Attokaran M. Natural Food Flavors and Colorants

Подождите немного. Документ загружается.

296 Individual Flavors and Colorants

Extraction

The dry meal is extracted with hexane. The successive miscella in the case of batch

extraction is combined and solvent distilled off without raising the temperature much

above the boiling point of hexane. When large quantities are involved, extraction is

carried out using a continuously operating moving chain. The meal will move in one

direction and the solvent with progressive enrichment moves in the opposite direction.

The extract is a dark brown pasty liquid. It will have a mild odor of marigold and the

typical putrid smell due to retting during silage operation. The product becomes loose

when warmed to 50 – 60 ° C.

The yield of the extract is about 8 – 10% of the dry meal. The product will have

80 – 120 g/kg of xanthophylls. The residual solvent is below 3000 ppm.

Because of its putrid smell, the product is useful only for chicken feed. Vacuum

distillation results in low residual solvent and some deodorization, but the product is

still not suitable for food use. There is a need for standardization of a process involv-

ing disintegration of ﬂ owers, careful partial drying, and extraction with a mixture of

hexane and acetone to get pigment from the cells. Some exploratory trials have shown

some promise of creating a product with satisfactory ﬂ avor.

Uses

Marigold extract rich in lutein has a bright yellow - orange color that is useful in a wide

range of food products. Presence of lutein is also valuable as a nutraceutical. The color

maintains stability during heat processing. For use in food, many standardized forms

such as oil - soluble, water - dispersible, spray - dried, and plated on solid matrix are

manufactured. These are used in mayonnaise, dairy products, confectionery, and baked

items to take advantage of its yellow - orange color.

However, the ﬁ ne color has not been fully exploited as a natural food colorant

(Sowbhagya et al. 2004 ). Most of the marigold extract now produced is made for use

in chicken feed, because of the intense off - ﬂ avor as a result of the silage process. It

is the belief of the author that if extracts are made by careful drying and extraction

with an appropriate solvent system, the use of this natural color will be more widely

used in food preparations.

Lutein present in the extract is a valuable nutraceutical. The macular region of the

retina is vulnerable to age - related degradation. Lutein, which cannot be synthesized

by humans and therefore has to be taken with food, is extremely important for the

health of the eye. Lutein is an antioxidant capable of protecting the macular region of

the retina from peroxidative damage. Generally, commercial preparations will also

contain zeaxanthin and cryptoxanthin.

Marigold extract is widely used in chicken feed to help color the yolks yellow. For

standardization of the yellow - orange shade of the yolk, a tremendous amount of

saponiﬁ ed marigold extract is used.

Analytical Method

Xanthophylls are estimated by the AOAC method. Here, xanthophylls are extracted

by a mixed solvent and absorbance is measured in a spectrophotometer at 474 nm.

75 Marigold 297

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Marigold absolute – 8016 - 84 - 0 – –

91770 - 75 - 1

Lutein – – – 161b

References

Antony , J.I.X. ; and Shankaranarayana , M.L. 2001 . Lutein . World of Food Ingredients , April – May, pp.

64 – 70 .

Sowbhagya , H.B. ; Sampathu , S.R. ; and Krishnamurthy , N. 2004 . Natural colorant from marigold – – chem-

istry and technology . Food Rev. Int. 20 ( 1 ), 33 – 50 .

Introduction

Marjoram, also called sweet marjoram, is a cold - sensitive perennial herb or under-

shrub with a ﬁ ne aroma. Oregano is sometimes referred to as wild marjoram, but it is

a different herb; marjoram belongs to the mint family. For a long time, marjoram was

known as Origanum marjorana , though presently the botanical name Marjorana

hortensis is used. Although it is a perennial, it is cultivated as an annual.

In Rome, a newly married couple is crowned with marjoram. It is a symbol of

honor in Crete. In Greek, the name of marjoram means joy of the mountains and the

plant represents happiness. In Sicily, it is believed to have the property of removing

unhappiness.

Plant Material

Marjoram is an erect plant which grows close to the ground and rarely has a height

over 30 cm. It is bushy, with grayish - green, oval, hairy leaves. It has groups of ﬂ owers

in knot - like formations. The dried leaves and ﬂ oral parts, after ﬁ eld drying, form the

herb that is used as a spice and for making extractives. It has a sweet and spicy aroma

and a bitter and camphoraceous taste and ﬂ avor.

The plant is cultivated in the European countries of France, Germany, the United

Kingdom, Hungary, Italy, Spain, and Portugal; North African countries of Morocco

and Tunisia; and some countries of South and Central America.

Marjoram leaves on dry basis have over 60% carbohydrates, 7% fat, 13% protein,

18% ﬁ ber, and minerals and vitamins. However, the most signiﬁ cant constituent is the

essential oil that is responsible for its aroma and ﬂ avor.

Essential Oil

Dry marjoram leaves yield around 1% of volatile oil. The major component of the oil

is its sabinene derivatives, which are bicyclic (Novak et al. 2008 ). GC - MS study of

oil from Albania shows 28 volatiles (Jirovetz et al. 2008 ). Terpinen - 4 - ol accounts for

14%, α - terpinene 9%, and sabinene 8%. From the oil produced in Egypt, 30 major

and minor compounds are detected. Terpinen - 4 - ol, linalool, γ - terpinene, α - terpinene,

and sabinene are the major components (El - Nakeeb et al. 2006 ).

Sweet marjoram oil, according to the FCC, is a yellow or greenish - yellow oil with

a warm, fragrant, and spicy note resembling cardamom and lavender. Its taste is sharp

Marjoram

Marjorana hortensis M ( Labiatae )

299

Natural Food Flavors and Colorants Mathew Attokaran

300 Individual Flavors and Colorants

and slightly bitter. It is soluble in most ﬁ xed oils and in mineral oil. It is only partially

soluble in propylene glycol and it is insoluble in glycerin.

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

Optical rotation + 14 to + 24 °

Refractive index 1.470 – 1.475 at 20 ° C

Speciﬁ c gravity 0.890 – 0.906

Solubility 1 mL dissolves in 2 mL of 80% alcohol

Oleoresin

Well - powdered, dried leaves, when extracted with hexane, give an oleoresin with a

yield of 1.5 – 2%. Depending on the quality of leaves, the volatile oil content of oleo-

resin will be between 12 and 20% v/w.

It is a dark greenish - brown, somewhat pasty product with a typical thyme/minty

aroma and ﬂ avor. It is miscible with ﬁ xed oil. Dilution with vegetable oil or any other

diluent will make it easier to use. It is partially soluble in propylene glycol and

insoluble in glycerin. The ﬂ avor of marjoram is deceptively potent and care is needed

to avoid adding an excessive amount to food. Therefore, the more balanced ﬂ avor of

the oleoresin is preferred.

Uses

Marjoram oil can be used as a ﬂ avor in liquor, liqueurs, sauces, and condiments. Both

the oil and oleoresin can be used in various meat preparations such as sausages,

chicken preparations, and special soups. The oil ﬁ nds use as a fragrance in soaps and

perfumes.

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Marjoram oil sweet 2663 8015 - 01 - 8 182.20 –

84082 - 58 - 6

Marjoram extract/oleoresin 2659 84082 - 58 - 6 182.20 –

References

El - Nakeeb , M.A. ; Fathy , S.M.F. ; and Salma , O.M. 2006 . GC - MS analysis, biostatic activities and biocidal

dynamics of the essential oil of Origanum marjorana cultivated in Egypt . Alex. J. Pharm. Sci. 20 ( 2 ),

150 – 156 ( Chem. Abstr. 147 :207647).

Jirovetz , L. ; Bail , S. ; Buchbauer , G. ; Denkova , Z. ; Slavchev , A. ; Stoyanova , A ; and Schmidt , E. 2008 .

Chemical composition, antimicrobial activities and olfactory evaluations of an essential marjoram oil

from Albania as well as some target compounds . Ernaehrung 32 ( 5 ), 97 – 201 .

Novak , J. ; Lukas , B. ; and Franz , C.M. 2008 . The essential oil composition of wild growing sweet marjorana

from Cyprus - 3 chromotypes . J. Essent. Oil Res. 20 ( 4 ), 339 – 341 .

Introduction

Long before the West started using mustard, the Chinese used it as a seasoning for

food. In Europe, it is used as a condiment for salted meat. Many strongly ﬂ avored

spices were used in winter not only for preserving meat, but also to mask off - ﬂ avor

due to spoilage. Some were believed to be useful for protecting the digestive system.

Ancient Greeks used mustard as seasoning for their meat and ﬁ sh. Ancient Romans

mixed the spice with grape juice, known at that time as “ must, ” to make what is known

as “ must ardens ” translated as “ burning must ” ; from this the name “ mustard ” probably

originated.

It is possible that Roman soldiers brought the spice to England where it became a

valuable ingredient of seasoning. The two main grades are English and French mustard.

All over the world, sulfur - containing ﬂ avors have been appreciated in specialty foods

to give a wasabi - like pungency. Mustard is also an important oilseed and, along with

rapeseed, is a major source of ﬁ xed oil. The low erucic acid variety of rapeseed, called

canola oil, makes it one of the major fatty oils. Because of this use, mustard along

with rapeseed became a major crop of the world. This also helped in the spread of

mustard ﬂ avor to all parts of the globe.

Plant Material

Black mustard ( Brassica nigra ) and brown mustard ( Brassica juncea ) are generally

grouped together and called black mustard. The tiny fruits are pressed to the inﬂ ores-

cence axis. The seed coat shows minute reticulation and adheres to mucilaginous

material. The outer skin is covered with a thin cuticle. The spice is cultivated in

Europe, although recently there has been a switch over to the white variety.

The light - colored mustard, referred to as white or yellow mustard ( Brassica hirta

or Brassica alba ) grows on a plant with a hairy stem. The leaves are irregularly pinnate

and the ﬂ owers are spreading and yellow. The hairy pods have empty, knife - like beaks

and contain relatively large and pitted seeds. There is a good deal of mucilaginous

material. The mustard plant and dried mustard are presented in Photo 22 .

Mustard

Brassica alba L, B. nigra K, and B. juncea L

(Cruciforae)

301

Natural Food Flavors and Colorants Mathew Attokaran

Photo 22. (A) Mustard in bloom. (B) Dried yellow mustard. See color insert.

302

77 Mustard 303

Chemistry

Mustard seeds are a source of ﬁ xed oil and about 30% of the dry seed consists naturally

of triglycerides. The seeds are an excellent source of protein which is present in levels

of 25 – 30%. It has about 10% crude ﬁ ber and minerals.

Black mustard contains allyl glucosinolate, popularly called sinigrin. When the

mustard is crushed, the enzyme myrosinase present in it degrades sinigrin, in the pres-

ence of water, to allyl isothiocyanate (AITC) (Fig. 77.1 ). AITC has a boiling point of

151 – 153 ° C, a speciﬁ c gravity of 1.0175, and solubility of 2 g in 1 L of water at 20 ° C.

White mustard, on the other hand, contains the glucosinolate known as sinalbin.

This, in the presence of water, is acted on by myrosinase to produce 4 - hydroxy

benzyl isothiocyanate, which has a half - life of a little over 1 hour. This pungent mate-

rial degrades into 4 - hydroxy benzyl alcohol and thiocyanate ion, which are only

weakly pungent. Another related glucosinolate, glucobrassicin, when in contact with

water and enzyme, also yields a nonpungent isothiocyanate.

Essential Oil

The essential oil of mustard is formed only after the action of the enzyme myrosinase

on the right variety of mustard. Black mustard ( B. nigra ) or brown mustard ( B. juncea ),

which contains sinigrin, is a suitable raw material. It is ﬁ rst expelled to remove all the

ﬁ xed oil. The cake obtained is then treated with water so that the enzyme can act to

produce AITC with a small amount of butenyl isothiocyanate. The proportion of cake

to water is maintained at 16.5:83.5.

This slurry is then transferred to a steam distillation unit ﬁ tted with stirrer and

steam jacket. The slurry is preheated to about 60 ° C for 1 hour and then open steam is

admitted so that steam - water distillation takes place. The mixture of oil and water is

collected by means of a water - cooled condenser in a closed receiver arrangement for

heavier - than - water oil. The mustard oil, which is mainly AITC, is removed. The yield

of the oil is only 0.3 – 0.4%.

The oil generally contains 85% allyl and 10% butenyl isothiocyanate. The speciﬁ c

gravity is over 1. The oil from some types of white mustard is 80% butenyl isothio-

cyanate and 12% AITC. This may have a lower speciﬁ c gravity and lower refractive

index than the product from black mustard.

Recent development has shown that the spinning cone column (SCC) method,

which was developed for aroma recovery from fruit pulp, can be effectively used to

separate isothiocyanate - rich essential oil from mustard. All the other operations except

distillation are similar. The SCC is a vertical stainless steel cylinder with a central

rotating shaft. To facilitate intimate contact, there are two sets of inverted cones. One

set is attached to the inside wall of the column and another to the central shaft. The

Figure 77.1. Allyl isothiocyanate.

304 Individual Flavors and Colorants

cones attached to the shaft rotate with the shaft while those on the wall are ﬁ xed in

such a fashion that they are alternate with one another.

The slurry is made to ﬂ ow from the top to bottom, and stripping steam ﬂ ows from

the bottom to the top. As the steam passes over the thin layer of slurry, it picks up

volatiles and is led to the condenser. Volatile - free slurry ﬂ ows down and can be

collected.

From the condenser, a mixture of volatile oil and water are sent through a series

of separators. Oil, being heavier, collects at the bottom. Since the oil is very expensive

and yield is low, generally, during the last separation, the entire volume of water is

kept overnight so that every droplet of volatile oil settles before the water is

discarded.

The yield of volatile oil from condensation is better than that from conventional

distillation. A new variety of Canadian yellow mustard is believed to be richer in

AITC, and with this the yield can be 0.8 – 1%. Against this, one has to consider the

high capital investment needed.

Mustard oil is highly volatile, pungent, and therefore hazardous. It needs special

packaging such as aluminum bottles, placed inside a mild steel jacket, protected inside

a dealwood box. The operation creates polluted water, which then needs special treat-

ment. There are reports of workers affected by discomfort and illness in the traditional

method of manufacturing.

Mustard oil, according to the FCC, is a pale yellow liquid with a sharp, pungent

odor and taste. It does not have angular rotation. Good quality oil requires over

93% AITC.

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

Refractive index 1.524 – 1.534 at 20 ° C

Speciﬁ c gravity 1.008 – 1.019

Oleoresin

There is very little oleoresin manufacture of mustard oil. Some sporadic but unsys-

tematic efforts have been made. It is not clear whether the preliminary step of expel-

ling and treatment with water to activate the enzyme must be carried out before

extraction is performed. If it were possible, it would have resulted in a process that is

simple, inexpensive, and relatively safe. But extraction with organic solvent can be

tricky when so much water is present in the slurry.

The saturated and unsaturated fatty acid composition can be analyzed using GC - MS

(Liu et al. 2001 ). The lysine content of Brassica napus and B. juncea is analyzed

employing near IR reﬂ ectance spectroscopy (Gan et al . 2005 ).

Uses

Mustard oil is used in mustard paste and other dishes that need the pungent, volatile

ﬂ avor of mustard or horseradish. Many Japanese food products use mustard oil .

Many processed meat preparations such as bologna, frankfurters, and salami require

mustard ﬂ avor. It is also useful in salad dressings, condiments, and soups.

77 Mustard 305

Identiﬁ cation Numbers

FEMA No. CAS US/CFR E - No.

Mustard oil (for AITC) 2034 57 - 06 - 7 172.515 –

Mustard extract – 8007 - 40 - 7 182.20 –

References

Gan , Li ; Pan , Zhe ; Zhao , Li ; Xu , Jiuwei ; Zhang , Yu ; and Fu , Tingdong . 2005 . Analysis of lysine contents

by near - IR reﬂ ectance spectroscopy in Brassica napus and Brassica juncea . Zuowu Xuebao 31 ( 7 ),

944 – 947 (Chinese) ( Chem. Abstr . 145 :313310).

Liu , Qian ; Li , Zhanjie ; Xie , Mandan ; and Zhu , Yufan . 2001 . Component analysis of fatty acids in mustard

seed . Fenxi Ceshi Xuebao 20 ( 3 ), 49 – 50 (Chinese) ( Chem. Abstr . 136 :150051).