Attokaran M. Natural Food Flavors and Colorants

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216 Individual Flavors and Colorants

Chemistry

The aroma and ﬂ avor of garlic is released on bruising or processing. When the cells

are broken, the alliin present is broken down on contact with the enzyme allinase to

produce the sulfur - containing compound allicin. This being unstable, it further disin-

tegrates into simpler sulfur - containing volatile compounds such as diallyl disulﬁ de

and other sulﬁ des.

Alliin, the precursor of allicin, is quite sensitive to heat, and extraction with ethanol

should be carried out at temperatures below 0 ° C. Allicin itself is also sensitive to the

high temperature employed in GC studies and can be converted into cyclized com-

pounds through dehydration reaction (Singh 2009 ). This factor has to be taken into

account while interpreting data on GC analysis.

The chemistry of aroma formation is quite complicated but well studied. For more

detail, the reader is referred to various reviews (Abraham et al. 1976 ; Choi et al. 2007 ).

Essential Oil

Special care is needed for distillation of garlic oil, which is a heavy oil. Modiﬁ cation

of the still is made to allow reﬂ uxing and water - steam distillation. Otherwise, it is

very difﬁ cult to release the oil from the cells. A practical arrangement would be recy-

cling of condensed water and simultaneous admission of steam to allow water - steam

distillation. The oil will be distilled and collected in 7 – 10 hours depending on the

Photo 17. Garlic. See color insert.

55 Garlic 217

garlic variety and the pressure of steam. The yield with Indian garlic will be 0.2 – 0.3%.

Some varieties of Chinese garlic have even higher yields.

Use of enzymes to break down structural tissues has led to an increase in the yield

of volatile oil. Cellulose, pectinase, and protease increased the yield during both steam

and water distillation (Sowbhagya et al. 2009 ). Crushed garlic is treated with aqueous

solutions of enzymes, pH - adjusted to 4.5 – 5.0 with aqueous citric acid, and incubated

at 50 ± 2 ° C for 90 minutes before distillation. The best result is obtained by pectinase

when the yield increased from 0.28% to 0.51%.

Garlic oil is yellowish - brown in color. It has a strong and pungent aroma which

may be disagreeable due to its high concentration; it must be suitably diluted when

used in food preparations. The constituents of the oil are about 60% diallyl disulﬁ de

and 20% diallyl trisulﬁ de, with traces of alliin and allicin. The characteristic aroma

of garlic may be derived from diallyl disulﬁ de.

Different varieties of garlic yield oils of different strength. Indian garlic is usually

much stronger than Chinese garlic. The oil can be 500 – 1000 times stronger in aroma

than fresh garlic .

According to the FCC, garlic oil occurs as a clear yellow to red - orange liquid

with a strong pungent odor and a ﬂ avor characteristic of garlic. It is soluble in most

ﬁ xed oils and in mineral oil. It is insoluble in glycerin, propylene glycol, and ethyl

alcohol.

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

Refractive index 1.550 – 1.580 at 20 ° C

Speciﬁ c gravity 1.050 – 1.095

The author ’ s lab has found no optical rotation for garlic oil but it can be given as

0 to + 1 ° .

Oleoresin

Both unroasted and roasted oleoresins are used in food ﬂ avoring. For the “ green ” or

unroasted oleoresin, the garlic is disintegrated and mixed with small quantity of water.

The aqueous juice is squeezed or drained out along with added water. This step can

be repeated once more with a small quantity of water. After this, the residue is

extracted with hexane. For this process, solvent is admitted from the bottom of the

vessel that contains the residue, and miscella is collected from the top at ambient

temperature. After two or three such extractions, the combined hexane miscella is

freed of the solvent to obtain an oily ﬂ avor concentrate with a yield of 0.2 – 0.3% on

raw material basis. This is then added to the water extract to obtain a green oleoresin

with satisfactory ﬂ avor characteristics. The yield of total water - soluble oleoresin will

depend on the quantity of water used, but for effective strength, it is best to limit the

total yield to 10 – 15%.

For roasted oleoresin, the garlic after disintegration is roasted at a temperature of

100 – 120 ° C for a short duration determined by the intensity of roasted aroma desired.

After cooling, the material is extracted with hexane. The solvent is removed from the

combined miscella to obtain a ﬂ avor concentrate with a yield as low as 0.1 – 0.2%.

218 Individual Flavors and Colorants

This is then suitably diluted with a ﬁ xed oil or mono - and diglyceride to obtain roasted

oleoresin.

Considerable variation in the manufacture of oleoresin is possible by combining

water extraction of the press - juice and hexane extraction of the nonpolar aroma con-

stituents and roasting to the desired level. Roasted hexane extract can also be blended

with water extract so that it becomes water - soluble. Addition of emulsiﬁ ers and dilu-

ents will not only reduce the cost per unit weight, but will also increase the conve-

nience of handling. Addition of some steam - distilled oil will improve the aroma but

the cost will also increase.

In recent years, a considerable amount of research on the chemical constituents of

garlic has been carried out, particularly in China. Organosulfur compounds in fresh

garlic are studied by using cold on - column injection and cold extraction under cryo-

genic conditions. The major compounds that exist before thermal degradation are

3 - vinyl - 4H - 1,2 - dithiin and 2 - vinyl - 4H - 1,3 - dithiin (Zheng et al. 2006 ). Various allyl

sulﬁ des, some previously known, have been studied in different conditions (Jirovetz

et al. 2001 ; Guo et al. 2005 ; Tian et al. 2005 ).

Extraction with supercritical carbon dioxide followed by analysis by GC - MS

reveals 16 compounds in garlic. They include diallyl disulﬁ de, 3 - ethenyl - 1,2 - dithia -

cyclohex - 5 - ene, 2 - ethenyl - 1,3 - dithio - cyclohex - 5 - ene, and diallyl trisulﬁ de (Zhang

et al. 2002 ). The oil volatiles obtained through supercritical extraction and steam distil-

lation have been compared: in supercritical extraction, 23 compounds were identiﬁ ed,

and by steam distillation, 21 are seen. The excesses in the former are 3 - methyl butyl -

allyl sulﬁ de and n - hexanal. The differences in the contents of constituents have been

discussed (Luo et al. 2008 ).

Uses

Garlic is a widely used ﬂ avor in savory foods. Extractives can be used in processed

foods such as soups, dressings, curries, and dry preparations.

Extracts of garlic are reported to inhibit platelet aggregation and to help lower

cholesterol level. They also show hypoglycemic effect and have antimicrobial effect

on fungi belonging to Aspergillus and Candida . These qualities can be exploited in

processed food. Consumption of garlic reduces the risk of cardiovascular disease and

cancer (Lin et al. 2000 ).

Garlic has a high sulfur content which makes it suitable for making skin, hair, and

nails supple and smooth. Garlic also has selenium, which, with an antioxidant such

as tocopherol, can arrest the aging process of tissues. Besides their antimicrobial

action, garlic extractives can also be an effective insect repellent (Singh 2009 ).

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Garlic oil 2503 8000 - 78 - 0 184.1317 –

Garlic oleoresin – 8000 - 78 - 0 184.1317 –

8008 - 99 - 9

55 Garlic 219

References

Abraham , K.O. ; Shankaranarayana , M.L. ; Raghavan , B. ; and Natarajan , C.P. 1976 . Alliums — varieties,

chemistry and analysis . Lebensm. - Wiss.Technol . 9 , 193 – 200 .

Choi , Mi Kyung ; Chae , Kyung - Yeon ; Lee , Joo - Young ; and Kyung , Kyu Hang . 2007 . Antimicrobial activity

of chemical substances derived from S - alk (en) yl - L - cysteine sulphoxide (alliin) in garlic, Allium sativum

L . Food Sci. Biotechnol. 16 ( 1 ), 1 – 7 .

Guo , Xiaofei ; Du , Ailing ; Guan , Congsheng ; Pan , Guangmin ; Du , Aiqin ; and Wang , Weiqiang . 2005 .

Analysis of volatile oil of garlic by gas chromatography – mass spectrometry Se Pu 23 ( 5 ), 548 – 550

(Chinese) ( Chem. Abstr. 144:288717).

Jirovetz , Leopold ; Ngassoum , Martin Benoit ; and Buchbauer , Gerhard . 2001 . Analysis of garlic ( Allium

sativum ) compounds using SPME - GC - FID, SPME - GC - MS and olfactometry . Recent Res. Dev. Agric.

Food Chem. 5 , 144 – 148 .

Li , Li - mei ; Wang , Rui - hai ; Chen , Lin ; Ding , Jia - xin ; and Zhang , Qiu - hai . 2006 . RP - HPLC analysis of diallyl

disulphide and diallyl trisulphide in garlic oil from Allium sativum . Zhongcaoyao 37 ( 9 ), 1345 – 1347

(Chinese) ( Chem. Abstr. 148:175989).

Lin , Alwin C. ; Salpietro , Salvatore, J. ; Deretey , Eugen ; and Csizmadia , Imre G. 2000 . Multidimensional

conformational analysis of methyl disulﬁ de: a key compound of garlic . Can. J. Chem. 78 ( 3 ),

362 – 382 .

Luo , Lan ; Liu , Jiajia ; and He , Shulan . 2008 . GC - MS comparative analysis of garlic volatile oil by different

extraction methods . Zhongchengyao 30 ( 1 ), 139 – 141 (Chinese) ( Chem. Abstr. 149:373888).

Singh , Soni Dharmendra . 2009 . Allium sativum L (garlic) in cosmetics . FAFAI J. 11 ( 4 ), 51 – 61 .

Sowbhagya , H.B. ; Kaul , T. Purnima ; Florence , Suma P. ; Appa Rao , A.G. ; and Srinivas , P. 2009 . Evaluation

of enzyme - assisted extraction on quality of garlic volatile oil . Food Chem. 113 , 1234 – 1238 .

Tian , Li ; Yang , Xiuwei ; Tao , Haiyan . 2005 . Analysis of volatile components of garlic ( Allium sativum L.)

by GC - MS . Tianran Chanwu Yanjiu Yu Kaifa , 17 ( 5 ), 533 – 538 .

Zhang , Zhongyi ; Lei , Zhengjie ; Wang , Peng ; and Wu , Huiqin . 2002 . Studies on chemical composition of

garlic by supercritical CO

ﬂ uid extraction and molecular distillation . Fenxi Ceshi Xuebao 21 ( 1 ), 65 – 67

(Chinese) ( Chem. Abstr. 137:75889).

Zheng , Ping ; Sheng , Xuan ; Ding , Yuansheng ; and Hu , Yanyun . 2006 . Study of organosulphur compounds

in fresh garlic by gas chromatography/mass spectrometry incorporated with temperature programmable

cold on - column injection . Se Pu 24 ( 4 ), 351 – 353 (Chinese) ( Chem. Abstr. 145:395785).

Introduction

Ginger was used in ancient India for its both culinary and medicinal properties. Its

beneﬁ ts in digestion and as a carminative have been recognized in Ayurvedic therapy.

The family to which ginger belongs, Zingiberaceae , has several shrubs including

turmeric and galangal. It is believed that many members of this group originated in

the tropical forests of Asia. Historical records show that ginger was popular in ancient

Greece and Rome, where it was supplied by Arab traders. It is believed that the ﬁ rst

gingerbread was made by a Greek baker in about 2500 BC. Romans distributed the

crop to different parts of their empire. Description of ginger is noted in the writings

of Confucius, the Chinese philosopher, and Dioscorides, the Greek medical expert.

Marco Polo also noted the beneﬁ cial effects of ginger during his travels in China. In

the ﬁ fteenth century, Vasco da Gama mentioned ginger in his account of his explora-

tion of the Kerala coast of India.

Ginger is cultivated throughout the world for culinary purposes, though some

countries process it as dry ginger. In earlier times, a large quantity of ginger was made

into dry ginger by being dipped in slaked lime solution. This was to control contami-

nation and especially infestation . With better drying conditions, storage systems, and

transportation, less and less “ lime ginger ” is made. Sun - dried ginger is the raw mate-

rial for extractions.

Plant Material

Ginger is produced by a perennial plant. It has a thin stem and reaches a height of

0.5 – 1 m. The leaves are narrow with a length of 15 – 20 cm and breadth of 1.5 – 2 cm

and with a green color. The midrib is somewhat prominent. Its ﬂ owers are greenish -

yellow in color, generally streaked with purple. Fruits are rarely formed, but when

formed, they are a triangular oval capsule bearing a large number of irregular and

dark - colored seeds. See Photo 18 .

The plant part of commercial interest is the rhizome, which grows under the soil

surface. It is thick - lobed, pale yellow, and of irregular shape and size. Several branches

of rhizome are referred to as ﬁ ngers. There are some secondary and occasionally

tertiary branches. The root proper grows from the side and underside of the rhizome.

Rhizomes have a typical spicy, aromatic ﬂ avor. Since the plant has to be pulled out

for harvesting of the rhizome, it must be planted each year like an annual.

Ginger

Zingiber ofﬁ cinale R ( Zingiberaceae )

221

Natural Food Flavors and Colorants Mathew Attokaran

Photo 18. (A) Ginger ﬁ eld. (B) Uprooted rhizome. (C) From bottom left clockwise:

peeled dry ginger, oleoresin ginger, two samples of ginger oil, and fresh ginger. See

color insert.

222

56 Ginger 223

Ginger is grown in different regions of varying geography and climate. This is

reﬂ ected in the characteristics of the ginger such as size, shape, amount of ﬁ ber, juici-

ness, and ﬂ avor. Countries that have excess process it in dry form. The major produc-

ers of dry ginger include India, China, Nigeria, Sierra Leone, and Jamaica. Until a

few years ago, Jamaican ginger was highly rated. Most of it was lime - treated. However,

the total quantity that is produced is so low that it is no longer considered an important

commercial variety of dry ginger. India ’ s Cochin ginger is now regarded as a top

variety. To facilitate sun drying, the ﬂ at sides of the rhizome are scraped with an iron

knife. It is a laborious process and the dry ginger obtained is called “ peeled ginger. ”

Nigerian ginger is also gaining in popularity. Here, the rhizome is cut longitudinally

to make two ﬂ at halves, which is known as “ split ginger. ”

Cochin ginger and Nigerian ginger are the most popular raw materials for oil and

oleoresin. China has ginger that is thicker and larger, but its ﬂ avor is generally con-

sidered inferior. However, because of its lower price and the possibility of production

in large quantities, it is gaining in importance. Australian ginger has an excellent

lemony ﬂ avor and so most of it is utilized in fresh condition to produce candied and

salted products useful in bakery, confectionery, and other products. Harvesting of this

type is also done a little early to obtain a good lemony note.

Chemistry

Dry ginger has about 8.6% protein, 6.4% fat, 5.9% ﬁ ber, minerals, water - soluble

vitamins, and vitamin A. While the aroma of ginger is very characteristic, it cannot

be attributed to any single compound as in some spices.

The main pungent components are a group of allied compounds known as gingerols

(Fig. 56.1 ). They are three homologues: 6 - gingerol, 8 - gingerol, and 10 - gingerol. Other

pungent compounds noted are shogaols, paradols, and zingerone. Connell and cowork-

ers have done pioneering work and have shown that shogaols, paradols, and zingerone

can be produced from true gingerols during storage and processing (Connell 1969 ;

Connell and Sutherland 1969 ). In a series of elegant work, they demonstrated the

possibility of converting gingerols into shogaols, paradols, and zingerone. Fresh

ginger will have more gingerol, while poorly processed and stored dry ginger will

have more shogaols and zingerone. A new component that has been identiﬁ ed in

Chinese ginger is zingiberolide (Peng et al. 2007 ).

Essential Oil

Considerable work has been carried out regarding the essential oil content of different

cultivars from different regions. On an average, dry ginger yields about 2% essential

Figure 56.1. 6 - Gingerol.

OCH

224 Individual Flavors and Colorants

oil. It has already been mentioned that the two commercial types that are used for

distillation are Cochin ginger from India and Nigerian ginger from Africa.

For commercial production of oil, ginger is coarsely ground using a hammer mill,

then ﬂ attened by passing through a roller mill. Steam is admitted at low pressure to

the ginger packed in a stainless steel still. Depending on the size of the batch, distil-

lation time can vary from 20 to 40 hours. In a tall still, steam distillation of volatiles

through a thick bed is time - consuming. Smaller batches require less time. However,

the great demand for this spice requires large batches and overnight distillation. On

an average, both peeled Cochin and split Nigerian gingers yield around 2% ginger oil.

Ginger oil is light yellow mobile liquid with a warm, spicy aroma. Several mono-

terpenes, sesquiterpenes, and oxygenated compounds have been reported (Govindarajan

1982 ). Zingiberene, β - bisabolene, and ar - curcumene can be considered to be major

constituents. Others that are present at signiﬁ cant levels are citrals, geraniol, 1,8 -

cineole, camphene, farnasene, sesquiphellandrene, and β - phellandrene. Detailed

studies have shown a large number of compounds, of which 83% are hydrocarbons,

10% oxygenated derivatives, and the rest unidentiﬁ ed (Lawrence 1984 ). A typical

examination of Cochin ginger oil by GC is presented in Table 56.1 . After many

attempts to determine the possible contribution of various constituents of ginger

aroma, it has been concluded that ginger aroma with a touch of pungency cannot be

explained by one or a few compounds. The characteristic aroma of ginger has to be

taken as a combined effect of most of its constituents.

Dry ginger and fresh ginger juice obtained on screw pressing have been analyzed

(Nirmala et al. 2007 ). Some minor constituents not previously reported have been

found by these authors. Lawrence (2008) has summarized a number of recent analyti-

cal studies. He emphasized rightly that pungent constituents such as gingerols and

shogaols, being nonvolatile, will not be present in the oil as reported by an investiga-

Table 56.1. GC analysis of cochin ginger oil

(Rajakumari region)

Constituent Area Percentage

α - Pinene 0.5 – 2.0

Camphene 3.0 – 6.0

β - Pinene < 1.0

Myrcene < 1.0

Limonene 2.0 – 4.0

Cineole < 0.5

Linalool 0.5 – 1.50

Camphor < 0.5

Geraniol < 1.0

Citral 0.5 – 1.50

Zingeberene 35.0 – 42.0

β - Bisaboline 3.0 – 8.0

Curcumene 2.0 – 6.0

β - Sesquiphellandrene 14.0 – 17.0

Column Innowax; carrier gas N

; ﬂ ame ionization detector

(FID); temperature 80 – 220 ° C.

56 Ginger 225

tor. Those who would like to learn the details of the composition of ginger oil are

advised to refer to the review.

According to the FCC, ginger oil is a light yellow to yellow liquid with the aroma

characteristic of ginger. It is soluble in most ﬁ xed oils and in mineral oil. It is soluble,

usually with turbidity, in alcohol but is insoluble in glycerin and in propylene glycol.

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

Optical rotation − 28 to − 47 °

Refractive index 1.488 – 1.494 at 20 ° C

Speciﬁ c gravity 0.870 – 0.882

Oleoresin

Oleoresin can be made either through direct extraction or by extracting deoiled mate-

rial and blending the resin obtained with the required amount of ginger oil obtained

earlier by steam distillation. Both acetone and ethylene dichloride are good

solvents.

By direct extraction with acetone, Cochin ginger yields about 5 – 6% oleoresin.

When Nigerian ginger is used, the yield is 6 – 7%. In the export market, there is speciﬁ c

requirement for both. The popular grade of oleoresin has 25 – 28% v/w of volatile oil

content. Under normal circumstances, Nigerian ginger will have a slightly lower price

than Cochin ginger, mainly because of slight increase in yield of oleoresin.

Ginger oleoresin is a dark brown viscous product with the characteristic odor

of ginger and the typical hot taste. By two - stage extraction, the volatile content

can be adjusted to the wide range of 5 – 40%. The price will be dependent on the oil

content.

For special pharmaceutical uses, there is demand for high gingerol content and low

shogaol content. Heating during processing increases conversion of gingerol to

shogaols. In such cases, processing is carried out at temperatures below 70 ° C. A

typical analysis of ginger for such purposes will give the value for true gingerols above

20% and shogaols below 6%.

As in some other spices, in ginger there is scope for making an absolute. This is

carried out by dissolving oleoresin in 95% ethanol and ﬁ ltering out insolubles. Alcohol -

soluble ginger oleoresin is necessary in soft drinks and alcoholic beverages to prevent

the formation of turbidity.

Analytical Methods

Total gingerols can be determined using HPLC separation and adding up the values

of all the pungent constituents such as gingerol, shogoals, and zingerone. Paradols

will usually be very low. Capsaicin is used as the standard.

Generally, gingerol content is not speciﬁ ed. But for special use in medical prepara-

tion, gingerols and shogaols may have to be estimated separately. HPLC separation

is carried out using C

column with mobile phase of mixture of acetonitrile (55%),

dilute aqueous 0.1% phosphoric acid (44%), and methanol (1%). UV detection is at

282 nm.