Special

Article

The plant cell wall as a source of dietary fiber: chemistry and structure1
Robert R Selvendran, PhD, CChem, FRSC

Introduction Definition review The

(1-3)

ofdietaryfiber

and

scope

of the

hypotheses of Burkitt and Trowell that many diseases of the Western world are associated with diets high in refined carbohydrates and low in fiber, have led to many studies on the composition and physiological effects of dietary fiber (DF). DF was defined by Trowel! in 1974 (4) as that part of plant material in our diet which is resistant to digestion by secretions of the human digestive tract. As this definition did not include polysaccharides present in some food additives (such as plant gums, algal polysaccharides, pectins, modified celluloses, and modified starches) Trowel! et a! (5) extended the definition to include all the polysaccharides and lignin that are not digested by endogenous secretions of the human digestive tract. Accordingly, the term DF now refers mainly to nonstarchy polysaccharides and lignin in the diet (6). Hence, plant cell walls are the main source of DF, and most of our DF intake comes from the cell walls in foods such as fruits, vegetables, and cereal products. The principal components of DF are complex polysaccharides some ofwhich are associated with lignin and proteins. The amounts of DF provided by cereal products depend on the type of cereal and particularly on the extent of its refinement; high extraction wheat products (eg, wholemeal bread, wholemeal breakfast cereals) contain more DF than products from low extraction white flours. Although most
320
The A,neriean Journal

ofthe DF constituents may survive digestion in the mouth, stomach, and small intestine, some of the constituents may be degraded by microorganisms of the human colon (7, 8). The average intake of DF in the United Kingdom is about 20 g/person/day and, of this, about a one-third comes from cereal sources. There is considerable variation between individuals; those with a high consumption tend to obtain more from cereal foods (9). As yet there is no official recommendation on a desirable level ofintake, but 30 g/person/day might be recommended. The British intake of DF is small compared with that ofa rural African diet, which might contain 100 to 170 g DF/day (9). Herein we discuss the chemistry of cell walls from various tissues of edible plants, some polysaccharide food additives, and DF preparations used in clinical feeding trials. The main emphasis is to show how this knowledge enhances our understanding of the chemistry and analysis of DF, and its possible fate in the human colon. The components of DF

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The main components which make up DF are summarized in Table I ; this lists the types of polymer that can be obtained from various types of plant material. The parenchymatous tissues are particularly important
I

From

the AFRC

Food

Research

Institute,

Colney should be

Lane,
2

Norwich NR4 7UA, UK. Author to whom requests for reprints September 27, for publication 1982. September

addressed. Received Accepted

20, 1983.

of clinical

Nutrition

39: FEBRUARY 1984, pp 320-337 Printed in U.S.A. (C) 1984 American Sociely tsr (linca1 Nutrition

CHEMISTRY TABLE I Components

Main

OF

DIETARY

FIBER

321

of DF
components
mixed diet

of a

Tissue

types

Main constituent

groups

of DF polymers

Fruits

and

vegetables

Mainly parenchymatous with some lignified and cutinised tissues

Cellulose, hemicelluloses (eg, xyloglucans), pectic substances, and some glycoproteins Cellulose, hemicelluloses (eg, glucuronoxylans), lignin and some glycoproteins Cutin and waxes Hemicelluloses (eg, arabinoxylans and -D-gIucans), cellulose, proteins, and phenolic esters Hemicelluloses (eg, glucuronoarabinoxylans), cellulose, lignin and phenolic esters, and proteins Cellulose, cans), pectic hemicelluloses substances, (eg, and xylogluglycoproteins Hemicelluloses (mainly galactomannans), and some cellulose, pectic substances, and (glyco)proteins Mainly arabinogalacturonosylrhamno-xylan Gums-gum arabic, geenan, guar gum, cellulose, modified alginates, can-acarboxymethylstarches, etc

Cereals

Seeds other uminous

than cereals seeds)

(eg, leg-

Parenchymatous (pea cotyledons) and cells with thickened endosperm walls (guar endosperm)

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Seed husk paghula Food

of Planiago husk)

ovata

(Is-

Mucilage

ofepidermal

cells

additives

in connection with DF, because the walls of these tissues comprise the bulk of the DF from fruits and vegetables, and the endosperm of cereals. The parenchymatous tissues have (mainly) thin primary cell walls, whereas the lignified tissues have cell walls that have ceased to grow and have undergone secondary thickening. The lignified tissues are of greater importance with some cereal products, eg, wheat bran and bran based products. In the development of the primary cell wall of dicotyledonous plants pectic substances (mainly as their calcium salts) are deposited first on the cell plate to form the middle lamella, which cements the cells together. Hemicelluloses, additional pectic substances, and glycoproteins are then deposited as an amorphous matrix of macromolecules closely associated with the cellulose microfibrils which are the main structural elements. The microfibrils contain highly ordered crystalline regions, in which linear chains of cellulose molecules are highly packed, and less ordered amorphous regions in which the cellulose chains are less

closely packed and in which other polysaccharides may be found. Cells in some regions ofthe plant, vascular tissues, become differentiated into specialized structures such as the xylem and phloem bundles; these form the veins and ribs of leaves, and continue into the petioles and stems. The xylem cells become thickened and hardened by lignification as the plant organ matures. Lignification begins in the primary wall region and then extends outward to the middle lamella and inward into the developing secondary wall, the final lignin concentration decreasing from the outside to the inside ofthe wall. The lignified walls have cellulose microfibrils dispersed in hemicelluloses and lignin. The relevant information on the biochemical processes that transform primary walls into secondary walls is summarized by Northcote (10). The main cell wall polymers of parenchymatous tissues of dicotyledons are pectic substances, hemicelluloses (eg, xyloglucans), and cellulose, whereas those of lignified tissues are lignin, hemicelluloses (eg, glucuronoxylans), and cellulose; usually different types of hemicellulosic polysaccharides oc-

322

SELVENDRAN

cur in the cell walls ofthe two types of tissue. In contrast to the cell walls of parenchymatous tissues of dicotyledons, those of cereal grains (wheat, barley, etc) contain very little or no pectic substances (1 1-1 3). The primary cell walls of most cereal grains have cellulose microfibrils, which are closely associated with glucomannan, and these fibrillar structures are embedded in an amorphous matrix of hemicelluloses, which consist mainly of arabinoxylans and/or $-Dglucans, some of which are cross-linked by phenolic esters and/or proteins. Rice endosperm walls seem to be intermediate in character between these and parenchyma of dicotyledons in that they contain about !0% of pectic substances and a substantial amount of cellulose. These differences in organization of the cell wall structure are reflected in their overall composition. The constituents ofcell walls therefore fall into three groups: The fibrillar and the matrix polysaccharides, which are formed simultaneously, and the encrusting substances (lignins), which are formed during secondary thickening of specialized cells ( 1 0, 14-16). The fibrillar polysaccharides, which are the basic structural units of microfibrils, are made up mainly ofcellulose. The a-cellulose fraction isolated from most plant tissues, however, usually contains small but significant amounts of nonglucan polysaccharides (and glycoproteins) associated with it (1720). This association of cellulose with other polysacchandes might occur by adsorption during the preparation of the material, or it might form part ofthe essential organization ofthe polysaccharides within the wall. If the latter is true, then the associated polysaccharides probably serve as linking compounds for the entanglement ofthe cellulose microfibrils with the matrix polysaccharides. The matrix polysaccharides are made up of linearly orientated polymers, which are present at all stages of the development of the wall, and also of highly branched polysaccharides that are deposited at particular stages of growth. These polysaccharides may, at the surface of the microfibri!, be incorporated into its structure. There are two major fractions in the matrix polysaccharides. 1) The pectic substances, which by definition are those polysaccharides that are

solubilized from the cell wall by aqueous solutions of chelating agents such as ethylenediaminetetra-acetate or ammonium oxalate. The solvent action of the chelating agents depends on their ability to combine with Ca and Mg. Some insoluble pectic material is always found in close association with other cell wall constituents, particularly the a-cellulose fraction. The soluble pectic substances comprise the methyl ester, pectin, the deesterified pectic acid and its salts, pectates, and certain neutral polysaccharides lacking the rhamnogalacturonan backbone, such as arabinans, galactans, and arabinogalactans. A large proportion of the neutral polysaccharides may be breakdown products of the more complex acidic pectic polysaccharides. 2) The hemicelluloses, which are those polysaccharides solubilized by alkali from the depectinated (and delignified) cell walls. Recent work suggests that some of the alkali-soluble polymers are polysaccharideprotein-polyphenol complexes. In addition to polysaccharides, small amounts of glycoproteins, both hydroxyproline-rich and hydroxyproline-poor, are also present, and the associated sugars are mainly arabinose and galactose (21). Water is also an important component of the cell wall, and is present in varying amounts, high in the primary cell walls of most tissues, except mature dry seeds, but low in secondary walls. The amount of water within the wall matrix can be partly controlled by the deposition of matrix polysaccharides which form close, intermolecular associations, or by the deposition of a hydrophobic filler such as lignin. During secondary thickening, the space occupied by water in the wall becomes progressively filled by lignin-polysaccharide complexes. The overall compositions (% w/w) of cell walls from parenchymatous and lignified tissues ofmature runner bean pods are as followsprimary cell walls: water 70%, cellulose 10%, pectic substances 12%, hemice!luloses 6%, and glycoproteins 2%; secondary cell walls: water 1 5%, cellulose 35%, lignin 18%, hemicelluloses 25%, pectic substances 5%, and proteins 2% (Se!vendran RR, unpublished results).

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CHEMISTRY

OF

DIETARY

FIBER

323

The chemistry angiosperms

of cell walls

from

Because the nature of the carbohydrate polymers associated with various types of tissue from dicotyledonous and monocotyledonous plants are different, the polymers present in these species will be discussed separately, with the main emphasis on the cell walls of edible plant organs. As several reviews dealing with the chemistry of cell wall polysaccharides are available (6, 14-16, 22, 23) the detailed chemistry ofthe individual polysaccharides will not be described. However, attention will be drawn to certain structural features of the polymers which may be of interest, in the context of the analysis of DF, or its mode of action in the human alimentary tract. For convenience, the relationship of the operationally defined groups of polysaccharides to structural families, and the main sugars and glycosidic linkages present in the major polysaccharides are tabulated. Where necessary, suitable examples from edible plant organs are given to illustrate certain special aspects of cell wall and DF composition. Cell walls ofdicotyledonous plants

Primary cell walls. In addition to the polysaccharide and glycoprotein components, the cell wall material (CWM) of parenchymatous tissues of runner beans, cabbage, apples, and carrot contains about 5 to 10% of polyphenolic compounds in the form of polysaccharide-protein-polyphenol complexes (Selvendran RR, ONeill MA, Stevens BJH, unpublished results; 24). The relative proportions ofthe different types ofcell wall polymers vary with the type and maturity of the tissue. The major structural features of the cell wall polymers are summarized in Table 2. Some indication of the nature and amount of polysaccharides present in the cell walls can be obtained from their overall carbohydrate compositions (Table 3). In this connection, see also the tables given in References 17 to 19, 24, 25, and 33, which describe the results of purifying cell walls and of chemical fractionation studies. The cell walls of the products listed in Table 3 contain mainly cellulose and pectic acid as

well as other pectic substances, and small amounts of xyloglucans and wall glycoproteins, and are devoid ofxylans. The first two components can be estimated from the values for glucose and uronic acid (35, 36); this method has the advantage that it measures the total pectic acid: chelating agent-soluble and insoluble pectic acid. The validity of the measurements depends on the following: 1) the bulk of the glucose released on Saeman-hydrolysis arises from cellulose; 2) a large proportion (-90 to 95%) ofthe uronic acid arises from the galacturonic acid of pectic substances; 3) the pectic substances of potatoes are rich in galactose, whereas those of apples and cabbage are rich in arabinose; 4) primary cell walls have little or no (glucurono)-xylans which are the predominant hemicelluloses of secondary walls; much of the xylose of primary walls arises from xyloglucans. Secondary cell walls. The differentiation of the primary wall into secondary wall involves considerable thickening of the wall and profound changes in its chemical composition. During the growth ofthe secondary wall, a-cellulose, hemicelluloses, and lignin are deposited, and the thickening results more from the a-cellulose than the hemicellulose deposition (10). Lignin occurs to the extent of 1 5 to 35% of most supporting tissues of higher plants and seems to form covalent linkages with the hemicelluloses (37), cementing together the wall polymers into a unified rigid matrix and stratifying the wall. The hemicelluloses are mainly (--90%) glucuronoand 4-0-methylglucurono-xylans, which have 3-(l 4)-linked DXylp residues with side chains of D-glucuronic acid or 4-0-methyl-D-glucuronic acid linked to C-2 of about 10% of the Xylp residues; about 50% of the xylose residues have an acetyl group, linked mostly to C-3. The carbohydrate compositions and hgnm content of the cell wall preparations from hignified tissues (parchment layers and strings) of mature runner bean pods are shown in Table 4; also included in Table 4 are the carbohydrate compositions of the CWM from beeswing wheat bran and some hemicelluloses (20). The carbohydrate compositions ofthe CWM show that the hignified tissues are rich in cellulose and acidic-xylans
-*

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324 TABLE 2 Classification

Polysacchande
and

SELVENDRAN

of some

polysaccharides

from

primary

cell walls

ofedible

dicotyledons

Monosaccharides Source Major Minor Structural features References

Representative type

Cellulose

All primary walls

o-Glc

Linear chains of 3-(I 4)-linked o-Glcp residues o-Xyl, n-Gal, L-Fuc, L-Ara 3-( 1 -* 4)-linked r-Glcp residues containing ct-o-Xyl p resi#{243}ues as side chains on C-6 of at least half the GIc residues, with some of the Xyl residues being further substituted with fl-o-Gal p, a-LArafor L-Fuc p residues
4)-linked o-Gal pA (or methyl esterifled Gal pA) residues containing(l -p2)linked $-i-Rhap; galactan and arabinan side chains on C-4 of Rha p. ( 1 -* 5)-linked i-Araf residues having branch points through C-3, as well as C-3 and C-2 (doubly branched).

14, 22

Hemicelluloses Xyloglucans

All primary walls

c-Glc

22, 23, 18, 25

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Pectic substances Pectin

All primary walls

o-Gal

L-Rha, L-Ara, o-Gal

a-(1

22, 23, 26

Arabinan

Galactan

Immature cabbage leaves, and cotyledons of mustard and soybeans Potato tubers

i-Ara

22, 27, 28

D-Gal

Arabinogalactan-l

Soybean cotyledon

n-Gal

L-Ara

Mainly 3-( 1 - 4)-linked o-Gal p residues, with some(l -+4,6)-linked residues fl-( 1 -+ 4)-linked r-Gal p residues containing a-L-Arafll -. 5)-LAraf-( l-+) residues as side chains on C-3 of some of the Gal residues

29

30

Wall glycoproteins Hydroxyproline-rich glycoproteins

Runner beans

L-Ara

o-Gal

Hydroxyproline tetraand tri-arabino-furano sides; a-D-Gal p-serine

21, 31, 32

and contain very small amounts of pectic substances. These inferences are corroborated by the carbohydrate compositions of the polysaccharide fractions. Cell walls ofseeds. The seeds of dicotyledonous plants can be classified into those

which are free of as nonendospermic those which have as endospermic species, eg, guar, mer types of seeds

an endosperm, referred to (eg, bean, pea, etc) and an endosperm, referred to (as in certain leguminous locust bean, etc). The forusually have starch as the

CHEMISTRY TABLE 3 Carbohydrate edible plants

OF

DIETARY

FIBER

325

compositions of the CWM (values are zg anhydrosugar/mg

Potatoes

and some CW polysaccharides drypreparation)

( 8) Apples

from

parenchymatous

tissues

of some
beans (32. 34)

Cabbage

(33)

Sugars
CWM

Runner

Ox-soI4

XG

a-CcItt

CWM

Ox-soi-t

CWM

Ox-sol.t

CWM

HP-GPI

6-Deoxyhexose Arabinose Xylose Mannose Galactose Glucoseli Uronicacid** * Stevens BJH,

20.4 14.2 1 1.5 46.1 39.4 67.4 12.5 16.5 190 9.3 Trace 14.1 20.3 284 192 75.3 32.6 315 Trace 430 690 270 720 190 Selvendran RR, unpublished results.

19.6 123 33.3 43.0 56.8 227 328

26.5 159 12.3 3.0 36.5 10.2 707

29.6 125 44.9 24.7 67.2 355 279

42.9 179 7.7 2.7 54.9 11.6 672

19.3 35.1 17.3 15.7 75 314 367

8.2 387 11.1 70.4 9.3 75

pectic substances. xyloglucan. a-Cellulose residue. It Purified hydroxyproline-rich glycoprotein fraction. #{182} The bulk (90%) ofthe glucose from the CWM arises from cellulose. ** The bulk (95%) ofthe uronic acid arises from pectins. Potatoes (var Desiree): Apples (var Coxs Orange Pippin); Cabbage (var Decema); line).
:1: Purified

t Oxalate-soluble

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Runner

beans

(var Stream-

4 Compositions preparation)
TABLE

ofCWM,

hemicelluloses

and
Runner

a-cellulose
beans Parchment ( I M KOH-sott)

from

lignifled

tissues

(values

are gig anhydrosugar/mg

Beeswing wheat I bran KOH solt (20)
-

dry

Sugar

Stringst (CWM)

Parchmentt (CWM)

Parchment (a-Cellulose)

CWM

I I

6-Deoxyhexose Arabinose Xylose Mannose Galactose Glucose Uronicacid

*

Selvendran

RR,

5.2 7.1 6.7 11.2 250 240 9.1 6.2 4.2 16.0 43#{216}** 420** 40 80 unpublished results.

7.0 3.8 810 Trace Trace 6.7 94

2.1 16.4 7.2 3.1 Trace 920**

216 168 Trace 12 204** 40

258 204 39 90 56

280 270 15.0 8.7 60

73 53

657** 20

t Strings and parchment layers j: Polysaccharides solubilized from a-Cellulose from the holocellulose #{182} Polysaccharides solubilized from II Oxalate-soluble polysaccharides, ** The bulk (-95%) ofthe glucose The Klason lignin content (% w/w) 17.2, 16.9, and 12.0, respectively.

of mature runner bean pods. the holocellulose with lM KOH. (delignified CWM). the oxalate-extracted CWM by IM KOH. which represent only about 1.6% of the amount arises from cellulose. of the CWM from strings, parchment layers,

solubilized and beeswing

by IM KOH. wheat bran are

main storage polysaccharide, and their CWM is derived mainly from the tissues of the cotyledons and there is some contribution from the testa (which are usually hignifled). The cell wall polysaccharides of the cotyledons are similar to those of parenchymatous tissues and are mainly pectic substances, cellulose, and hemicehluloses (eg, xyloglucans). The notable difference is that arabinans either free or linked to rhamnogalacturonans tend to predominate in the

seeds. In this respect the pectic substances of the cotyledons resemble those of immature cabbage leaves. By contrast to nonendospermic seeds, all the endospermic leguminous seeds contain galactomannans, which are located in the endosperm cell walls (38). The galactomannans are deposited on the cell walls of the endosperm during seed development and are later mobilized during germination of the seeds. The galactomannans are essen-

326

SELVENDRAN

tiahly linear molecules but are highly substituted on C-6 of the f3-( 1 - 4)-hinked-D-Man p residues with single Gal p residues, which confers on them properties which are quite different from those of unbranched, cellulose-like, water-insoluble mannans and glucomannans. The galactomannans are hydrophihic and are usually obtained from the crushed seeds (or endosperms) by hot water extraction (39). The interactions of galactomannans with water and other polysaccharides form the basis of the widespread industrial uses of galactomannans from guar and locust bean seeds (40). Because guar gum lowers blood glucose level (41), guar-enriched breads have been tested on diabetics (42), and the results are encouraging. Guar appears to slow glucose absorption in the small intestine by interacting with intestinal mucosa (43). The mucilages ofthe seeds ofthe plantain family (Plantinaginaceae) are localized in the thick mucilage cells which form the outer epiderm ofthe spermoderm. The mucilage from the seed husk of Plantago ovata Forsk (usually referred to as Ispaghula husk), has important physiological effects on large bowel action and is widely used for treating large bowel disorders such as diverticular disease (44). The husk contains much polysaccharide which forms a gel in water, retaming many times its own weight of water (45, 46). This property of the husk, coupled with the fact that the constituent polysaccharide has a highly substituted xylan backbone (and is therefore not readily degraded by microorganisms of the human colon) is probably one ofthe main factors responsible for its laxative action. The structural features of the above polysacchande, and those of guar gum, are given in Table S along with those of other food gums. For a detailed account of the chemistry and properties of guar gum see References 47 and 48. The carbohydrate compositions of the starch-free alcohol-insoluble residues (AIR) ofthe hulls and cotyledons ofpeas, and those of guar seeds and guar seed splits (which contain mainly the endosperm) and Ispaghula husk are shown in Table 6; also included in Table 6 are the DF content of the products. Selvendran and DuPont (36) give details of the method of preparation and

analysis of the AIR. The results of such analyses show that 1) the cell walls of cotyledons are rich in arabinose-containing pectic substances, pectic acid, and cellulose; 2) the cell walls ofpea hulls are rich in cellulose, pectic acid, (acidic) xylans, and hignin; this last inference is based on the positive staining reaction with phloroglucinol/HC1; 3) the cell walls of guar seed splits are very rich in galactomannans and contain small amounts of pectic substances and cellulose; and 4) Ispaghula mucilage is very rich in arabinoxylans. Cell walls ofmonocotyledonous plants
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The cell walls of certain organs of monocotyledonous plants, particularly those of cereal grains, are an important source of DF. Cereal grains are used for the production of flour required for bread, cakes, biscuits, etc. Products derived from grains are also commonly used as breakfast foods in the form of bran based products, flakes, or porridge. All cereals have endospermous seeds; the endosperm ofwheat, for example, represents about 80 to 85% of the grain, and is the source of white flour, which is usually preferred for bread-making. To obtain white flour, almost pure endosperm must be separated and ground. Thus the milling process for wheat is a complex operation, involving separation into three main fractions: bran or pericarp, with the attached testa and aleurone layer (in all about 12 to 17%), the endosperm itself(about 80 to 85%), and the embryo or wheat germ (about 3%). The removal of the bran may result in a loss of up to 50% of the total DF content of the grain. The cell wall polysaccharides of parenchymatous tissues of cereals are mainly arabinoxylans and 3-i-glucans, but they all contam small but significant amounts of cellulose, usually associated with glucomannan ( 1 1-1 3). The relative amounts of the first two polysaccharides could vary considerably among cereals. Thus wheat endosperm walls are very rich in arabinoxylans but poor in f-glucans, whereas those of barley are rich in fl-glucans but relatively poor in arabinoxylans. The polymers present in the primary cell walls of wheat and barley together with those of lignifled tissues of wheat, and the

CHEMISTRY
TABLE 5 Classification of some
.

OF

DIETARY

FIBER

327

food

gums
Source

Representative type ofgum

o-Man,
Major

Monosaccharides Minor

Structural

features

Guar

Endosperm of guar seeds Mucilage cells of Plantago ovata* Forsk

o-Gal

Highly substituted -( 1 -* 4)linked o-Man p residues having a-D-Gal p residues as side chains on C-6 L-Ara i-Rha, D-Gal A Highly branched arabinoxylan, the xylan back-bone having both (1 - 4)- and (1 -* 3)-linkages; side chains of a-L Araf (mostly), /3-D-Xyl p and Gal pA-( 1 - 2)-a-i-Rhap-( 1 -*), linked to C-3 (mostly) and C-2 of Xyl residues $-(1 -+ 3)-linked o-Gal p residues some ofwhich are substituted at C-6 with side chains bearing ( 1 -+ 6)-linked Gal p residues; side chains on the latter include terminal L-Araf, L-Rha p and 4-0-Me-fi-o-Glc pA Linear chains offl-(l -. 4)-linked D-mannuronic acid and a-( I -. 4)-linked L-guluronic acid Consists of alternating sequence of0-4 substituted 3, 6-anhydroa-D-Gal p and 0-3 substitutedc-Gal p which is sulphated at 0-4 $-(l - 4)-linked D-Glc p residues, with a maximum substitution ofO.95 carboxymethyl (-CH2 COOH) group per glucose unit arenaria, and Plantago ovala under the first two species are included as Psyllium of Pharmacognosy. 9th ed, Thease &

Mucilages

o-Xyl,

Arabic

Exudate of Acacia senegal

n-Gal,

L-Ara

i-Glc pA, L-Rha

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Alginate

Laminaria species

D-Mannuronic acid, L-guluronic acid 3, 6-Anhydro,-o-Gal p. -o-Gal p sulphated at 0-4 o-GIc

Kappa

Carrageenan

Gigartina species

Carboxymethyl-cellulose

Cellulose

The

US National

Formulary

includes

Plantago

psylluim,

Plantago

name Plantago seed. In the British Pharmaceutical Codex the seeds ofthe BPC, while those of P ovata form Ispaghula BPC. Reference: Textbook Evans, PubI Bailliere, Tindall & Cassell, London.

parenchymatous tissues of certain monocotyledons which are rich in pectic substances will be discussed briefly. Primary cell wallsfrom the endosperm and aleurone layer. The most notable differences between the cell walls ofthe endosperm (and aleurone layer) of cereals and those of parenchymatous tissues ofdicotyledons are that unlike the latter, the former are virtually free of pectins and pectic substances, and the amount of cellulose is very low. These differences are reflected in the carbohydrate compositions of the cell walls and some cell wall polysaccharide fractions, from the endosperm and aleurone layer, which are given in Table 7. The arabinose and xylose arise

from arabinoxylans and the bulk of the glucose from the cell walls of aleurone layer arises from mixed-linkage fl-glucans and not from cellulose. The arabinoxylans of wheat and barley endosperm cell walls have a highly branched fl-( 1 -+ 4)-linked D-Xylp backbone, containing Araf residues as side chains on C-3, as well as C-3 and C-2; some side chains, however, contain (1 - 5)-linked Arafresidues as well (1 3, 5 1, 52). The mixed linkage 13-glucans are linear molecules and contain fl-( 1 -+ 3)- and fl-(1 - 4)-linked I)Glc p residues (51). Despite the relatively low levels of cellulose, chemical extraction studies, coupled with electron microscopy, have shown that

328 TABLE 6 Carbohydrate compositions of the starch-d pg anhydrosugar/mg dry preparation)

Sugar Pea hull

SELVENDRAN

epleted

alcohol

-insoluble

resi dues

of some

issues

of seed s (values
ispaghuta

are

Pea tiourl

Guar

seed

Guarseed

ispaghula

splits
5.4

mucilage

mucilage (50)

6-Deoxyhexose Arabinose Xylose Mannose Galactose Glucose Uronicacid DF (%w/w) * Selvendran t The pea :1: Mucilage compare well The bulk II The DF weight basis.
TABLE

RR,

DuPont

16.3 27.2 118 3.2 11.3 570 154 (73) MS. unpublished

8.5 132 11.7 4.9 27.8 58.1 60.2 ( I I .6) results.

8.9 35.9 54.2 326 198 156 78 (65) which values

18.9 3.6 506 301 22.5 42.3 (88)

32.9 222 627 21.9 74.9 14.1 (94)

234 626 7.4 29.5 27.3

flour was derived mainly from the cotyledons, from the seed husk of Ispaghula; the sugar with our data, given in column 5. (-90%) ofthe glucose arises from cellulose. content of the products, based on their content

contain much intracellular proteins. are from Englyst et al (50) and these

values

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of nonstarch

polysaccharides

only,

is given

on a dry

7 Carbohydrate compositions wheat and barley (values

Sugars CWM

of the CWM and some hemicelluloses from are monosaccharide composition % w/w)
endosperm (II) HC CWM Barley endosperns (12) HC CWM

the endosperm
Wheat aleurone (13)
HC

and aleurone
Barle

layers
aleurone (13) HC

of

Wheat

CWM

Arabinose Xylose Mannose Galactose Glucose * The Wheat

major

34.0 53.5 7.0 2.5 3.0 hemicellulosic

34.5 63.5 2

9 10 2 79t of the CWM.

11 14 0 75t

17 48 1 3 31t

20 60 2 l8t

23 44 2 2 29t

27 54 1 17t

fraction

t The bulk (>95%)

endosperm

of the glucose arises from and aleurone (var Insignia):

(i-D-glucans. Barley endosperm

(var Julia);

Barley

aleurone

(var Clipper).

the endosperm cell walls consist of a microfibrillar phase embedded in an amorphous matrix (1 1); in this respect they are similar to most primary plant cell walls. The microfibrils probably consist of glucomannans in close association with cellulose (1 1). The predominant polysaccharides of wheat endosperm cell walls are arabinoxylans (88%), of which one-third are soluble in water; alkahine agents are needed to dissolve the remaining two-thirds. The cellulose content of the walls is about 2% and it is notable that the /3-glucan content is only about 1 %. The latter finding is in striking contrast with the unusually high levels of mixed-linkage figlucans in barley (12, 5 1) and rye grass endosperm walls (53); the bulk of the glucose of barley endosperm walls arises from j3glucans (Table 7). The requirement of alkaline conditions to solubilize the bulk of the

arabinoxylans suggests the possible involvement of phenohic ester (or phenohic) crosslinkages in the wall (1 2). Some supporting evidence for the occurrence of phenolic ester cross-linkages is provided by the work of Neukom and colleagues (54, 55). They have shown that a diferuhic acid-arabinoxylan complex was formed when a solution of a water-soluble arabinoxylan (containing feruhic acid) from wheat flour was oxidized with H2O2 in the presence of peroxidase (55). The work of Ballance and Manners (51) has shown that about 70% of the barley endosperm walls is composed of mixed-linkage 3-glucans. The ratio of(l -+ 3)- to (1 -* 4)-linkages in the fl-glucans is about 3:7. The 3-glucans of barley seem to be proteoglycans (polysaccharide-protein complexes) (5 1 , 56, 57); the available evidence to the present time has been summarized in Ref-

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erence 16. Chemical fractionation suggests the involvement of phenolic acids (esters) and proteins in cross-linking some of the wall polymers. The walls of wheat and barley aleurone cells are composed mainly of fl-glucans and arabinoxylans, and small amounts of cellulose, glucomannan, and phenohics ( 13). The bulk (-95%) ofthe glucose ofthe walls, from both species, arises from mixed-linkage 9glucans. The xylose and arabinose of the walls arise from arabinoxylans, which are differentially soluble in a range of neutral and alkaline solvents. Cells walls of lignified tissues of wheat. Beeswing wheat bran consists mainly of the outer coating ofthe wheat grain and is about three cells thick, containing the epidermis, hypodermis, and cross cells, which are hgnifled. The studies of various groups of workers have shown that the CWM of beeswing bran consists of hemicelluloses, cellulose, lignin and phenohic esters, and proteins (20, 58). The Klason lignin and protein contents ofthe CWM are I 2 and 6% (w/w), respectively (20). The hemicelluloses are highly branched glucuronoand 4-0methylglucurono-arabinoxylans; some of the xlose residues of the backbone appear to be substituted in quadruphicate. In contrast to arabinoxylans of endosperm cell walls, which are neutral, those of hignifled tissues are acidic, due to the presence of glucuronic acid and 4-0-Me glucuronic acid; the bulk of the uronic acids are directly linked to C-2 of the ( 1 4)-linked Xyl p residues. Most of the (acidic) arabinoxylans can be solubihized only with alkali, suggesting the occurrence of phenolic ester crosslinkages in the walls; indeed, ferulic and pcoumaric acids have been detected in the alkaline extracts (20, 59). The (acidic) arabinoxylans are linked to other macromolecules such as hignin or proteins, or both. This is inferred 1) from the occurrence of lignin and proteins in the CWM, as well as in the isolated polysaccharide fractions, and 2) because the constituent (anhydro) sugars account for only 50 to 60% of the dry weight of the polysaccharide fractions (20). The carbohydrate compositions of the CWM and alkali-soluble hemicellulose fraction of beeswing bran are shown in Table 4.

The arabinose and xylose ofthe CWM arise from acidic arabinoxylans and most (90%) of the glucose arises from cellulose. These results coupled with those of Table 7 clearly show that the cell walls ofthe hignified tissues ofwheat grain are quite different from those of the parenchymatous tissues. Primary cell walls rich in pectic substances. In contrast to cereal grains, the cell walls of parenchymatous tissues of certain monocotyledonous plants such as onion bulbs, decutinized leeks, and asparagus shoots (pith region of young shoots) are rich in pectic substances, and their overall compositions (% w/w dry CWM) are as follows: onions (var Giant Fen Globe)-rha 1 . 1 , ara 1.5, xyl 1.3, man 0.7, gal 13.5, glc 31.2, and uronic acid (ua) 32.5; asparagus (var Conovors Colossal)-rha 1.9, ara 3.7, xyl 4.0, man 1.8, gal 7.9, glc 39.7, and ua 33.0; leeks (var Musselburgh)-rha 1.8, ara 4.2, xyl 4.2, man 1.5, gal 1.6, glc 22.0, and ua 24.2 (Selvendran RR, unpublished results). The walls of the mesophyll cells of grass leaves, however, are poor in pectic substances (60); the composition of the CWM (% w/w) is as follows: rha 1.0, ara 13.9, xyl 17.6, gal 4.0, glc 57.2, and ua 6.5. In leeks there would be some contribution to the CWM from vascuhar tissues. The CWM was prepared by sequentially extracting the fresh tissues with 1 % (w/w) aqueous sodium deoxycholate and phenol/acetic acid/water (1 7). As the starch content of the tissues was low, extraction with 90% aqueous dimethylsulphoxide was omitted. Although the uronic acids were not rigorously identified, galacturonic acid (of pectic substances) probably makes a major contribution to the total uronic acid content. The overall carbohydrate compositions of the above cell wall preparations are comparable with those of parenchymatous tissues ofdicotyledons (cfTable 3), and are in striking contrast with those of cereals (cf Table 7). Fractionation studies on the cell wall preparations have shown that they contain mainly pectic substances, cellulose, and hemicelluloses. The occurrence of pectic substances in onions has been recently reported (61). Lignins Lignin weight, is an amorphous, aromatic polymer high molecular composed of

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330

SELVENDRAN

phenylpropane residues. It is formed at the sites of hignification by the enzymatic dehydrogenation and subsequent polymerization of coniferyl, sinapyl, and p-coumaryl alcohols; the monomeric units derived from these alcohols are called guaiacyl (3-methoxy-4-hydroxyphenylpropane), syringylpropane (3,5-dimethoxy-4-hydroxyphenylpropane), and p-coumaryl (4-hydroxyphenylpropane) residues, respectively (62). Phylogenetic origin determines the relative proportions of the phenylpropane residues in the lignins. The lignins can be divided into three broad classes, which are called softwood (gymnosperm), hardwood (dicotyledonous angiosperm), and grass (monocotyledonous angiosperm) hignins. Of these the softwood hignins contain mainly guaiacyl residues, with small amounts of p-coumaryl and syringylpropane residues; the hardwood hignins contain about equal amounts of guaiacyl and syringylpropane residues, with only minor amounts ofp-coumaryl residues; and the grass hignins are composed of approximately equal amounts of all three residues. However, grass cells walls contain in addition some esters of p-coumaric and feruhic acids in the bound form, and these esters are not incorporated into the hignin polymer itself. The angiosperm hignins, which are the ones of interest in the DF context, demonstrate considerable variation from species to species (63). Lignification serves two main functions. It cements and anchors the cellulose microfibrils and other matrix polysaccharides, and because the lignin-polysaccharide complexes are hard, they stiffen the walls, thus preventing biochemical degradation and physical damage to the walls. These properties of hignifled walls are important in the DF context, because they minimize the bacterial degradation ofthe walls in the human colon. The implications of these properties are discussed later. The skins wall and protective coverings of the

polysacchandes (eg, pectin and cellulose) of the wall. Underground organs, eg, tubers, and healed wound surfaces of plants are protected by another type of lipid-derived polymeric material, called suberin, which is related to cutin. Both cutin and suberin are embedded in and overlaid with a complex mixture of relatively nonpolar lipids, which are collectively called waxes. Cutin is hydrophobic and contains a number of hydroxy monocarboxyhic acids with 16 and/or 18 carbon atoms in linear chain with hydroxyl groups at C-9, C-8, or C-7. The waxes are complex mixtures, of which the common constituents are long chain hydrocarbons, alcohols, aldehydes, ketones, fatty acids and hydroxy-fatty acids, and esters. The length ofthe above compounds usually range from Cl6 to C34 (64, 65). Among other functions, the cuticle provides the first potential barrier to attack by fungi, insects, or other pathogens. Because cutin and waxes are resistant to bacterial degradation, cutinized tissues may serve an important role in restricting the access of intestinal bacteria (and bacterial enzymes) to the cell wall polysaccharides of some vegetables and fruits. This phenomenon may be particularly significant in the case of leafy vegetables, which have spongy parenchyma cells sandwiched between cutinized layers. The chemistry gums of some food additives-

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The outer walls of the epidermal cells of leaves, fruits, and many other aerial organs of plants are covered with a protective layer ofwaxes and cutin. Generally the cutin penetrates and is intermingled with the outer

The technical definition of a gum is a polymeric material that can be dissolved or dispersed in water to give a thickening and/ or a gelling effect (66). Among the leading materials, in decreasing order of use in food, are pectins, gum arabic, alginates, guar gum, carboxymethylcellulose, carrageenan, locust bean gum, and modified starches. These gums have valuable properties and many commercial foods contain small amounts of them. As they are not hydrolyzed by the human digestive enzymes they are classified under the term DF, as defined earlier. With the exception of modified starches and (possibly) gum arabic all the polymers listed above are derived from plant cell walls. For example, the cell wall polysaccharides and mucilaginous material of some sea weeds

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(certain species of brown algae) are important sources of alginates and carrageenans. The modified starches used in the food industry are prepared by either slightly crosslinking the starch or by esterifying with acetyl groups; the levels of substituents range from 0.03 to 0.06 acetyl groups/anhydroglucose residue. The major structural features of some of the gums listed above are shown in Table 5; for convenience the gums are classified into different groups. For more details on the structural characteristics of gums see References 6, 66, and 67. The DF content of some plant foods

The DF content of some vegetables, fruit and seed products, and of some cereal products, are given in Tables 8 and 9, respectively. Also included in Tables 8 and 9 are the main types of tissues comprising the products. As the major types of cell wall polymers present in most of the products have been discussed earlier, attention will be drawn only to some of the distinctive features. Additional information on the DF content of a range of plant foods can be obtained from References 68 to 75. In Reference 75 the various methods available for the analysis of DF are discussed critically and objectively.
TABLE. 8 Carbohydrate compositions of the s tarch-deplet anhydr sugar/mg dry preparation)
Prxlucts Tissie types
Mainly

Interestingly, despite the high starch content of potatoes, their DF content is comparable with that ofapples and cabbage. The DF content of mature runner bean pods is considerably higher than that of the above products, because it contains a significant amount of hignified tissues; this is reflected in the relatively high level of xylose derived from acidic-xylans. Processed starch-rich products, such as potato powder, contain a significant but variable level of modified or resistant starch. The modified starch is not fully degradable by treatment with a-amylase and puhlulanase. It is formed when gelatinized starch is cooled and dried and could arise from strong hydrogen bond formation between OH groups on adjacent starch molecules, or by elimination of water under heat treatment, or both. The main DF polymers of soya flour are pectic substances (arabinogalactans, pectins, etc), hemicelluloses (xyloglucans), and cellulose, whereas those of soya bran, which contains mainly the hignified hulls, are cellulose, hemicelluloses (acidic xylans), and pectic substances. The values for the DF content of cereal products, given in Table 9, were obtained from the results of Englyst et a! (50), who have used an alternative method to isolate the DF-fractions. The DF of white flour is mainly derived from the primary cell walls
soluble residu es of some
Potatot powder (36) Mainly P

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ed alcohol-in

p1 ant foods
Soya bran Mainly L

(val ues are g

Soya* flour Mainly P

Potatoes

AppIes

Cabbage Mainly + me LandC P

Runner t,eans (36) Mainly P + L and someC

Mainly

Sugars

6-Deoyhexose Arabinose Xylose Manncse Galactose Glucose (glucose) Uronicacid

10.2 37.7 11.5 9.8 204 240 (43.8) 159 RR, DuPont (1.8) MS.

P!!
*

w/w)II Selvendran

23.0 128 48.7 18.5 57. 1 300 (20.2) 331 (1.9) unpublished

17.5 46.5 30.7 15.3 30.3 279 (19.1) 235 (2.2) results; the

11.4 29.4 68.4 15.1 7 1.4 323 (37.3) 220 (4.0) products were

5.8 20.6 4.9 4.2 100 210 (130) 128 (9.5) analyzed

12.6 10.1 60.8 37.4 107 14.1 54.8 10.6 23.5 66.2 472 45.7 (17.0) (5.1) 168 70.3 (79.5) (14.0) essentially by our methods

described in References 36 and 75. Tissue types: P. parenchymatous; L, lignified; C, cutinized. t Commercial Cadbury Schweppes potato powder, contains modified starch. With the exception of potato powder, the bulk (>90%) ofthe glucose arises from cellulose; the glucose values in parentheses are from direct lM H2 504 hydrolysis. II DF values based on the content of non-starch polysaccharides only; for potatoes, apples, cabbage, and runner beans he values are expressed on a fresh weight basis and for the other products on a dry weight basis.

332 TABLE 9 Carbohydrate compositions 100 g dry matter basis)

Products Tissue typcs, White Mainly

SELVENDRAN

of non starch

polysa ccharides
Rye flour P
+

in some

plant

f oods

(50) (valu es are expresse

Wholewheat breadt Wheat product L P

d on a gJ
Corn fiakest P
+

flour P

Pearl barley Mainly

Wholewheat flour P I Mainly some P L

bran P L

Mainly some

Mainly some

Mainly some

Sugars Arabinose Xylose Mannose Galactose Glucosell (glucose) Uronic acid DF(% w/w) * All the results

0.91 1.38 0.07 0. 18 0.66 (0.19) 3.20 are from Reference

1.18 1.62 0.34 0.07 4.52 (0.36) 0.06 7.79 50.

3.63 5.76 0.33 0.3 1 3.67 (1.49) 0.20 13.9

2.67 4.32 0.15 0.29 2.56 (1.64) 0.28 10.27

2.62 4.17 0.21 0.30 2.36 (1.61) 0.25 9.91

5.87 9.68 0.25 0.50 6.79 (4.67) 0.74 23.83

0.11 0.14

0.35 (0.24) 0.05 0.65

t These products contain a significant amount of starch resistant to enzymic hydrolysis; the resistant starch values for wholewheat bread and cornflakes are 0.84 and 2.92 g/lOO g dry weight respectively, and these figures are not included in the values for DF. The DF content of this wheat bran product (All-Bran, Kelloggs Company, UK) is somewhat low, most commercial wheat bran samples have DF values between 40-50g/lOOg dry matter (Selvendran RR, DuPont MS. unpublished results). Tissue types: P, parenchymatous; L, lignified. II Glucose released by a modified Saeman-hydrolysis procedure; the glucose values in parentheses are from cellulose only.

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which are rich in neutral arabinoxylans but relatively poor in /3-glucans. In contrast, the major DF-polymers of pearl barley are /3glucans. The rye flour used for making rye biscuits (ryvita) is relatively rich in /3-glucans, but contains significant amounts of cellulose and (acidic) arabinoxylans derived from the hignified bran layers of the grain. The main DF polymers ofwhole wheat flour are neutral arabinoxylans, acidic arabinoxylans, and cellulose. The last two are derived mainly from the hignified bran layers. In addition to the above polymers, whole wheat bread contains some modified starch which is resistant to enzymic degradation. The main DF polymers of wheat bran are acidic arabinoxylans and cellulose. Wheat bran fiber also contains small but significant levels of neutral arabinoxylans and /3-glucans which are derived mainly from the endosperm and aleurone layers, respectively. In addition to cellulose and acidic arabinoxylans, cornflakes contain a very significant amount ofresistant starch. A measure of the resistant starch can be obtained by dissolving it in alkali (for details see References 50 and 75) and measuring the amount of enzymica!ly degradable starch solubilized.

A comparison DF preparations trails

of the compositions used in clinical

of some feeding

In order to test the effect of the type of DF on fecal weight and transit time, Cummings et a! (76) fed concentrated fiber preparations from wheat bran, cabbage, carrot, apple, and guar gum to healthy volunteers. The fibre was concentrated by preparing the AIR of the products. These were fed to the volunteers who were on a metabolically controlled diet, the composition of which was similar to a British diet and contained 22 g of DF/day. Fiber from each of the materials (20 g/day) was added to the controlled diets of separate groups and the changes in fecal weight and transit time were recorded (for details see Reference 76). Their results showed that 1) fecal weight increased by 127% on bran and 20% on guar gum, with cabbage, carrot, and apple producing intermediate changes (69-40% respectively); 2) the mean transit time was shortened by the addition of fiber to the diet, with bran producing the greatest change; 3) these differences are related to the pentose content of the fiber, cereal fiber (wheat bran) being much more effective than vegetable (and fruit) fiber, and 4) individuals on a standard

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fiber intake showed widely differing colonic responses. In view of these findings, the detailed chemical compositions of the above fiber preparations were studied by us, with a view to explaining the observed physiohogical effects, and some of the results have already been published (19, 28, 77, 78). Herein, the compositions of the above DF preparations are discussed briefly, and a possible mechanism for the mode of action of DF in the human colon is postulated. Carbohydrate preparations compositions ofthe DF

gave mainly drolysis.

mannose

and

galactose

on hy-

Chemicalfractionation preparations

ofthe

DF

The AIR of wheat bran, cabbage, carrot, and apple were rendered free ofstarch, using the procedure of Selvendran and DuPont (36), and the carbohydrate compositions and hignin content ofthe starch-free residues were determined. The results of these analyses are given in Table 10; also included in Table 10 is the carbohydrate composition of guar gum. Compared with the other fiber prepaiations wheat bran is clearly richer in arabirtose and xylose. The pentose content of the samples decreased in the order wheat bran, cabbage, apple, carrot, and guar gum. The hexose contents of the vegetable fibers are, however, higher than those of wheat bran. Another feature is the relatively high level of uronic acid-containing polymers in vegetable fiber relative to that in bran. This is mainly because the former are rich in pectic substances, whereas the latter has very little (ifany) pectic material. Guar gum contains mainly galactomannans, which are neutral pohysaccharides, and as expected
TABLE 10 Carbohydrate anhydrosugar/mg
Sugar

In order to obtain further information on the constituent polymers, the DF samples were first purified to free them of intracellular polymers (eg, proteins and starch). The purified cell wall preparations were then fractionated by sequential extraction with aqueous inorganic solvents, and the isolated polymers were further fractionated on ionexchange columns, and analyzed for the constituent sugars (and amino acids) and glycosidic linkages. The results of purifying the DF-preparations and fractionating the CWM are given in Table 1 1 . During the purification stages appreciable amounts of pectic substances were solubihized from the cabbage, and carrot, and apple preparations, but only a relatively small amount of arabinoxylan was solubihized from wheat bran. This trend was further reflected in the hot water and 0.5% (w/w) oxalate-soluble fractions. However, the solubihity characteristics of cabbage and carrot pectins were impaired as a result of the drying process during the preparation of the AIR; some of the pectins were therefore extracted with 1 M KOH, resulting in a higher yield in this fraction. This was shown by fractionating the CWM isolated from fresh cabbage (33). The cabbage pectic substances are rich in arabinans, a small proportion of which are free, but the bulk are linked to rhamnogalacturonans; the carrot pectic substances, on the other hand,

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compositions of the DF preparations dry preparation)

Wheat bran

used
Cabbage

in the feeding
Carrot

trials

(76, 78) (values

Apple

are g
Guar gum

6-Deoyhexose Arabinose Xylosc Mannse Galaciose Glucose Uroniacid Lignir*

*

The

w/w)t lignin

content

5.5 139 210 12.3 15.1 179 58.6 85 (58.0) of the preparations

29.1 100 33.7 25.9 45.1 221 334 39 (60.4) was determined (ie. the alcohol-insoluble

27.6 65.1 10.6 19.9 108 241 351 33 (64.8) by the acetyl bromide residues) as eaten

28.7 60.2 49.1 18.3 48.3 303 391 35 (80.0) method are given

3.7 21.8 2.9 516 298 32.2

(72).

and

(90.2) is expressed brackets, and

as pg Iignin/mg dry preparation. 1 1 he DF content ofthe preparations include the values for lignin.

within

334 TABLE 11 Yields of material solubilized from [yield (mg/g recovered material)]
Fraction

SELVENDRAN

the DF-preparations
Wheat bran

during

purification
Cabbage

and

subsequent
Carrot

fractionation
Apple

(78)

NonstarchyPSsolubilizedt Hot water and Oxalate-soluble Chlorite/acetic acid-soluble 1 M KOH-soluble 4MKOH-soluble a-Cellulose * These preparations were

not treated

with

24.2 8.8 81 408 103 375 chlorite/acetic

233 68

301 93

167 106 51 53 623 very small amounts material. stages-these

168 92 95 66 436 448 acid because they contained only

oflignin. The a-cellulose from these preparations contained small but significant t Nonstarchy polysaccharides solubilized from the DF preparations during polysaccharides are mainly pectic substances.

amounts of pectic the purification

are rich in acidic-arabinogalactans (Stevens BJH, Selvendran RR, unpublished results). The bulk ofthe pentosans ofwheat bran can be solubihized only with alkali, and have been found to be mainly (acidic) arabinoxylans. For a detailed analysis of fiber from cabbage and wheat bran see References 19 and 77, respectively. The results of analysis of fiber from carrot and apple are in preparation for publication. For an account of the composition and properties ofapple cell wall polysaccharides see References 80 to 83. Possible mode preparations ofaction ofthe DF

The above studies show that the compositions and solubility characteristics of vegetable DF polymers are very different from those of wheat bran. Whereas the former contain mainly pectic substances, cellulose, and hemicelluloses (eg, xyloglucans), the hatter contain mainly acidic arabinoxylans, celhuhose, some /3-D-glucans, hignin, and phenolic esters. The chemical properties of these polymers (water-binding capacity, solubility, degree of substitution of the glycan backbone, presence or absence of galacturonic acid, association with lignin, cross-linkages by phenohic esters/acids, and proteins) may have an important bearing on the mode and extent ofdegradation ofthe parent DF preparations by bacteria in the large intestine. It has been shown that bacteria in the human colon can degrade some of the components of DF, such as pectins, arabinogahactans, xyhans, gahactomannans, and some arabinoxylans (8, 84-86), although these polymers, particularly those insoluble in buffer, are much less accessible when present as part

of the cell wall matrix. In a continuation of the earlier work of Cummings et a! (76), Stephen and Cummings (7) have reported that 36% of the wheat bran fiber was degraded in the gut compared with 92% of the cabbage fiber. The increase in fecal weight (127%) which was observed with bran was mainly due to incompletely degraded fiber and water held by it. Supporting evidence is provided by scanning electron microscope studies, which show that the cell wall structures of the hignified tissues of wheat bran are only slightly altered during passage through the gut (87, 88), or during incubation of the CWM from wheat bran with mixed populations of human fecal bacteria for 24 to 72 h at 37#{176}C (Stevens BJH, Selvendran RR, unpublished results). The latter studies also showed that on prolonged exposure to fecal bacteria (72 h), the relatively thick aleurone cell walls, which are not hgnified but have phenolic ester cross-linkages, underwent significant breakdown. This could be due to the structural characteristics of the acidic arabinoxyhans of bran and the protective action of hignin and phenohic esters (16, 77, 89, 90). The residual polymers bind water and appear to make a major contribution to the observed increase in fecal weight, compared with the bacterial mass. However, with cabbage fiber the smaller increase in fecal weight (69%) could be largely accounted for by the extrabacterial mass and its associated water with some contribution from partly degraded fibrous elements, which come mainly from cutinized and hgnified tissues. This is because fiber rich in pectic substances but poor in hignin and phenohic esters, such as those from cabbage

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(carrot and apple), stimulates microbial growth.. because very little fiber survives digestion by bacteria (7, 9 1). However, the structural and solubility characteristics of pectins could be important in determining the mode and extent ofdegradation of pectic substances by bacteria. With guar gum the contribution from undegraded fibrous tissues to the net increase in fecal weight would be minimal. However, since relatively few strains of colonic bacteria can degrade the highly branched galactomannan of the gum (85, 92, 93), the increase in fecal weight could be due to partly degraded gum as well as increased bacterial mass and the water associated with these components. Clearly more work is required on the mode and extent of degradation of DF polymers by the microorganisms of the human colon, in order to increase our understanding of the physiological effects of DF. El
The author thanks Miss Susan DuPont and Mr BJH Stevens for some of the unpublished results and for their help in preparing the manuscript.

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