MOLECULAR ASSOCIATION IN DEXTRAN AND IN BRANCHED AMYLACEOUS CARBOHYDRATES

BY ALLENE JEANES, N. C. SCHIELTZ,* AND C. A. WILHAM

(From the Starch and Dextrose Division and the Analytical and Physical Chemical Division, Northern Regional Research Laboratory,t Peoria, Illinois)

PLATE 3 (Received for publication, June 21, 1948)

A property of polysaccharides which is of major importance both prac- tically and fundamentally is orderly association between portions of the same or of adjacent molecules. This property depends upon both the physical and chemical constitution of the polysaccharide and data on it provide a means for correlating physical properties with chemical structure. Little specific information is available on molecular association in branched polysaccharides. The industrial importance of starch and the biological significance of glycogen and certain bacterial polysaccharides make such information desirable.

This paper presents information on molecular association in the bac- terial polysaccharide, dextran from Leuconostoc mesenteroides, and in branched amylaceous substances. Orderly molecular association has been detected by x-ray analysis, and the tendency towards orderly association has been related to the physical and chemical constitution of these poly- saccharides. Data are given on typical x-ray diffraction powder patterns of dextran, and on the relation of molecular association to the hydration and ease of dissolution of branched polysaccharides.

Chemical and Physical Nature of Dextran-Dextran is known to be a polymer of a-n-glucopyranose (1). Methylation studies on a water-soluble dextran (2) have shown that the molecule has a branched structure in which the predominant glucosidic linkage is 1,6- while 1,4-linkages occur at the points of branching. A point of branching for every 5 glucose units was indicated by these data. Less quantitatively exact methylation studies on other dextran preparations have indicated fewer side chains (1, 3). In amylaceous substances the predominant glucosidic linkage is a-1,4- while 1,8linkages occur at the points of branching (4). The presence of 1,6- linkages in starch makes further knowledge of other polysaccharides con- taining this linkage desirable for comparative purposes.

* Present address, United States Department of the Interior, Bureau of Recla- mation, Denver, Colorado.

t One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.

617

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618 DEXTRAN AND AMYLACEOUS CARBOHYDRATES

Dextran has been shown to be filiform in nature by electron microscopy (5), by ultracentrifugation (6), and by birefringence of flow (6). Grijnwall and Ingelman (6) reported that the molecular weight of the dextran studied by them was of the order of “many millions,” but accurate evaluation was prevented by the inhomogeneity of size of the molecules.

Dextran molecules appear to differ in size (7) and probably in some de- tails of chemical structure when prepared under different conditions and by different strains of Leuconostoc mesenteroides. Our observations on the water-soluble dextran from Leuconostoc mesenteroides NRRL B-512 which was used in this study indicate that, with the possible exception of the degree of branching, this dextran appears to conform to the structural char- acteristics indicated above. It cannot be assumed that the methylation data available (2) apply exactly to our dextran.

Molecular Order and Association-Samples of polysaccharides which pro- duce x-ray diffraction powder patterns containing a set of diffraction lines are called “crystalline.” A crystalline polysaccharide is ordinarily a mixture of regions which range in degree of molecular order between the theoretical extremes of complete crystallinity and complete randomness. A single polysaccharide molecule may extend through several different re- gions (8). In the crystalline regions segments of primary valence chains are in ordered spatial arrangement where energy relations favor systematic lateral association between chains through hydrogen bonds. In amorphous regions chain segments are in disorderly arrangement. X-ray patterns from ordinary crystalline polysaccharides are composites of the diffraction lines which originate in the crystalline regions and of the halo of diffuse reflections from the amorphous regions. Amorphous polysaccharides, which produce only diffuse x-ray reflections, are believed to vary in the ex- tent and in the degree of randomness of molecular association.

EXPERIMENTAL

Materials and Methods--Unless otherwise stated, the dextran used has been the water-soluble product from Leuconostoc mesenteroides NRRL B-512 and was prepared and characterized as described in a previous study (7).

Humidification in an atmosphere having 100 per cent relative humidity at 25” has been used to convert amorphous samples of glutinous corn- starch, amylose-free corn amylopectin, and certain fractions from acid- hydrolyzed dextran to the crystalline state. Dextrans and acid-hydrolyzed dextrans have produced line patterns after treatment under special con- ditions with specific optimum concentrations of aqueous ethanol. Crystal- lization has also been found to develop in dextran when its aqueous pastes were dried at elevated temperatures. These general methods, or the fun- damental principles underlying them, have been used previously in studies on starch (9, 10) or other polysaccharides (11).

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A. JEANES, N. C. SCHIELTZ, AND C. A. WILHAM 619

X-ray patterns were made with unfiltered copper radiation transmitted through the finely pulverized samples which were packed in holders 1 mm.

thick. Before the pattern was taken, all samples which had been stored several days in an atmosphere having 100 per cent relative humidity at 25” were permitted to dry in the air from 1 to several hours to reach a satisfactory condition for mounting. The exact state of hydration of samples when x-rayed has not been defined.

Amorphous Des&an-Dextran is normally isolated as a fluffy white solid (7) which gives an amorphous x-ray pattern, and in which the random- ness of molecular association is very high. Unless otherwise stated, amor- phous dextran has been the starting material used in all the experimental work described here.

Amorphous dextran takes up 12 to 13 per cent moisture when equilibrated in an atmosphere having 50 per cent relative humidity at 25”. When a small amount of amorphous dextran was exposed in an atmosphere having 100 per cent relative humidity at 25”, it changed to a clear, thick syrup within 2 to 3 hours. After 3 days under these conditions, x-ray examina- tion showed the dextran still to be amorphous. These observations have been made on dextrans with relative viscosity1 of 2.003, 1.816, and 1.414.

X-ray Data and Patterns-Three general types of x-ray diffraction pow- der patterns, one of which has two modifications, have been obtained from dextran and acid-hydrolyzed dextran. The x-ray data for these typical patterns are given in Table I and illustrations are given in Fig. 1.

Preparation and Properties of Samples

Dextran Treated with Aqueous Ethanol-O.5 gm. samples of dextran (rela- tive viscosity’ 1.816) were dissolved in 15 cc. of distilled water in small glass-stoppered flasks, and absolute ethanol was added to make ethanol con- centrations of 40, 50, 60,70, and 80 per cent by volume, respectively. The dextran precipitated and was allowed to stand under the aqueous ethanol for 7 days at 25”. The precipitates were then removed and dried in vacua over anhydrous calcium chloride at 25”. When dry, the sample from 60 per cent ethanol pulverized with great ease and the sample from 70 per cent ethanol pulverized easily, but all the other samples could be broken only into lumps. The samples from 40 and 50 per cent ethanol produced amorphous x-ray patterns, those from 60 and 70 per cent ethanol produced line patterns of type L-l, and the sample from 80 per cent ethanol gave a pattern with traces of lines on a diffuse background.

Humidification for 3 days in an atmosphere saturated with water vapor at 25” produced no apparent change in the dry, pulverized samples from 60 and 70 per cent ethanol, but resulted in increased sharpness of the type

1 Viscosities were mcasurecl on 0.5 per cent solutions in water at 25” (7).

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620 DEXTRAN AND AMYLACEOUS CARBOHYDRATES

L-l patterns produced. When humidified, the sample from 40 per cent ethanol dissolved readily to a clear syrup, which, after drying, produced an amorphous pattern. Similarly, the samples from 50 and 80 per cent etha- nol formed cloudy syrups, which, after drying, produced amorphous x-ray patterns showing traces of lines.

Extension of the time of treatment in aqueous ethanol to 35 days re- sulted in an amorphous product from 40 per cent ethanol and a crystalline product from 50 per cent ethanol.

Interplanar Spa&l

Type L-l

w

T A

13.0 6.50 5.76 5.05 4.69 4.32

3.90 3.56 3.33 3.04

2.79

2.65

2.50 2.37 2.26

Weak “

Medium “ “

Medium strong

Very weak ‘I ‘L

Medium “

Very, very weak

“ “

“ “ ‘L “ “ “

L

TABLE I

s and Estimated Intensities of Typical Dextran Patterns

Type L-2

A

5.65 4.95 4.52 4.00

3.57 3.24 3.06

2.55

2.36

-

Very weak Medium

“

Very, very weak

Very weak Weak Very, very

weak

Very, very weak

“ “

T

-

Type L-3 I T -7

A

6.93 6.13 5.01 4.52

Medium “ “

Very strong

A

3.0 7.80 6.02 5.05 4.55 4.25

3.89 3.49

Strong Medium

3.90 3.47

Very weak “ “

Medium Weak Strong Very, very

weak Medium

“

3.11 Very weak

3.00 Weak 3.04 Medium

2.84 Very weak 2.84

2.71 “ “ 2.65 2.59 “ “ 2.59 2.43 Weak 2.45 2.26 “ 2.26 2.18 “ 2.19

Very, very weak

“ “ “ “ “ “ “ “ “ “

I

Type L-3’

-

Essentially the same results were obtained by use of dextrans having a relative viscosity of 2.003 and 1.414. The pattern from the latter dextran is shown in Fig. 1, a.

Dextran; Drying of Aqueous Pastes--A viscous paste of dextran (relative viscosity’ 2.003) was dried in two parts; one at 25”, the other at 115”. The former gave an amorphous pattern, the latter gave a poor quality x-ray line pattern of the type L-2 (see Fig. 1, b). A much thinner paste, when dried more slowly at 50”, produced an x-ray pattern of type L-l of good quality.

Dextran; Products of Acid Hydrolysis---Dextran was hydrolyzed by 0.5

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A. JEANES, N. C. SCHIELTZ, AND C. A. WILHAM 621

N sulfuric acid at 90” for 1, 2, and 4 hours, respectively, and the fractions of highest molecular weight were isolated from the hydrolysates. Complete details of these hydrolyses and fractionations will be given elsewhere.2

The fractions of highest molecular weight were separated from hydrolysis products of smaller size by dialysis of the sulfate-free solution and by re- peated precipitation from aqueous solution by the addition of ethanol to make a 60 per cent ethanol concentration. During the fractional precipi- tations, the products from 2 and 4 hour hydrolyses became incompletely soluble in hot water. After the last fractional precipitation, the subfraction which had become insoluble in hot water was removed and found to give a good quality x-ray line pattern of type L-3. The main fraction was isola- ted from the clear supernatant in a manner analogous to that described for amorphous dextran (7).

These 60 per cent ethanol-insoluble fractions from 1 and 2 hour hydroly- ses gave amorphous x-ray patterns and had [a] i5 = -l-199” (in 1 N sodium hydroxide, C = 1) and about 65 and 40 glucose units, respectively, per reducing group. Ethoxyl analysis showed them to contain no ethanol. X-ray line patterns of the type L-3 and of very good qua1it.y were obtained after humidification or after treatment for 2 days with aqueous ethanol. Although humidification, which caused the amorphous samples to turn to cloudy pastes, appeared to make no significant change in the dried, pow- dery products from the treatment with aqueous ethanol, it caused these samples to produce intensified and sharper x-ray reflections.

Other fractions from 2 and 4 hour hydrolyses, the isolations of which are not described specifically here, have produced strong x-ray patterns, as is shown in Figs. 1 c and 1 d.

Dextrans Prepared by Other Investigators-X-ray examination of the dextran of Hassid and Barker3 (1) and of the dextran from Leuconostoc dextranicum,4 which is, presumably, the dextran referred to by Fairhead, Hunter, and Hibbert (13), gave results comparable to those for Leuconostoc mesenteroides dextran. In the states in which they were obtained, these samples produced amorphous x-ray patterns, but after treatment with 60 per cent ethanol the products gave x-ray line patterns of type L-l.

The dextran from Leuconostoc dextranicum dissolved readily to form aqueous pastes of very low viscosity. The dextran of Hassid and Barker, the dense, horny appearance of which was indicative of close molecular

2 Wilham, C. A., and Jeanes, A., unpublished data. 3 We are indebted to Professor W. Z. Hassid of the University of California for

this sample. 4 This sample was furnished by Dr. Richard E. Reeves of the Southern Regional

Research Laboratory, New Orleans, Louisiana, who obtained it from Professor Harold Hibbert and used it in the investigation reported in (12).

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622 DEXTRAN AND AMYLACEOUS CARBOHYDRATES

packing and which has been described as water-insoluble (l), was obtained in 2 per cent aqueous solution by vigorous mechanical shaking. After pre- cipitation of the dextran from this solution in the manner described for the preparation of amorphous dextran (7), the fluffy product was much more readily soluble in water than was the original sample.

Water-Insoluble Dextran-In the state in which they were isolated, both of the purified fractions of the water-insoluble dextran from Leuconostoc mesenteroides NRRL B-523 (7) produced essentially amorphous x-ray pat- terns. Weak interferences were produced at 9.5 and 4.25 A by the fraction which was insoluble in the culture medium, and at 20.0 and 9.5 A by the fraction which was originally soluble in the culture medium but which became insoluble during purification. After exposure in 100 per cent relative humidity for 3 days at 25”, the first mentioned fraction produced a weak crystalline pattern which had an interference at 9.5 A, and the third through the ninth interferences of the dextran pattern, type L-3’ (see Table I).

Each of these fractions appeared luminous under crossed Nicol prisms but no extinction was observed.

Amylaceous Carbohydrates-3 days humidification of corn amylose, which had been isolated from the amylose-butanol complex (14) as a chemi- cally reactive, dry powder,5 changed it to a coherent, elastic mass, and caused its x-ray pattern to change from a V to a B type. (When starch crystallizes in the presence of alcohol, usually a V pattern results; when it crystallizes in the presence of water alone, A or B patterns result.) Humi- dification of similarly prepared potato amylose resulted, after 3 days, in the replacement of its original well defined V pattern by an amorphous pat- tern. Continuing humidification for 3 weeks resulted in the development of a poor line pattern. Katz (9) observed that the V pattern of precipi- tated wheat starch was changed to the B pattern by humidification.

Methanol-extracted (15) glutinous corn-starch, contaminated with about 2 per cent ordinary corn-starch, was prepared in an amorphous state by precipitation of an aqueous paste in ethanol.5 Humidification for 7 days caused the starch, which originally produced the amorphous x-ray pattern shown in Fig. 1, e, to produce the type A pattern shown in Fig. 1,f. Native granules of glutinous corn-starch are known to produce an x-ray line pat- tern (10).

A dry, amorphous sample of corn amylopectin, which had been treated with cotton to remove last traces of amylose (16), produced an A type starch pattern after 3 days humidification.

Glycogen has been reported to give only amorphous patterns under

6 Jesnes, A., Deane, R. A., Whistler, R. L., and Hilbert, G. E., in preparation.

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A. JEANES, N. C. SCHIELTZ, AND C. A. WILHAM 623

treatments which cause starch to give line patterns (17, 18). Application of the technique of treatment with aqueous ethanol as described for dextran resulted, even after 8 weeks under aqueous ethanol, in amorphous patterns only. Similarly, only amorphous patterns were obtained from the p- amylase limit dextrin of glutinous corn-starch.

Humidification caused both glycogen and fl-amylase limit dextrin to turn to clear syrups, which, after drying, produced amorphous x-ray patterns.

Observations on Other Physical Properties

The behavior of samples under conditions of 100 per cent relative humid- ity at 25” not only reveals small differences in their ability to hydrate and dissolve but is also an indication of the x-ray pattern which the sample will give after this treatment. The variation of the humidified samples from rather dry, apparently unchanged powders through opaque to cloudy pastes to clear syrups directly paralleled the decreasing degree of orderly association, as indicated by the x-ray patterns.

Likewise, the order of solubility paralleled the physical condition of the sample. Thus, fluffy, amorphous dextran dissolved readily merely by exposure in an atmosphere saturated with water vapor at 25”, but the pul- verized “glassy” product from a dextran paste dried at 115’ dissolved slowly in cold water (20”), and the pulverized, “glassy” product from a paste dried slowly at 50” required heating to 70” to dissolve it in water. Fluffy, amorphous samples of acid-hydrolyzed dextrans dissolved readily in cold water, but the powdery crystalline products from the action of 60 per cent ethanol on these fractions as well as the pulverized, “glassy” crystalline products of humidification required heating in water at 100” to give clear solutions.

Formation of Filaments from Dextran-Filaments have been obtained from dextrans having a relative viscosity1 of 1.855 and 2.003 and from “autolyzed” dextrans having a relative viscosity of 1.414 and 1.565. Aqueous pastes of the proper consistency for filament formation were ob- tained from “autolyzed” dextrans by 2 days humidification in air saturated with water vapor at 25”, but pastes obtained from the other dextrans under these conditions were too rubbery and viscous and had to be thinned by addition of water. When, under normal atmospheric conditions, a probe was touched to these pastes and then steadily pulled away, a lustrous fila- ment was obtained. A filament many feet in length has been obtained by the use of a small mechanical reel. X-ray examination of a bundle of these fibers gave an amorphous pattern.

Filaments could not be obtained similarly from the dextran of Hassid and Barker3 nor from glutinous corn-starch.

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624 DEXTRAN AND AMYLACEOTJS CARBOHYDRATES

DISCUSSION

The emphasis that has been given to the amorphous nature of branched amylaceous substances in contrast to the crystalline nature of the linear substances has led recently to the erroneous belief that only the linear molecules can produce x-ray line patterns (19). In general, irregularity in molecular shape or structure is believed to interfere with orderly associa- tion (8). For example, the amorphous nature of the unbranched poly- saccharide, lichenin, has been attributed to molecular irregularity resulting from the presence of both 1,3- and 1,4-glucosidic linkages (20). In amyla- ceous substances, branches are generally believed to provide the irregu- larity that interferes with crystallization. However, the view has been expressed that orderly association occurs between branches of sufficient length (21, 22) but not if the branches are modified or shortened (22). The results reported here on corn amylopectin, glutinous corn-starch, the /3-amylase limit dextrin of glutinous corn-starch, and glycogen, in agree- ment with observations of Schoch and French (22), show that the tendency towards orderly molecular association decreases in the order stated; that is, in the order of increasing number or shortness of side chains (21, 23). However, the difference reported here in the behavior of potato as compared with corn amylose indicates that some still unrecognized factor can inter- fere with crystallization even in linear molecules which are apparently uniform in structure.

From the extremely careful methylation study of Levi, Hawkins, and Hibbert on a water-soluble dextran from Lezcconostoc mesenteroides (2), it appears that this substance has greater structural irregularity and more numerous as well as shorter branches than glycogen. In view of this and of the influential rale that branching seems to play in retarding crystalli- zation in amylaceous polysaccharides, t,he observation of crystallinity in dextran seems to be anomalous. It is possible that crystallization might be more favored in dextran than in glycogen by the predominance of glucosidic linkages involving a primary position on carbon 6. It is also possible that the concept of the structure.of dextran is inaccurate and that clarification may have to await further structural information on dextrans of specific origin.

Dextran produces a series of typical x-ray diffraction powder patterns which are entirely different from the patterns of starch. The relative intensities of the lines and the background in patterns from the high molecu- lar weight dextrans indicate that the amount of crystalline material present is rather small. A treatment which resulted in crystallization of the high molecular weight dextran from Leuconostoc mesenteroides NRRL B-512 also resulted in about the same degree of crystallinity in two other dextrans

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A. JEANES, N. C. SCHIELTZ, AND C. -4. WILHAM 625

from widely different sources. This is interpreted to indicate that the x-ray line pattern common to these three dextrans is due to a structure which is characteristic of dextran rather than to the presence of a small fraction of material with exceptional crystallizing ability.

The fractions of highest molecular weight from 1, 2, and 4 hour acid hydrolyses of dextran progressively developed crystallinity more readily and completely than dextran. This might result from random reduct.ion of molecular size or from increased regularity in size or structure of the molecules during acid hydrolysis. Increased regularity in struct,ure is to be expected from preferential hydrolysis of the a-1,4-glucosidic link- ages, which we have found to have a critical increment 3000 calories per mole less than that of a-1 ,6-linkages.2

Numerous water-insoluble polysaccharides such as amylose (14)) cellu- lose (19), pectins (24), and some of the fractions produced by Leuconostoc mesenteroides NRRL B-512 (7), or obtained from its water-soluble dextran by acid hydrolysis, produce st,rong x-ray line patterns. finlike all these other substances, the dextran from Leuconostoc mesenteroides KRRL B-523 gave an amorphous x-ray diffraction pattern, was not horny, and yet was water-insoluble. Molecular association in this dextran must be extensive but arrangement of the associated chain segments in a 3 dimensional periodic pattern is lacking.

Investigations on cellulose esters (25) and proteins (26) have established that water, or water and heat, facilitate motion and crystallization of chain segments of these substances in the solid state. Similar observa- tions have been made on starch granules (27) and on starch coacervates (22). Our observations provide further examples of this principle. Expo- sure of solid samples in an atmosphere saturated with water vapor at 25” caused some amorphous substances to assume a crystalline state, crystalline substances to change from one modification to another or develop sharper patterns, and one substance passed through an amorphous state during its transition from one crystalline state to another. Crystallization re- sulted when a dextran paste was warmed while being dried slowly, but did not result when the slow drying was at 25”. Hydrated masses of dextran developed crystallinity when allowed to stand under specific optimum con- centrations of aqueous ethanol, presumably because a critical state of dehydration was obtained which was favorable to molecular orientation and association.

SUMMARY

1. Orderly molecular association has been demonstrated by x-ray an- alysis in branched chain polysaccharides including water-soluble dextran from Leuconostoc mesenteroides NRRL B-512, corn amylopectin, and glu-

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626 DEXTRAN AND AMYLACEOUS CARBOHYDRATES

tinous corn-starch. Under the same conditions, glycogen and the & amylase limit dextrin from glutinous corn-starch did not develop detectable molecular organization.

2. In view of the fact that amylaceous substances which have short branches do not develop orderly molecular association, the crystallization of water-soluble dextran was not to be expected on the basis of the gen- erally held concept that dextran has numerous, short branches.

3. With an increase in the degree of orderly molecular association, as detected by x-ray analysis, there was a decrease in the ability of water- soluble dextran, acid-hydrolyzed dextran, and amylaceous substances to dissolve in water. A more sensitive test of the ability of these substances to hydrate was their behavior under conditions of 100 per cent relative humidity at 25”.

4. Data for a series of typical x-ray diffraction powder patterns have been obtained and used to characterize not only dextrans from three differ- ent sources but also acid-hydrolyzed dextrans.

5. Filaments many feet in length have been spun from aqueous pastes of dextran from Leuconostoc mesenteroides NRRL B-512.

Grateful acknowledgment is made of the helpful criticisms of Mr. C. E. Rist and Dr. N. N. Hellman.

BIBLIOGRAPHY

1. Hassid, W. Z., and Barker, H. A., J. Biol. Chem., 134, 163 (1940). 2. Levi, I., Hawkins, W. L., and Hibbert, H., J. Bm. Chem. Sot., 64, 1959 (1942). 3. Peat, S., Schltichterer, E., and Stacey, M., J. Chem. Sot., 581 (1939). 4. Barker, C. C., Hirst, E. L., and Young, G. T., Nature, 14’7, 296 (1941). Mont-

gomery, E. M., Weakley, F. B., and Hilbert, G. E., J. Am. Chem. Sot., 69, 2249 (1947).

5. Ingelman, B., and Siegbahn, K., Nature, 164, 237 (1944); Ark. Kemi, Mineral. Geol., 18 B, 1 (1944).

6. Gronwall, A., and Ingelman, B., Acta phgsiol. Scand., 7, 97 (1944). 7. Jeanes, A., Wilham, C. A., and Miers, J. C., J. Biol. Chem., 176, 603 (1948). 8. Alfrey, T., Jr., Mechanical behavior of high polymers, New York, 340 (1948). 9. Katz, J. R., 2. phys. Chem., Abt. A, 170, 430 (1934).

10. Bear, R. S., and French, D., J. Am. Chem. Sot., 63, 2298 (1941). 11. Berner, E., Ber. them. Ges., 64, 842 (1931). 12. Reeves, It. E., J. Biol. Chem., 164, 49 (1944). 13. Fairhead, E. C., Hunter, M. J., and Hibbert, H., Canad. J. nes., Sect. B., 16, 151

(1938). 14. Schoch, T. J., J. Bm. Chem. Sot., 64, 2957 (1942). 15. Schoch, T. J., J. Am. Chem. Sot., 64, 2954 (1942). 16. Pacsu, E., and Mullen, J. W., 2nd, J. Am. Chem. Sot., 63, 1168 (1941). 17. Samec, M., Katz, J. R., and Derksen, J. C., 2. phys. Chem., Abt. A, 168,321 (1932). 18. Bear, R. S., and Cori, C. F., J. Biol. Chem., 140, 111 (1941). 19. Peat, S., in Annual review of biochemistry, Stanford University, 16, 78 (1946).

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20. Meyer, K. H., and Giirtler, P., Helv. chim. acta, 30, 751 (1947). 21. Meyer, K. H., and Bernfeld, P., Helv. chim. acta, 23, 875 (1940). Meyer, K. H.,

and Fuld, M., Helv. chim. acta, 24, 375 (1941). 22. Schoch, T. J., and French, D., Cereal Chem., 24, 231 (1947). 23. Haworth, W. N., Kitchen, H., and Peat, S., J. Chem. Sot., 619 (1943). 24. Speiser, R., Copley, M. J., and Nutting, G. C., J. Phys. and Colloid Chem., 61,

117 (1947). 25. Baker, W. O., Fuller, C. S., and Pape, N. R., J. Am. Chem. Sot., 64, 776 (1942). 26. Senti, F. R., Copley, M. J., and Nutting, G. C., J. Phys. Chem., 49, 192 (1945). 27. Sair, L., and Fetter, W. R., Ind. and Eng. Chem., 36, 205 (1944).

EXPLANATION OF PLATE

PLATE 3 FIG. 1. X-ray diffraction patterns of dextran, acid-hydrolyzed dextrans, and glu-

tinous corn-starch. a, type L-l from dextran of relative viscosity 1.414 after treat- ment with 69 per cent ethanol followed by humidification; b, type L-2 from a dextran paste dried at 115”; c, dextran type L-3 from a fraction of 4 hour acid hydrolysis after treatment with 70 per cent ethanol followed by humidification; d, dextran type L-3’ from a fraction of 2 hour acid hydrolysis after humidification; e, pattern from amor- phous glutinous corn-starch; f, type A starch pattern from amorphous glutinous corn-starch after humidification.

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THE JOURNAL OF BIOLOGICAL CHEMISTRY, VOL. 176 PLATE 3

(Jeanes, Schielte, and Wilham: Dextran and amylaceous carbohydrates)

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WilhamAllene Jeanes, N. C. Schieltz and C. A.

AMYLACEOUS CARBOHYDRATESDEXTRAN AND IN BRANCHED

MOLECULAR ASSOCIATION IN

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