamon by supercritical ﬂ uid CO

extraction . Zhongguo Shipin Tianjiaji ( 6 ), 91 – 98

(Chinese) ( Chem. Abstr. 151 :376132).

He , Zhen - Dan ; Qiao , Chun - Feng ; Han , Quan - Bin ; Cheng , Chuen - Lung ; Xe , Hong - xi ; Jiang , Ren - wang ;

But , Paul Pui - Hay ; and Shaw , Pang - Chui . 2005 . Authentication and quantitative analysis on the chemical

proﬁ le of cassia bark (Cortex cinnamon) by high pressure liquid chromatography . J. Agric. Food Chem.

53 ( 7 ), 2424 – 2428 .

Liu , Jiangyun ; Yang , Xuedong ; Xu , Lizhen ; and Yang , Shilin . 2002 . Studies on chemical constituents in

the dried tender stem of Cinnamomum cassia . Zhongcaoyao 33 ( 8 ), 681 – 683 (Chinese) ( Chem. Abstr.

139 :162049).

Song , Myoung - Chong ; Yoo , Jong - Su ; and Back , Nam - in . 2005 . Quantitative analysis of t - cinnamaldehyde

of Cinnamomum cassia by 1H NMR spectrometry. 2005 . Han ’ guk Eungyong Sangmyong Hwahakhoeji

48 ( 3 ), 267 – 272 (Korean) ( Chem. Abstr. 144 :398470).

Introduction

The celery plant was known to the ancient world. There is mention of celery in

archeological reports covering of the ninth century BC. In Homer ’ s Odyssey , there is

mention of wild celery, and in the Iliad , there is description of horses grazing on wild

celery, which grows in the marshy outskirts of Troy. Celery leaves and inﬂ orescence

were part of the garland discovered in the tomb of Tutankhamen, a pharaoh of Egypt.

The plant is closely related to parsley and carrots. Celery ’ s leaf stalk and ﬂ eshy

taproot are used as a vegetable in colder climates of Europe and America. However,

in temperate climates, celery is cultivated for the seeds, which give valuable extrac-

tives used for ﬂ avoring. Generally, the cultivar used in producing essential oil and

oleoresin from seeds, and cultivated in a temperate climate may not be the best suited

for use of its leaf stalk and taproot as a vegetable; similarly, the cultivar used as a

vegetable is not suitable for producing essential oil and oleoresin.

Plant Material

Celery seed is the seed of a perennial herbaceous plant, which grows to a height of

0.5 – 1.5 m. The plant has succulent and numerous roots. Stems are branched and

produce leaves that are radical, pinnate, and large, divided into three segments.

Flowers are small and white in color. Fruits are small with 1 - mm diameter and 1.5 - mm

length and, on drying, produce very small seeds, which are brown in color and bitter

in taste (see Photo 7 ).

The plant is cultivated in various countries including France, Holland, Hungary,

China, and the United States. But the cultivation of the seed - yielding cultivar is most

prevalent in India, especially in the Punjab State around Amritsar. Here, in relatively

cooler, hilly climatic conditions, the plant is biennial, producing seeds only in the

second year; in the plains, it is an annual, producing seeds in the ﬁ rst year. In the

plains, where the bulk of cultivation is carried out, seeds are sown in September,

transplanted in January and harvested during May and June. Being bitter, celery seed

was primarily used for therapeutic purposes. Various medicinal properties, such as

the lowering of blood pressure, relief from joint pains, antiseptic properties for the

urinary tract, diuretic action, and promotion of the onset of menstruation are attributed

to the seed. But the main use of the seed is to produce extractives useful in food

ﬂ avoring.

Celery Seed

Apium graveolens L ( Umbelliferae )

129

Natural Food Flavors and Colorants Mathew Attokaran

130 Individual Flavors and Colorants

Chemistry

The seed on analysis shows about 23% fat, 41% carbohydrate, and 18% protein. It is

rich in minerals and water - soluble vitamins. However, since the seed is used for

extracting oil and oleoresin, its nutritional quality is of no signiﬁ cance. Seeds contain

1.5 – 2% of essential oil, which needs prolonged steam distillation. While the main

constituent is limonene, the value of the oil is determined by two isomers of a cyclic

sesquiterpene hydrocarbon, α - selinene and β - selinene (Fig. 32.1 ). Bitterness of oleo-

resin is caused by phthalides, of which sedanolide is the most prominent (Fig. 32.2 ).

This is lactone of sedonolic acid. Another phthalide present is sedonic anhydride or

tetrahydro - N - butlidene phthalide.

Essential Oil

For release of oil, treatment with water is recommended. For this, dry seeds and about

40% of water are mixed well in a mechanical screw mixer. This is then fed into a

Photo 7. Dried celery seeds. See color insert.

Figure 32.1. Selinenes of celery seed oil. (A) α - Selinene. (B) β - Selinene.

32 Celery Seed 131

stainless steel distillation unit, and steam is admitted from the bottom at normal pres-

sure. Steam distillation of celery seed is a slow process. The value of the oil is more

in its sesquiterpene constituents. Full distillation takes 40 hours, giving a yield of

1.8 – 2.2 %.

The main constituents of celery seed oil are d - limonene and selinene. The former

(1 - methyl - 4 - isopropenyl - 1 - cyclo - hexene) is present in the amount of 69 – 75%.

Selinene, which is cyclic sesquiterpene, is present in levels of 10 – 15%. High boiling

selinene is actually a mixture of α - and β - isomers. The β - isomer is more abundant

than the α - isomer.

Celery seed oil is a yellow to yellowish - brown mobile liquid with a curry - like,

pleasant aroma. According to the description given by the FCC, celery seed oil occurs

as a yellow to greenish - brown liquid with a pleasant aromatic odor. It is soluble in

most ﬁ xed oils with the formation of ﬂ occulent precipitate and in mineral oil with

turbidity. It is partially soluble in propylene glycol, but it is insoluble in glycerin.

Physical characteristics as deﬁ ned by the FCC are as follows.

Optical rotation Not given

Refractive index 1.480 – 1.490 at 20 ° C

Speciﬁ c gravity 0.870 – 0.910

Solubility 1 mL dissolves in 8 mL of 90% alcohol usually with turbidity

(Author ’ s data for optical rotation is + 48 to + 78 ° .)

Oleoresin

The best way to obtain a good yield is to extract the deoiled residue and blend the

resin that is obtained with the essential oil. For this, the deoiled material after steam

distillation is dried. To get maximum yield of nonvolatile constituents, mainly triglyc-

erides and other lipids, the dried material is passed through an expeller in which cells

will be broken for combination with a solvent. If the powder is overdried, slight

moisturizing with about 5% of water on the basis of weight of the extractable deoiled

material may be needed. If completely dry, heat will be formed during the passage

through the expeller. During the process, no oil is actually taken out since the purpose

is to break up the cells. If any fatty oil oozes out, that is taken into the percolator

along with disintegrated deoiled material.

Solvent extraction is carried out by batch countercurrent method. Usually, the

quantities handled may not justify a continuous extraction plant. The rich miscella is

Figure 32.2. Sedanolide.

132 Individual Flavors and Colorants

distilled free of the solvent to obtain the resin fraction. The weaker miscella that comes

out after the withdrawal for distillation is passed on to the next percolator. The ﬁ nal

wash will be with pure solvent. The yield of resin fraction will be 17 – 18% on the

basis of original dry raw material.

An appropriate quantity of oil obtained earlier is added to form oleoresin of

required speciﬁ cation. Commercial requirement is from 7% to 10% of volatile oil

content. The resin fraction will have some oil that escapes steam distillation.

Considering this, only a smaller quantity of oil will need to be added. This will leave

some salable celery seed oil. Celery seed oleoresin is a greenish - brown oily liquid

with typical warm aroma and bitter taste.

Bitterness of the oleoresin is caused by phthalides, which are present to the

extent of 2.5 – 3%. While sedanolide is the most important, sedonic anhydride and

tetrahydro - N - butlidene phthalide present to a level of 0.5% also contribute toward

bitterness.

Phthalides are mostly present in the nonvolatile hexane - extracted fraction. However,

small quantities can be present in the high boiling fraction of the volatile oil as recent

research shows.

Sedanolide is used as an herbal remedy to treat inﬂ ammatory conditions such as

gout and rheumatism. It is relatively nontoxic to cells in culture but the protection it

affords against hydrogen peroxide and tertiary butyl hydroperoxide - induced toxicity

was not statistically signiﬁ cant (Woods et al. 2004 ). It can be washed out from resin

with methanol or ethanol, as they are relatively polar. Alternatively, concentrated

phthalide fraction can be obtained by extraction of deoiled material with methanol or

ethanol. After the removal of solvent, the resin can be freed of nonpolar lipid constitu-

ents by washing with hexane. The residual, near solid material has intense bitterness

used in special ﬂ avoring and for medicinal use.

Direct single - stage extraction with hexane results in a lower yield of extractives.

During the step of passing through the expeller to break up the cells, there is loss of

essential oil. Two - stage extraction, ﬁ rst steam distillation to separate oil and then

solvent extraction to obtain the nonvolatile resin (followed by appropriate blending),

therefore has merit.

GC - MS studies of Indian celery seed oil has been carried out by Rao et al. (2000) .

It shows 44 constituents, out of which limonene (50.90%), β - selinene (19.53%), 3 - n -

butyl phthalide (6.92%), nerolidol (2.29%), and α - selinene 1.63% are the most promi-

nent. On hydrodistillation, celery seed volatile oil reveals several terpene hydrocarbons

and oxygenated derivatives including limonene, β - selinene, and butyl phthalide

(Chowdhury and Kapoor 2000 ). In the study of Chinese oil, the compounds noted are

terpenes, phenolic compounds, and some phthalides (Liu and Liao 2004 ).

Uses

Celery seed essential oil is used in food ﬂ avoring to give a pleasant aroma to a range

of products such as soup, beverages, confectionery, and baked goods. The oleoresin

with a bitter taste is used in various savory preparations of meat and vegetables.

The solid extract rich in phthalides ﬁ nds use in some special foods that need a bitter

note and also for medicinal purposes.

32 Celery Seed 133

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Celery seed oil 2271 8015 - 90 - 5 182.20 –

Celery seed extract (including CO

extract) 2270 89997 - 35 - 3 182.20 –

Celery seed extract solid 2269 89997 - 35 - 3 182.20 –

References

Chowdhury , A.R. ; and Kapoor , V.P. 2000 . Essential oil from the fruit of Apium graveolens . J. Med. Aromat.

Plant Sci. 22 ( 1B ), 621 – 623 .

Liu , Li ; and Liao , Lixin . 2004 . Study on chemical constituents in essential oil from celery seed . Tianran

Chanwu Yanjiu Yu Kaifa 16 ( 1 ), 36 – 37 (Chinese) ( Chem. Abstr. 143 :474910).

Rao , L. ; Jagan , Mohan ; Nagalakshmi , S. ; Puranaik , J. ; and Shankaracharya , N.B. 2000 . Studies on chemical

and technological aspects of celery ( Apium graveolens L) seed . J. Food Sci. Technol. 37 ( 6 ), 631 – 635 .

Woods , J.A. ; Jewell , C. ; and O ’ Brien , N.M. 2004 . Sedanolide, a natural phthalide from celery seed oil:

effect on hydrogen peroxide and tert - butyl hydroperoxide - induced toxicity in HepG2 and CaCo - 2 human

cell lines . In Vitr. Mol. Toxicol. 14 ( 3 ), 233 – 240 .

Introduction

Chicory root is a well - known coffee substitute. It is also known as “ blue sailors ” or

“ coffee weed. ” The cultivated forms are grown also for the leaves, which are eaten

raw as salad. But the main use of chicory is for the root, which after roasting and

grinding becomes a coffee substitute or additive.

Chicory has a long history in France, cultivated as a potherb. In Napoleon ’ s time,

it became important as an adulterant or substitute for coffee. This is a practice that

was later followed in the United States, England, and India. Coffee containing more

than 50% of chicory powder is referred to as “ French coffee ” in the English - speaking

world. In Roman cuisine, chicory root is used after frying with garlic and chili to give

a welcome bitter and spicy ﬂ avor to meat dishes.

Plant Material

Chicory is a bushy perennial herb, which is commonly seen growing on the roadside

in Europe, the United States, and Australia. The plant, when it starts ﬂ owering, attains

a height of 30 – 100 cm. The leaves are stalked, lanceolate, and unlobed. It generally

has bright blue and, in a few cases, white, ﬂ owers whose heads will be 2 – 4 cm in

diameter. There will be two rows of involucral bracts, the inner being longer and erect

and the outer shorter and spreading. It has spindle - shaped taproot, which is used as

raw material for ﬂ avor.

The root has a polysaccharide, inulin, which is similar to starch. It is a storage

carbohydrate that may be present from 20% to over 50% according to cultivar. On

hydrolysis, inulin yields mostly fructose and some glucose. It is sometimes used as a

mild sweetener in the food industry and as a prebiotic in yogurt. It is also becoming

popular as a source of soluble dietary ﬁ ber.

Chicory root has an aroma fraction made up of pyrazines, benzothiozoles, carbonyl

compounds, furans, phenol, and organic acids (Leung and Foster 1996 ). It has also

bitter components, small amounts of indole alkaloids, phenolics, pectin, and some

ﬁ xed oil. Volatiles isolated from roasted chicory by simultaneous steam distillation

and solvent extraction on headspace analysis have been investigated by GC - MS

(Baek and Cadwallader 1997 ). They include some pyrazines and N - furfuryl pyrroles

as well as some minor aroma - contributing chemicals. Five known (and one unknown)

Chicory

Chichorium intylus L ( Compositae or Asteraceae )

135

Natural Food Flavors and Colorants Mathew Attokaran