Attokaran M. Natural Food Flavors and Colorants

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86 Individual Flavors and Colorants

Besides the usual terpene compounds, oil contains nigellone, which has property

to relieve bronchial spasm in guinea pigs. The extract of the oil contains thymoqui-

none, believed to prevent cancer cell growth. Many physiologically active components

such as nigellicine, nigellidine, dithymoquinone, and thymohydroquinone, besides

nigellone and thymoquinone, have been reported (Randhawa 2008 ). These account

for the spice ’ s many medicinal properties including anticancer action and immune

stimulation. Two samples from Sahara desert regions on hydrodistillation followed by

detailed analysis give p - cymene 8.9% and 7.2%, 4 - terpineol 0.6% and 8.9%, thymo-

hydroquinone 6.1% and 12.2%, thymoquinone 1.6% and 21.8%, carvacrol 12.9% and

12.9%, carvone 4.4% and 0.3%, and thymol 1.5% and 0.7% (Benkaci - Ali et al. 2007 ).

From the southern region of Algeria, most of the above have been noticed in slightly

different proportions. But in addition, sabinene, trans - sabinene, hydrate, γ - terpinene,

longifolene, and α - longipinene have also been noted (Benkaci - Ali et al. 2005 ).

Uses

Because of its pungent bitter taste and smell, black cumin and its oil are used in con-

fectionery and liquors. It has great potential in medicinal preparation. In fact, it is

surprising that the oil and seeds are so little used in food ﬂ avoring. Perhaps the use

will increase once its beneﬁ cial properties are better understood.

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Black cumin seed oil 2337 90064 - 32 - 7 182.10 –

References

Benkaci - Ali , F ; Baaliouamer , A ; and Meklati , B.Y. 2005 . Comparative study of the chemical composition

of Nigella sativa L from the Media region extracted by hydrodistillation and microwave . Rivista Italiana

Eppos 40 , 15 – 24 (French) ( Chem. Abstr. 145 :33598).

Benkaci - Ali , F ; Baaliouamer , A. ; Meklati , B.Y. ; and Chemat , Farid . 2007 . Chemical composition of seed

essential oils from Algerian Nigella sativa extracted by microwave and hydrodistillation . Flavour

Fragrance J . 22 ( 2 ), 148 – 153 .

Cheikh - Rouhou , Salma ; Besbes , Souhail ; Hentati , Basma ; Blecker , Christophe ; Deroanne , Claude ; and

Attia , Hamadi . 2007 . Nigella sativa L. Chemical composition and physiochemical characteristics of lipid

fraction . Food Chem. 101 ( 2 ), 673 – 681 .

Pruthi , J.S. 1976 . Spices and Condiments . Delhi : National Book Trust , pp. 106 – 108 .

Randhawa , Mohammed Akram . 2008 . Black seed, Nigella sativa , deserves more attention (Editorial) .

J. Ayub Med. Coll. Abbottabad 20 ( 2 ), 1 – 2 .

Warrier , P.K. 1995 . Indian Medicinal Plants Orient . Madras : Longman , vol. 4 , pp. 139 – 141 .

Introduction

Spices have always evoked thoughts of exotic places in the minds of Western people.

Among the spices, it was black pepper that gained the most attention. The conquest

of Egypt and the Indus region of India by Alexander the Great made pepper and other

spices of the Orient well known in Mediterranean countries even before Christ. In the

ﬁ rst century AD, direct sea routes were established between Europe and Egypt, which

was a distribution center for pepper. The lure of pepper and other spices of the East

was so great that toward end of the ﬁ fteenth century, many daring sea expeditions

were undertaken mainly to establish a direct sea route between the lands of spices,

such as India and the East Indies, and Europe. These included the expeditions of

Columbus and Vasco da Gama. The colonization of the East by European powers

made the ﬂ ow of black pepper to Europe easy. It is believed that black pepper was

used both for preservation of meat during winter and for masking off - ﬂ avor formed

due to long storage.

Plant Material

Black pepper is produced by a perennial climber, which has a woody stem. It needs

support which the plant attaches itself using adventitious roots from joints. It has dark

green ovate leaves that are somewhat thick. The climber reaches a height of 5 – 8 m.

Flowers are minute. Fruits are grown on a central stalk into an elongated bunch, known

as a spike. Each fruit will be dark green and spherical with an average diameter of

4 mm. On drying of the fruit, popularly known as a berry, but botanically a drupe,

black pepper is formed. On ripening, the berries turn yellow and red. Photo 3 shows

pepper vine and white and black pepper.

Pepper grows well in humid, warm weather such as found in areas near the equator.

Rainfall of 1500 mm or above is needed. Temperatures below 10 ° C are not good for

the plant. Propagation of pepper is done vegetatively from cuttings. Small plants

are generally grown in nurseries for 3 – 4 months before they are transplanted to the

desired place.

India, Indonesia, Brazil, and Malaysia are the major traditional growers. A recent

entrant to pepper production is Vietnam, which has attained the position of top

exporter. Unlike in India, they do not have a substantial internal market. Sri Lanka is

a producer of extraction - grade pepper with high level of piperine, the constituent

responsible for hotness. Cambodia and Madagascar also produce black pepper. By

Black Pepper

Piper nigrum L ( Piperaceae )

Natural Food Flavors and Colorants Mathew Attokaran

Photo 3. (A) Pepper vine with pepper berries as spikes. (B) White pepper. (C) Dried

black pepper. See color insert.

24 Black Pepper 89

harvesting at a slightly immature stage, a higher piperine content is obtained. The

piperine content of extraction - grade immature pepper, popularly known as “ light

berries, ” will be in the upper range with Sri Lankan material showing 9 – 11%. Light

berries from other major producers show piperine content of 8 – 9% (India) and 7 – 8%

(Indonesia and Vietnam).

Chemistry

Piperine is the most signiﬁ cant constituent of dry black pepper and is present to the

level of 4 – 6% (Fig. 24.1 ). At the immature stage, piperine content may be up to 10%.

It, along with its isomers, contributes to the hotness. There are two points of cis – trans

isomerism. Piperine, which is trans – trans , is the most pungent. This is followed in

hotness by chavicine ( cis – cis ), isopiperine ( cis – trans ), and isochavicine ( trans – cis )

(Govindarajan 1977 ).

Starch is the major constituent, accounting for 40% in black and over 50% in white

pepper. While starch is mainly in the core, crude ﬁ ber is in the skin. The amount of

protein has not been investigated, probably because it is not a signiﬁ cant source,

particularly since only a very low quantity of pepper is consumed. Piperine accounts

for most of the nitrogen in pepper. The volatile oil content of dry pepper is about 4%.

As the maturity increases, piperine and the volatile oil content decrease, mainly

because of dilution by fast formation of starch and crude ﬁ ber (Table 24.1 )

(Sumathykutty et al. 1979 ).

The outer skin has essential oil in the inner portion. It also has polyphenols, which

by phenolase - induced oxidation, are converted into dark - colored compounds. This is

Figure 24.1. Piperine.

Table 24.1. Changes in chemical composition of pepper at different stages of maturity

Maturity Stage Moisture

Content

(%) (Wet)

Average

Berry

wt. mg

Content on Moisture Free Basis (%)

Vol. Oil

v/w

Piperine

w/w

Crude

Fiber w/w

Starch

w/w

Pinhead size 82.5 4 2.0 0.4 18.0 15.3

Between pinhead and immature 77.5 15 2.0 1.9 14.7 18.5

Immature (light berries) 75.0 25 4.8 6.8 13.0 38.4

Under mature 65.0 53 4.4 6.2 11.8 38.4

Mature 60.0 62 3.7 4.2 10.5 40.9

Ripening 40.5 78 2.2 4.0 8.7 46.2

90 Individual Flavors and Colorants

the reason for change of the green color of mature pepper (due to chlorophyll) to black

on drying. The inner core is rich in starch and piperine.

The use of speciﬁ c color reagent on microtome sections followed by microscopy

has given an insight into the localization of many signiﬁ cant constituents. In the

pinhead stage of pepper berries, piperine could not be located. However, estimation

showed some piperine. From the immature stage onward, however, piperine cells

could be located in the endocarp alone. The number of cells increased gradually, and

at maturation, there was a considerable increase in piperine - containing cells. The size

of piperine cell varied from 60 to 65 μ m. Again by histochemical method, piperine

could not be located in the skin; however, estimation showed 7 – 8% of total piperine

in the skin but more than 90% was in the inner core (Mangalakumari et al. 1983 ). A

cross section of a pepper berry is presented in Fig. 24.2 .

Scanning electron microscopy has shown that the essential oil is stored in

comparatively large and thin - walled cells, with size ranging from 50 to 55 μ m.

Essential oil cells were mainly in the inner portion of the skin. In the inner core, the

distribution was restricted to the tip (i.e., stigmatic end) and where the embryo was

situated.

Histochemical studies using phenolic reagents showed that polyphenols are present

in the epicarp and mesocarp. The pattern of blackening of the pepper on drying coin-

cides with the distribution of polyphenols. The substrate is identiﬁ ed as 3,4 - dihydroxy -

6 - ( N - ethyl amino) benzamide (Bandyopadhyay et al. 1990 ). It is a case of enzymatic

browning wherein the enzyme phenolase is contributed by the spores of the fungus

Glomerella cingulata , which is invariably present in the berries (Mangalakumari

et al. 1983 ).

Figure 24.2. Cross section of pepper.

24 Black Pepper 91

White and Green Pepper

If the ﬁ brous outer skin is removed from berries by retting and abrasion, especially

when they are ripe or overmature, the hard core emerges as white pepper. White pepper

has a typical putrid smell in addition to a hot taste. Steaming of green pepper or black

pepper followed by efﬁ cient abrasion peeling using a mechanical pulper is suggested

as a quick method. However, the absence of the slightly putrid note from retting is

seen as a disadvantage.

At a very immature stage, pepper has a special “ green ” ﬂ avor, which is retained

by inhibiting enzyme action to produce products such as green pepper in brine, dehy-

drated green pepper, and canned green pepper. The method employed in retaining the

green color is inactivation of the phenolase enzyme. In dehydrated green pepper and

canned green pepper, heat inactivation does this. In pepper in brine, continued steeping

in acidiﬁ ed brine inactivates the enzyme.

Essential Oil

Dried black pepper is made into ﬂ akes by roller grinding. On steam distillation of this,

pepper oil can be obtained with a yield of 2 – 4%. It is customary to obtain it in two

fractions, so that the second fraction will have more of the heavier compounds such

as caryophyllene and less of monoterpene hydrocarbons such as pinenes and limonene.

The second fraction, therefore, will have a desirable mellow aroma, whereas the ﬁ rst

fraction will have a harsher note due to the higher content of monoterpene hydrocar-

bons. The ﬁ rst fraction is used for blending in oleoresin and the second as salable

pepper oil.

Major constituents of pepper oil are α - and β - pinene, sabinene, limonene, δ - careen,

α - phellandrene, and β - caryophyllene (Govindarajan 1977 ). GC - MS study has shown

39 terpene compounds, which account for 99.51% of volatile oil. trans - Caryophyllene

is the major constituent (Dong and Pan 2007 ).

According to the FCC, black pepper oil occurs as an almost colorless to slightly

green liquid with characteristic odor of black pepper. It is soluble in most ﬁ xed oil

and in propylene glycol but sparingly soluble in glycerin.

Physical characteristics of black pepper as deﬁ ned by the FCC are as follows.

Optical rotation − 1 ° to − 23 °

Refractive index 1.479 – 1.488 at 20 ° C

Speciﬁ c gravity 0.864 – 0.884

Solubility in alcohol 1 mL in 3 mL of 95% alcohol

Oleoresin

When ﬂ attened, black pepper is extracted with solvents such as ethylene dichloride,

a mixture of acetone and hexane, or ethyl acetate; miscella contains both aroma and

pungent fractions. On removal of solvent, oleoresin is obtained. In recent years, it has

become customary to produce oleoresin by a two - stage operation. As explained earlier,

oil is distilled off as the ﬁ rst step. The deoiled pepper is freed of moisture and extracted

92 Individual Flavors and Colorants

with solvent. The resin rich in piperine will emerge on desolventization. This is then

blended with pepper oil, usually the ﬁ rst fraction, so that the mellow - ﬂ avored second

fraction can be sold as high - quality pepper oil.

Most international quality standards specify a solvent residue of less than 30 ppm.

This level is obtained by use of open steam, efﬁ cient stirring during evaporation, and

vacuum.

Black pepper oleoresin is generally sold in the speciﬁ cation of 40 : 20, which means

40% piperine and 20% volatile oil. Oleoresins with lower or higher content of either

constituent are also traded. For use in light - colored products, decolorized oleoresin is

made by using carbon as adsorbent. For special ﬂ avors, both oil and oleoresin are

prepared from white pepper and green pepper. A new product that has emerged

recently is 95% piperine in crystal form. This is obtained by repeated crystallization

from piperine - rich resin obtained from deoiled pepper, which is rich in piperine.

Piperine is used as a bioactive material as it aids in better absorption of other drugs

taken along with it. Piperine is the major hot component of oleoresin.

Method of Testing

Piperine determination is by UV spectrophotometric reading at 342 – 345 nm (ASTA,

AOAC ). The pure standard is supplied by Sigma - Aldrich Chemical Company.

Uses

Black pepper is one of the most well - liked spice ﬂ avors in the world. No savory

preparation can go without black pepper. It is used in meats, seafood, vegetable prepa-

rations, snacks, soups, sauces, and salad dressing. Pepper powder is sprinkled on egg

preparations, salads, and cheese.

Pepper oil is used in food as a ﬂ avor when aroma and not hotness is valued. A

small quantity is used as fragrance material, especially in men ’ s cosmetics. Pepper oil

is believed to give an oriental note to perfumes.

When both aroma and taste are required, oleoresin black pepper should be used. It

is widely used in processed foods of meat, seafood, vegetables, snacks, and soups.

Piperine crystals with 95% purity are used as a bioactive agent, which helps the body

to absorb other drugs taken along with it.

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Pepper oil (black) 2845 8006 - 82 - 4 182.20 –

84929 - 41 - 9

Pepper oil (white) 2851 8006 - 82 - 4 182.20 –

Pepper oleoresin (black) 2846 84929 - 41 - 9 182.20 –

Pepper oleoresin (white) 2852 84929 - 41 - 9 182.20 –

24 Black Pepper 93

References

Bandyopadhyay , Chiranjib ; Narayan , Vaduvatha S. ; and Variyar , Prasad S. 1990 . Phenolics in green pepper

berries ( Piper nigrum L) . J. Agric. Food Chem . 38 , 1696 – 1699 .

Dong , Dong ; and Pan , Shengli . 2007 . Analysis of chemical constituents of volatile oils from Piper laetispi-

cum and Piper nigrum by GC - MS . Zhongguo Zhongyao Zazhi 32 ( 7 ), 647 – 650 (Chinese) ( Chem. Abstr.

149 :252615).

Govindarajan , V.S. 1977 . Pepper - chemistry, technology and quality evaluation . CRC Crit. Rev. Food Sci.

Nutr . 9 , 115 – 225 .

Mangalakumari , C.K. ; Sreedharan , V.P. ; and Mathew , A.G. 1983 . Studies on blackening of pepper ( Piper

nigrum L), during dehydration . J. Food Sci. (IFT) 48 ( 2 ), 604 – 606 .

Sumathykutty , M.A. ; Rajaraman , K. ; Sankarikutty , B. ; and Mathew , A.G. 1979 . Chemical composition of

pepper grades and products . J. Food Sci. Technol. 16 , 249 – 252 .

Introduction

Capsicum, or chili, is sometimes referred to as cayenne pepper or red pepper. It has

a very hot taste or pungency. Asians in general and Indians in particular love this hot

taste, and their food contains a fair amount of this spice. But about 500 years ago, it

was not available in the Old World. Chili is thus a gift from the New World, as are

tobacco, cassava, sapota, rubber, and cashew nuts.

Spanish explorers discovered this crop in South and Central America and the

Caribbean islands. From there, it was transplanted to Europe where in the cold

weather, less pungent varieties thrived. The Portuguese introduced chili to India,

where only the hot variety thrived and became a favorite food seasoning.

Chili is probably a native of Mexico from where it spread to the rest of Latin

America. Use of this hot spice in Mexico is recorded as early as 7000 BC. There is

historical evidence of the Aztecs having used this spice. It was also used in the

Caribbean islands both for food ﬂ avoring and as a medicine. The specialists who

accompanied Columbus ’ s expedition made important observations about the plant and

its usage in food and medicines.

Because of differences in agro - climatic conditions and natural hybridization, chilis

differing in size, shape, color, and intensity of hotness appeared. Chili or red pepper

is one of the most colorful spices. The presence of whole dried red chili in a prepared

dish and fresh green chili in salads has great display value. (See Photo 4 .)

Plant Material

Chili is an annual plant, attaining a height of 0.5 – 1.4 m and has a branched stem. The

ﬂ ower is white in color and bears a single fruit, which is the chili. It is green before

ripening, but changes to red on ripening. The intensity and color vary with cultivars.

Exotic varieties have white, yellow, purple, and orange colors, but they do not form

raw material for extractives (Govindarajan 1985 ).

Commercially signiﬁ cant chilis are red in color. There are rows of seeds inside,

attached to a sheath - like dissepiment (Fig. 25.1 ). While seeds come free of hotness,

dissepiment is rich in capsaicin, the chemical constituent that causes hot taste.

Separated seeds usually contain small pieces of dissepiment, giving an impression

that seeds are indeed hot. Pericarp contains most of the color and capsaicin. The

Capsicum

Capsicum annuum L; C. frutescens L ( Solanaceae )

Natural Food Flavors and Colorants Mathew Attokaran