14
Pure & Appi. C1-zem., Vol. 56, No. 7, pp. 879—892, 1984. 0033—4545/84 $3.OO+O.OO Printed in Great Britain. Pergamon Press Ltd. ©1984 IUPAC MICROBIAL POLYSACCHARIDES: NEW PRODUCTS AND THEIR COMMERCIAL APPLICATIONS Paul A. Sandford, Ian W. Cottrell, and David J. Pettitt Kelco Division of Merck & Co., Inc., San Diego, California 92123, USA Abstract - In the past two decades, significant progress has been made in the identification, characterization, and commercialization of microbially-derived polysaccharides. Although xanthan gum is the only commercially significant microbial '5olysaccharide to be used in food, industrial, and oil field appli- cations, other new microbial polysaccharides are the main topic of this paper. Gellan gum, a microbial polysaccharide from Pseudomonas elodea, is sold now for use in microbiological media as a gelling agent to replace agar. Gellan gum's unique properties also appear to have great potential in structured food products. S-13O, a biopolymer from a strain of Alcaligenes has excellent heat stability, suspending capabilities, and rheological properties which are useful in a variety of oil field applications. S-194, another biopolymer, has unusual compatibility with high levels of salts, is stable to shear, and has excellent suspending properties. S-194 is particularly useful in agri- cultural applications, especially suspension (liquid) fertilizers and flowable pesticides. New applications for xanthan gum, including its use in retort pouch foods, candy, farinaceous foods, jet and foam printing will be briefly reviewed also. It appears as if new microbial polysaccharides will continue to be dis- covered and some of these will undoubtedly outperform current polysaccha- rides in the market place. INTRODUCTION This paper will illustrate the wide diversity of properties found in microbial polysaccharides that have commercial applications. Currently, xanthan gum is the major significant commercial microbial product, but gellan gum, which is in its initial stages of commercialization, is currently being sold as an agar replacer for use in microbiological media (Table 1). Several pertinent reviews on microbial polysaccharides have appeared (1—11). TABLE 1. Microbial polysaccharides of commercial interest Type Microbial Source a. Commercially Available Xanthan Gum Anionic Xanthomonas campestris Gellan Gum Anionic Pseudomonas elodea Dextran Neutral Leuconostoc spp. b. Under Current Development S-13O Polysaccharide Anionic Alcaligenes spp. S-194 Polysaccharide Anionic Alcaligenes S1I. c. Developed to Large Scale Scieroglucan Neutral Sclerotium spp. Curdlan Neutral AgrobacteriThispp. Alcaligenes faecalis Pullulan Neutral Aureobasidium pullulans Bakers' yeast glycan Neutral Saccharomyces cerevisiae Bacterial al gi nate Anionic Azotobacter vi nelandi i Pseudomonas aeruginosa 879

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Pure & Appi. C1-zem., Vol. 56, No. 7, pp. 879—892, 1984. 0033—4545/84 $3.OO+O.OOPrinted in Great Britain. Pergamon Press Ltd.

©1984 IUPAC

MICROBIAL POLYSACCHARIDES: NEW PRODUCTS AND THEIR COMMERCIAL APPLICATIONS

Paul A. Sandford, Ian W. Cottrell, and David J. Pettitt

Kelco Division of Merck & Co., Inc., San Diego, California 92123, USA

Abstract - In the past two decades, significant progress has been made in theidentification, characterization, and commercialization of microbially-derivedpolysaccharides. Although xanthan gum is the only commercially significantmicrobial '5olysaccharide to be used in food, industrial, and oil field appli-cations, other new microbial polysaccharides are the main topic of this paper.Gellan gum, a microbial polysaccharide from Pseudomonas elodea, is sold nowfor use in microbiological media as a gelling agent to replace agar. Gellangum's unique properties also appear to have great potential in structured foodproducts. S-13O, a biopolymer from a strain of Alcaligenes has excellentheat stability, suspending capabilities, and rheological properties which areuseful in a variety of oil field applications. S-194, another biopolymer,has unusual compatibility with high levels of salts, is stable to shear, andhas excellent suspending properties. S-194 is particularly useful in agri-cultural applications, especially suspension (liquid) fertilizers and flowablepesticides.

New applications for xanthan gum, including its use in retort pouch foods,candy, farinaceous foods, jet and foam printing will be briefly reviewed also.

It appears as if new microbial polysaccharides will continue to be dis-covered and some of these will undoubtedly outperform current polysaccha-rides in the market place.

INTRODUCTION

This paper will illustrate the wide diversity of properties found in microbial polysaccharidesthat have commercial applications. Currently, xanthan gum is the major significant commercialmicrobial product, but gellan gum, which is in its initial stages of commercialization, iscurrently being sold as an agar replacer for use in microbiological media (Table 1). Severalpertinent reviews on microbial polysaccharides have appeared (1—11).

TABLE 1. Microbial polysaccharides of commercial interest

Type Microbial Source

a. Commercially Available

Xanthan Gum Anionic Xanthomonas campestrisGellan Gum Anionic Pseudomonas elodeaDextran Neutral Leuconostoc spp.

b. Under Current Development

S-13O Polysaccharide Anionic Alcaligenes spp.S-194 Polysaccharide Anionic Alcaligenes S1I.

c. Developed to Large Scale

Scieroglucan Neutral Sclerotium spp.Curdlan Neutral AgrobacteriThispp.

Alcaligenes faecalisPullulan Neutral Aureobasidium pullulansBakers' yeast glycan Neutral Saccharomyces cerevisiaeBacterial al gi nate Anionic Azotobacter vi nelandii

Pseudomonas aeruginosa

879

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880 P. A. SANDFORD et al.

DRIVING FORCES IN MICROBIAL POLYSACCHARIDE DEVELOPMENT

Unlike traditional gums, microbial polysaccharides can be produced uniformly and reliably byfermentation. Thus, microbial polysaccharides are not subject to variations in climatic con-ditions. Besides stability in supply, other factors favoring microbial polysaccharides, suchas xanthan gum, include their improved and sometimes novel functionality. Often microbialpolysaccharides allow superior commercial products to be formulated and in somes cases at alower cost.

MAJOR MARKETS OF POLYSACCHARIDES

Polysaccharides are used commercially to thicken, suspend, or stabilize aqueous systems.Also they are used to produce gels and to act as flocculants, binders, film-formers, lubri-cants, and friction reducers.

Tables 2 lists the most important industrial markets, and Table 3 the food markets of

polysaccharides, including plant, seaweed, and microbially—derived products, (1, 12—14).Traditionally, industrially useful polysaccharides have been derived from algal and plantsources, but in more recent times polysaccharides such as xanthan gum, microbially derived,have found increased usage.

TABLE 2. Polysaccharide Applications

ADHESIVES (also see Paper)- Latex- Tile Mortars (Cement)- Wallpaper

AGR ICULTURE- Flowable pesticides

- Liquid fertilizers- Liquid feed supplements

CERAMIC, REFRACTOR IES,WELDING RODS

CLEANERS, POLISHES

DETERGENTS

EXPLOSIVES- Ammonium nitrate

slurries

- Package gels

FIRE-FIGHTING

INK (FLEXO, GRAVURE, JET)LITHOGRAPHY

METAL-WORKING- Refractory Coatings

MINING (HEAVY MEDIA

SEPARATION)

RheologyFluid loss/rheology

Thickening

Suspensi on—dri ft

control

Suspensi on

Suspensi on

Slip AgentSuspensionAbrasive, suspension,

acid and Base stabilityAnti redeposition,

antisoil

Water resistnace

Foam stabilization,ignition retardati on

RheologyLow-Vi scosity-

High-Solids

Suspension

Suspensi on

Cel lulosic den vatives

Methylcel lulose

Algin, starch, modifiedstarch

Xanthan gum

Xanthan gum

Xanthan gum, guar gum,Al gin

Xanthan GumXanthan Gum

Carboxymethylcellulose

Guar gum,

hydroxypropyl guar gum,xanthan gum

Guar gum,

hydroxypropyl guar gum,xanthan gum

Guar gum, guar derivativesand xanthan gum

Gum arabic

Table 2 contd. on p. 881

Market and

Application Properties Polysaccharides

Ca(N03)2 compatibility

Xanthan gum, starch, guar

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Microbial polysaccharides 881

TABLE 2. Polysaccharide Applications: cont.

Market!Application Properties Polysaccharides

OILFIELD— Drilling Muds

- Enhanced Oil Recovery

Polymer Flooding- Fluid-loss additives- Slimulation

Hydraulic fracturing

- Acidizing

Viscosity, suspension

Viscosity

Fluid loss propertiesSuspension, fluid loss,

viscosity reduction bychemical/enzymaticbreakers, crosslinkabl

Suspension, stabilityto strong acids atelevated temperatures

Xanthan gum, celluloseethers

Xanthan gum

CMC

Hydroxypropyl guar gum,Hydroxyethyl cellulosexanthan gum, Carboxy-

e methyl celluloseXanthan gum

PAINT- Latex Trade Sales

- Maintenance Coatings- Industrial Coatings

PAPER- Wet end binder

- Coatings

— Surface Sizes

- Particle board,corrugated board

PHOTOGRAPHY

POLYMER I ZAT ION- Emulsion— Suspension

ROOM DEODORANT GELSTEXTILES

— Warp sizing

- Printing

- Batch dyeing- Pad dyeing- Pigment printing

Formation-beater aid

Rheology

Film-Forming, water-loss, printing

Extend glue

Antistatic Coating,extensi on

Protective colloid

Suspensi on

Stable gel

Film forming

Rheologyantimi grant-di sperse

dyesSame as PrintingSame as PrintingRheol ogy-bi nder

compatabi 1 i ty

Hdroxyethyl cellulosemethyl cel lulose,

(microbial biopolymers)

Modified starch,

guar derivatives,locust bean gum,

and karaya gumAl gin, Carboxymethyl -

celluloseStarch, modified

starch and algin

Sodium cellulose sulfate

Hydroxyethyl celluloseXanthan gumCa rrageenan

Starch, modifiedstarch and CMC

Al gin

Algin, KarayaModified starch, Hydroxy-

ethyl cellulose, methylcellulose, hydroxypropylguar gum, guar, locustbean gum

Modified starch, Hydroxy-ethyl cellulose, methylcellulose, hydroxypropylguar gum, guar, locustbean gum

Cel lulosics

Rheology-suspensi on

- Jet printing Rheology

Fabric finish Fiber substantivity

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882 P. A. SANDFORD et al.

TABLE 3. Polysaccharide food markets (1)

U) U) U)

U)1)004—

>)L

U)

004--

Va)CC(0L)

U)C004—

Va)U)U)rO

((3

4-)U

0LC)

>,La)

((3

U)+-)000L0>)L—((3

U)0o04—

Ca)NLU

CCU)va)LVV(0((3V)

U)a)(0L0)>a)

U)

C'-LV4-'4-0V)

C•-L

>)-a)c00a)4-C0L)

(00•-4-)

a)Q(0EL(0CCL

U)0•-4)a)EU)0L)

U)4-)CDLa)

0)

U)0004-

a)CL

Microbial

XanEFiigum x x x x x x x x x x x x

Seaweed

Af4fnates x x x x x x x x x x x xAgar x x x x x

Carrageenan x x x x x x

PlantGuar Gum x x x x xLocust Bean Gum x x xPsyllium Husks x

Quince Seed x

GumArabic x x x x x x x

Gum Tragacanth x x x x x x x

Gum Karaya

Cel lulosicsCMC x x x x x x x x x x xHPC x x xHEC x x

MicrocrystallineCellulose x x x

GELLAN GUM

Source - The fermentation and isolation of gellan gum have been previously described indetail and will not be discussed further here (15-17) There are two commercial forms ofgellan gum: one that forms a brittle gel and one that forms an elastic gel.

Composition/Structure - In the search for microbial polysaccharides with solution propertiesof commercial interest, the exocellular polysaccharide elaborated from the bacterium Pseudo-

elodea (14, 15) was found. This polysaccharide contains 0-acetyl groups, which whenremoved by hot, alkaline treatment gave aqueous solutions which have low viscosity at elevatedtemperatures but which form strong gels on cooling in the presence of cations (17). Thispolysaccharide, now called gellan gum, has been shown to be composed of tetrasaccharide

repeating units having the following structure. [->3)-c3 -D-Glcp-(1->4)-a -D-Glcp A-(1->4)-c-D_Glcp_(1->4)-oc_L-Rhap_(1->] (18-19). NMR indicates that the position of the 0-acetylgroup(s) is on the C-6 position of one of the glucose units.

Properties — Brittle gellan gum gels are similar to carrageenan gels and like carrageenan,gellan gum requires cations for gelation (20) (Table 4). Like agar, brittle gellan gum gelsexhibit marked melting/setting hysteresis. Figure 1 illustrates that maximum gel strengthsare achieved with lower divalent cation levels than with monovalent cations.

TABLE 4. Gellan gum gel properties: comparison with Carrageenan and Agar

Gel

Nature

MeltingPoint

(°C)

SettingPoint

(°C)

Hysteresis(°C)

Gellan Gum Brittle 90 40 45-60

Kappa Carrageenan Brittle 40-95 25-75 12-20

Agar Brittle 60-97 32-39 <65

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EU

a)

Cl)

0)a

Fig. I

Microbial polysaccharides 883

Fig. 1. Effect of cations on the gel strength of gellan gum (Gelrite").

Fig. 2. Gel strength of gellan gum (Gelrite") as a function of gellan gum andMgF concentrations.

Microbiological Media - Currently a gellan gum product with excellent clarity is being soldunder a trade name of GELRITE" as a gelling agent for the preparation of microbiological

media (22-23). In this application, GELRITE forms high gel strength gels that are stable tomultiple autoclavings, chemically inert to most biological growth media additives, generallyresistant to enzymatic degradation, and melt/set reversibly like agar. Figure 2 shows theeffect of gellan gum and magnesium (Mg) concentration on gel strength. By adjusting theconcentration of gellan gum or magnesium ions, a large range of gel strengths is available.Typically, the gel strength of microbiological media is between 200-400 g/cm2. Three appar-ent advantages of GELRITE over agar are 1) improved clarity, 2) equivalent gel strength atabout 1/3 to 1/2 the use level, and 3) reduced toxicity to sensitive microorganisms and planttissue cultures. A recent study (23) also indicates that GELRITE is superior to agar as a

gelling agent in media for the growth of thermophilic microorganisms (Table 5). Most gelsformed by heating and cooling gellan gum remelt on heating.

TABLE 5. Comparative growth of thermophiles on media solidified with GELRITE'" or agar (23)

Organism Basal medium Gelling Agent Gelling AidIncub

Temp(°C)

ationTime

(h)

Gel

St.

(g/cm2)

Med.

Appear.after Inc

CFU(mean

±SD)

B. acidocal-darius

Bacillus mediumBacillus medium

2% Agar0.55% GELRITE 0.057% CaCl2.2H20

5555

2424

550470

CloudyClear

15 + 2780+T63

B. stearother-

mophilus

Nutrient brothNutrient brothNutrient broth

2% Agar0.8% GELRITE

2% Agar0.1% MgCl2.6H200.1% MgCl2.6H20

555555

242424

402620-

CloudyClear

Cloudy

1,216+27446+30536+26

T. thermo-phiTus

Thermus medium

Thermus medium

3.0% Agar

1.1% GELRITE 0.1% CaCl2.2H20

70

70

48

48

1,150

910

Cloudysemigel

Clear;intact

gel

0+0

792+30

T. aquaticus Castenholz TYEmedium

Castenholz TYEmedium

1.5% Agar

0.8% GELRITE

70

70

48

48

275

455

Cloudy;bubbles

Clear; nobubbles

16+1

767+13

a For each organism similar inoculum levels were used for all media, CFU = Colony Forming Units.

0.2 0.4 0.6 0.8 0.05 0.0625 0.075 0.0875 0.10

Concentration of Salt (%) CONCENTRATION OF MgCI2 • 6H20 (%)

Fig. 2

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884 P. A. SANDFORD et al.

TABLE 6. Typical potential food applications of Gellan Gum

Major foodarea Typical Products

Function of Gellan Gum

Confectionery Starch jellies, pectinjellies, fillings,marshmallow

Provide structure/texture,reduce set time

Jams and jellies Reduced-calorie jams,imitation jams, hak-

cry fillings, jellies

Provide consistency/gel,reduce syneresis

Fabricated foods Fabricated fruits, veg-etables, meats

Gel matrix, freeze/thawstability

Water-based gels Dessert gels, aspics Good mouth feel, gelatinreplacer

Pie fillings and Instant desserts, Starch replacer, eliminatepuddings canned puddings,

precooked puddings,pie fillings

syneresis

Pet foods Canned meat chunks,

gelled pet foodsProvide structure/shape

Icings and Bakery icings, canned Prevent moisture loss,frostings frostings cracking, sugar crystalli-

zing, agar replacerDiary products Ice cream, gelled milk,

yogurt, milkshakesGel structure

Food Systems - Properties such as those described above make gellan gum suitable for use infood systems (24-26). Gellan gum has not yet been cleared by FDA for use in food. Table 6shows typical food applications where gellan gum has potential. Particularly attractive arethe gel melting temperatures that gellan gum offers. Some food products may be required tomelt for reprocessing, while others may require a gel structure that is stable to heat treat-ment (e.g., frying). The setting temperature is usually between 300 to 45°C while the meltingtemperature can be either above or below 100°C, depending on conditions of formation such astypes and amounts of cations. In some products, desirable texture, body and mouthfeel can beachieved by using gellan gum in combination with other food hydrocolloids such as xanthan

gum, locust bean gum, guar gum, carboxymethylcellulose (CMC), modified starches, agar,carrageenan, gelatin, algin, or pectin.

Microencapsulation - Gellan gum forms rigid coacervate gels in the presence of gelatin.These coacervate gels have been found to be suitable for use in microencapsulation (27).Above 60°C, gellan gum forms a fluid low viscosity coacervate with gelatin, while at 25°Cit produces a high strength coacevate gel. Gellan gum/gelatin coacervates are stable over awide pH range and in the presence of soluble salts. Gellan gum coacervate gels containcarboxyl groups that are available for chemical crosslinking.

Industrial Gels - Both aqueous and glycol (ethylene glycol, propylene glycol, glycerol) gelshave industrial uses (28). For example, air freshener gels can be made and the rate ofevaporation can be varied by varying the glycol content.

S-130 POLYSACCHARIDE

Source - S-130 polysaccharide, produced by an Alcaligenes species in an aerobic submergedfermentation, is described in U.S. Patent 4,342,866 (29).

Composition/Structure - Initial data indicates that the S-130 polysaccharide is composed ofglucose: rhamnose: glucuronic acid in the ratios of 2:2:1 with varying amounts of mannose

(v1 part).

Outstanding Properties - Besides having high viscosity at low concentrations, excellentsuspending properties, pseudoplastic rheological properties (shear thinning), and excellentstability towards pH (2-12) and shear, polysaccharide S-130 has the outstanding property ofunusual and excellent viscosity retention at temperatures up to 150°C ("300°F). In Figure 3the viscosity-temperature profiles of S-130, xanthan gum, and hydroxyethylcellulose (HEC) arecompared, demonstrating that the viscosity of S-130 is more stable at high temperatures thaneither HEC or xanthan gum. Table 7 compares the viscosity half lives of these three gums atvarious temperatures. Again S-130 can be seen to have excellent viscosity stability at high

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Microbial polysaccharides 885

temperatures, suggesting that 5-130 will have potential in applications where viscosity attemperature is required. One such application would be drilling fluids used to drill deep,and hence hot, wells.

S-130 is an excellent suspending agent. Whether the solids are cuttings, weighting material,bridging particles, fracturing sand, or gravel for packs, S-130 suspends better than otherpolymers used in oil field applications such as HEC or hydroxypropyl guar (See Figure 4).

S-130 develops high viscosity in most saline waters (e.g., 3% KC1, seawater, brackish waters,saturated NaC1 and CaCl2 up to 20%), although it is not recommended for use in saturatedheavy brines above a density of 1.3 (eg. saturated CaCl2, CaBr2). The viscosity of S-130 isrelatively stable to pH changes, although viscosity loss does occur at pH values above 11.0in the presence of elevated levels of Ca.

S-130s rheological characteristics, however, are ideal for a low-solids drilling mud and forother aqueous oil field fluids at high temperature in the deeper oil wells.

TABLE 7. Viscosity half-lives at temperature

Half-lives (minutes) at Temperature

Product 225°F 250°F 265°F 275°F 300°F 325°F

Hyd roxyethylCellulose 65 10 0 0 0 0

Xanthan Gum 428 273 100 0 0 0

S-130 N.D. N.D. N.D. 900 50 2.5

Viscosity of 0.4% gum inviscometer at 100 sec-1.

60

50U0

Lt)CCC,L1 40

U

30

©a-U

U,0UU)>

20

10

050° 80° 100°

3% KC1 with 300 ppm Na2503, measured with Fann 50C

Fig. 3. Viscosity versus temperature curves. Comparsion of S-130 with hydroxy-

ethylcellulose (HEC) and xanthan gum (KELZAN XC®).

150° 200° 250° 300° 325° 350°Temperature, °F

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886 . A. SANDFORD et al.

S-194 POLYSACCHARIDE

Source - S-194 polysaccharide, produced by an Alcaligenes species in an aerobic fermenta-tion process, is described in U.S. Patent 4,401,760 (30). After growth on a medium with glu-cose as a carbon source, the polysaccharide is recovered by alcohol precipitation, dried, andmilled.

Composition - S-194 is composed of glucuronic acid, glucose, and rhamnose in the approximatei€ios of 1:4:1 and also contains 0—acyl groups (4% as acetyl). The structure of S-194 isnot currently known.

Outstanding Properties - S—194's key features are its compatibility with high levels of saltand its ability to suspend components of suspension fertilizers (31). Like S-130, S-194provides high viscosity at low concentrations and low shear rates. The viscosity of S-194solutions is not affected by high temperatures even at 100°C (see Figure 5). Figure 6 showsthat S-194 has pseudoplastic rheology (shear thinning) much like xanthan gum.

C20

a)

c5 15

0,C10

a)C/)

Fig. 4. Suspension capabilities of S-130 using 10—20 mesh sand: Comparsion with

xanthan gum (KELZAN XC®), hydroxypropyl guar (HP Guar), and hydroxyethylcellulose(HEC). Conditions: 1 pound gum/barrel; 3% KC1; 175°F; 10-20 mesh sand.

I I I

Fig. 5. Viscosity of S-194 versus temperature. Conditions: 0.5% S-194: Fann 50 cviscometer, 100 sec-1.

Fig. 6. Viscosity versus shear rate of S-194 and xanthan gum. Brookfield LVF

viscometer, appropriate spindle, 25°C; gum concentration, 0.25%.

30

25

Greater than 25 ft/mm

nfl5

S.130 Xanthan Gum HPGuar175°F

HEC

100

10

a.U

a)0Ua)>

Fig. 5

I__I

U

a)8a)

80 120 160 200 240 260 280

Temperature (° F)Brookfleld RPM

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Microbial polysaccharides 887

Suspension fertilizers have become popular because lower production costs are achieved by use

of lower grades of materials, grades of higher analysis than normal liquids are possible,especially higher percentages of potassium, and micronutrients can be uniformly distributed.

Although most polysaccharide suspending agents are usually incompatible (e.g., salt out) withthe high concentrations of ammonium polysphosphate or orthophosphate used in suspensionfertilizers, S-194 has excellent suspension capabilities and salt compatibility and formula-tion of a wide variety of suspension fertilizers (See Figures 7 and 8).

26,000

C.)

100

0a)E•: 50

Fig. 7. Suspension capabilities of S-194 and other gums using resin beads. Allsolutions were adjusted to 200 cP (Brookfield LVF, spindle No. 2, 60 rpm, 25°C).The beads were"5 mm in diameter and had a density of 1.25 g/cc. CMC = carboxy-methylcellulose, HEC = hydroxyethylcellulose, GUAR = guar gum.

Fig. 8. Relative compatibility of S-194, xanthan gum and guar gum with ammoniumpolyphoshate (10-34-0). S-194 will accomodate more ammonium polyphosphate without

salting out.

TABLE 8. Major food and industrial applications of xanthan gum

FOOD

Dressings (high oil, low oil, no oil)Relishes and sauces

Syrups and toppingsStarch-based products (canned desserts, sauces, fillings, retort pouches)Dry mix products (desserts, gravies, beverages, sauces, dressings)Farinaceous foods (cakes)

BeveragesDairy products (ice cream, shakes, processed cheese spread, cottage cheese)Confecti onery

INDUSTRIAL

Flowable pesticides

Liquid feed supplementsCleaners, abrasives, and polishesMetal-workingCeramics

Foundry coatingsTexturized coatings

Slurry explosivesDye and pigment suspensions

OIL FIELD

Drilling fluids (muds)Workover and completion fluidsStimulation - hydraulic fracturing

- acidizingEnhanced oil recovery - polymer flooding

Fig. 8

XanthanGum

Guar Gum

Resin Beads

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888 P. A. SANDFORD et al.

Commonly use levels of about 0.1% of S-194 can replace 1-3% attapulgite clay, the suspending

agent frequently used.

Another outstanding property of S-194 is its stability towards shear. In the preparation offlowable pesticides it is standard practice to grind the active ingredient to a fine particlesize (e.g., <5ym). Often used is a Dyno Mill that uses glass beads as the grinding mediumand imparts such intense shear that the viscosity of most polymer solutions is irreversiblylost. Figure 9 shows that S-194 is very stable to shear in a Dyno Mill.

a.0>1

; 100000U)

Fig. 9. Effect of DYNO-MILL treatment on the viscosity (Brookfield LVF Viscometer,3 rpm, 25°C, appropriate spindle) of S-194, xanthan gum and hydroxyethylcellulose(HEC). Glass beads are the grinding medium.

NEW APPLICATIONS FOR XANTHAN GUM

Since xanthan gum is the only microbial polysaccharide used extensively in food and indus-trial applications, a few new uses of xanthan gum will be mentioned briefly. Xanthan gum hasbeen successfully used in various commercial applications since the 1960's and its use infood and industrial applications is due to its remarkable properties that include 1) high

viscosity at low concentration, 2) high pseudoplasticity (shear thinning), 3) yield value!suspending power, and 4) stable viscosity towards salts and a wide range of temperature andpH.

Although Table 8 lists the major commercial applications of xanthan gum, I would like tohighlight a few of the most recently identified applications (32).

Retort Pouch Foods (33) - An alternative to the conventional cans, jars and foil trays, re-tort pouches are finding increased usage for foods because the resulting foods have bettercolor, firmer texture, and fresher flavor as a consequence of reduced sterilization times inretorts. Xanthan gum is being used in retort pouch foods to maintain filling consistency,improve heat penetration, replace (partial) starch, and provide a clean, non-pasty mouthfeel.

Starch-jelly Confections (34) - Combinations of xanthan gum and locust bean gum (KELGUM®)form a useful thermally-reversible gelling system that provides accelerated gelling to re-duce set time, extended shelf life, improved water control and retention, and clean mouthfeelwithout pastiness.

Farinaceous Foods/Cakes (35) - In these products, the subtle interactions of xanthan gum withother ingredients (sucli as starch and protein) can result in increased moisture binding andretention, improved volume with less fragility, better rheological control of batters duringmixing, pumping, and baking, improved cell structure in the finished cake, due to foam/aircell stabilization, better suspension of fruits or nuts during processing, and improvedtolerance to variation in production conditions and ingredient quality.

5 10

Time, mm.

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Microbial polysaccharides 891

SUMMARY

The purpose of this paper has been to illustrate that microbial polysaccharides have a widediversity of properties and potential/new uses. It is anticipated that industry's trendtowards water-based thickeners, foaming and gelling agents, industry's continual seeking forlower cost and higher functional products, and the need for new and improved polymers willallow microbial biopolymers to capture markets traditionally occupied by traditional gums.

REFERENCES

1. P. A. Sandford, and J. Baird, "Industrial Utilization of Polysaccharides", Thesaccharides 2, p. 411-490, Academic Press, New York (1983).

2. J. K. Baird, P. A. Sandford, and I. W. Cottrell, Bio/Technology 778-783 (1983).

3. K. S. Kang, G. T. Veeder, and I. W. Cottrell, "Some Novel Bacterial Polysaccharides ofRecent Development, "Progress in Industrial Microbiology 18, p. 231-253, Elsevier,New York (1983).

4. P. A. Sandford, Adv. Carbohydr. Chem. 36, 265-313 (1979).

5. P. A. Sandford, Polysaccharides in Food, p. 251-262, Butterworth, London (1979).

6. D. J. Pettitt, Polysaccharides in Food, p. 263-282, Butterworth, London (1979).

7. I. W. Cottrell and J. K. Baird, Kirk-Othmer Encycl. Technol., 3rd Ed. 12, 45-66 (1980).

8. K. S. Kang and I. W. Cottrell, Microbiol. Technol. 1, 417-481 (1979).

9. I. W. Cottrell, K. S. Kang, and P. Kovacs, "Xanthan Gum", Handbook of Water-SolubleGums and Resins, McGraw-Hill, New York, 24-1 to 24-31 (198Df.

10. P. A. Sandford and A. Laskin, eds., Extracellular Microbial Polysaccharides, ACS Sympo.Ser. 45, Am. Chem. Soc., Washington (1977).

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(1973)

12. Anon., Thickening Agents: Consumer Products, Charles H. Kline & Co., Fairfield, New

Jersey fI75).

13. Anon., Thickening and Sizing Agents: Industrial Products, Charles H. Kline & Co.,

Fairfield, New Jersey (i97).

14. Anon., Paper Industry, 4th ed., Charles H. Kline & Co., Fairfield, New Jersey (1980).

15. K. S. Kang and G. T. Veeder, U.S. Pat. 4,377,636 (1983).

16. K. S. Kang and G. T. Veeder, U.S. Pat. 4,326,053 (1982).

17. K. S. Kang, G. T. Colegrove, and G. T. Veeder, U.S. Pat. 4,326,052 (1982).

18. P.-E. Jansson, B. Lindberg, and P. A. Sandford, Carbohydr. Res. 124, 135—139 (1983).

19. M. A. O'Neil, R. R. Selvendran, and V. J. Morris, Carbohydr. Res. 124, 123—133 (1983).

20. R. Moorhouse, G. T. Colegrove, P. A. Sandford, J. K. Baird, and K. S. Kang,Am. Soc. Soc. Symp. Ser. 150, 111-124 (1981).

21. K. S. Kang, G. T. Veeder, P. J. Mirrasoul, T. Kaneko, and I. W. Cottrell, Appl.Environ. Microbiol 43, 1086-1091 (1982).

—22. 0. Shungu, M. Valiant, V. Tutlane, E. Weinburg, B. Weisberger, L. Koupal,

H. Gadebusch, and E. Stapley, Appi. Environ. Microbiol. 46, 840-845 (1983).

23. C. C. Lin and L. E. Casida, Jr., Appi. Environ. Microbiol. 47, 427-429 (1984).

24. I. W. Cottrell, "Industrial Potential of Fungal & Bacterial Polysaccharides," FungalPolysaccharides, ACS Symp. Serv. 126, Am. Chem. Soc., Washington, 251-270 (198QJ.

25. Anon., Food Eng. 55, 52-53 (1983).

26. G. R. Sanderson and R. C. Clark, Food Technol. 37, 63-70 (1983).

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892 P. A. SANDFORD et al.

27. Anon., "Gellan Gum in Micro-encapsulation", Commercial Development Bulletin CD-31,Kelco Div. of Merck & Co., Inc., San Diego, CA. (1983).

28. Anon., "K9A50 for Use in Aqueous Gel systems", Commercial Development Bulletin CD-30,Kelco Div. of Merck & Co., Inc., San Diego, CA.719S3).

29. K. S. Kang and G. T. Veeder, U.S. Pat. 4,342,866 (1982).

30. J. A. Peik, S. M. Steenbergen, and H. R. Hayden, U.S. Pat. 4,401,760 (1983).

31. G. 1. Colegrove, md. Eng. Chem. Prod. Res. Dev. 22, 456-460 (1983).

32. M. Lawson and E. E. Fitzgerald, Abstr. 185th Am. Chem. Soc. Meeting, Carb.Seattle, WA (1983).

33. Anon., "KELTROL® Xanthan Gum for Use in Foods Packaged in Retort Pouches", TechnicalBulletin F-79, Kelco Div. of Merck & Co., Inc., San Diego, CA. (1980).

34. Anon., "KELTROL® Xanthan Gum With Locust Bean Gum in Starch Jelly Candies", TechnicalBulletin F-79, Kelco Div. of Merck & Co., Inc., San Diego, CA. (1981).

35. Anon., "KELTROL® and KELTROL® F Food Grade Xanthan Gums for Farinaceous Foods",Technical Bulletin F-78, Kelco Div. of Merck & Co., Inc., San Diego, CA. (1982).

36. G. C. Varner, U.S. Pat. 4,170,883 (1979).

37. Anon., "KELZAN® Xanthan Gum as a Foam Stabilizing Aqent in Textile Applications",Technical Bulletin TX-12, Kelco Div. of Merck & Co., Inc., San Diego, CA. (1982).