Table Of ContentACS SYMPOSIUM SERIES 458
Biotechnology of Amylodextrin
Oligosaccharides
Robert B. Friedman, EDITOR
g 1 American Maize-Products Company
s.orw00
2 | http://pubs.acbk-1991-0458.f
st 1, 20110.1021/
n Augu1 | doi:
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4.136 30, 19
63.3pril Developed from a symposium sponsored
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by 89.Date: by the Divisions of Carbohydrate Chemistry
d n and of Agricultural and Food Chemistry
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wnloadblicati at the 198th National Meeting
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Miami Beach, Florida,
September 10-15, 1989
American Chemical Society, Washington, DC 1991
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Library of Congress Cataloging-in-Publication Data
Biotechnology of amylodextrin oligosaccharides / Robert Friedman,
editor.
p. cm.—(ACS symposium series; 458)
"Developed from a symposium sponsored by the Divisions of
Carbohydrate Chemistry and of Agricultural and Food Chemistry at the
198th National Meeting of the American Chemical Society, Miami
Beach, Florida, September 10-15, 1989"
Includes bibliographical references and indexes.
ISBN 0-8412-1993-1
g 1
s.orw00 2. 1O. liAgomsayclocdheaxrtidrienss—— BBioiotetecchhnnoolologgyy——CCoonnggrreesssseess. .
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on Augu91 | doi: T6Dfo6PNr1 2L'L.48Mi8—b.6r/Da5dr.LcAy2C 4o0 6f B C5o6n gr1e9s9s1 91-138C9I3P
4.136 30, 19
163.3April The paper used in this publication meets the minimum requirements of American National
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d n Copyright © 1991
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In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
Washington, D.C. 20036
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
ACS Symposium Series
M. Joan Comstock, Series Editor
1991 ACS Books Advisory Board
V. Dean Adams Bonnie Lawlor
g 1 Tennessee Technological Institute for Scientific Information
s.orw00 University
2 | http://pubs.acbk-1991-0458.f PMaeuRrclek sSe Sa. hrcAahrnp Ld &aebr Dsooroanht omriee s DJRooohwbne C rLht. e MmMiccaGaslso iCrnrgoiminll p any
n August 1, 2011 | doi: 10.1021/ AUnleivxeirss iTty. oBfe Clla lifornia—Berkeley KPJulraalnifutt sSG cJeien. nMercaeesln FInno sotditsu te,
o9 Malcolm H. Chisholm U.S. Department of Agriculture
4.136 30, 19 Indiana University
163.3April Natalie Foster MOfafircseh oafl lA Pghriicluliltpusr al Biotechnology,
by 89.Date: Lehigh University U.S. Department of Agriculture
d n
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wnloadblicati DUneinvenrissit yW o.f H Ceaslisfo rnia—Berkeley DUnainveierls itMy o. Qf Iuowinan
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Mary A. Kaiser A. Truman Schwartz
E. I. du Pont de Nemours and Macalaster College
Company
Stephen A. Szabo
Gretchen S. Kohl Conoco Inc.
Dow-Corning Corporation
Robert A. Weiss
Michael R. Ladisch University of Connecticut
Purdue University
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Foreword
THE ACS SYMPOSIUM SERIES was founded in 1974 to provide
a medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typeset, but are reproduced as they are submit
g 1 ted by the authors in camera-ready form. Papers are reviewed
s.orw00 under the supervision of the editors with the assistance of the
2 | http://pubs.acbk-1991-0458.f AbHsyedomcvwapiuseoovssreeiyar ,.sB yoBmvaeoprrtdobhs a airtaneim vdime awarryese psaeernmoleddcb utrreceadtpcioo etnr otsb sm o otaohfif n r tetaypsieprnaee rvstchi ohoeu fasi nrlypete r gaeprcsuicetenbyptl iatosathfib oetlnhed,.e
st 1, 20110.1021/ papers are not accepted.
n Augu1 | doi:
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4.136 30, 19
63.3pril
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by 89.Date:
d n
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wnloadblicati
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In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Preface
BIOTECHNOLOGY is one of the oldest technologies, though, at the same
time, it is also one of the newest. Since the age of Noah, biotechnology
has been employed as a means of producing products that are both desir
able and specific in function. In this contemporary age of biochemistry
and molecular biology, however, biotechnology has assumed a totally dif
ferent dimension of applicability regarding specificity and usefulness. As
cs.org pr001 tahbeu nddeamnatlnyd a ivnacirlaeabslees rafowr menahtaenricaelds fbrioomco mnpatautirbaillliyty r ienn epwraobdluec trse saonudrc feosr,
12 | http://pubs.a1/bk-1991-0458. mpharoovWrdeeu i ptchartn ost dvhae enmdidr ot gorrae ebnw epe r meaao alpv taaleelvru iaaahillbasalv befeoi l sirutb ytbeh esitennr antttheuexer tfnvo iderneg gbcea ittoadotbee slcb.eh i onktoienlcoghgdnyoo.m loIn,g cdyae retbdoo, hptyhrdeor daputrecose
02 duction of corn sweeteners is a triumph of modern commercial biotech
20
n August 1, 1 | doi: 10.1 nadnoomdlo ,g aybv.ua itCl atabhrlebe ovihenyg dehtraiagbthelees-r da erqreui vaaenlsdtoi t pifeuosln.y csItainoc cnphaaallrrytidi ciemusl paaorrr,e tsa tmnartuc ichnh- dt mhereoi vraeend iam cpcaoell sykssiiabnclge
4.136 o30, 199 ach barroidaeds sapnecdt roulimgo soafc icnhdaursidtreisa lh aanvde fporoodv eadp ptoli cbaeti oenxsc.e ptionally valuable in
163.3April theB edciavuerssei tyth oe fm fuaninc trioepneaalittiyn go fm tohneosme esru bosft atnhceesse mbiuospto lryemsuelrt sf riso mgl ustcrousce ,
by 89.Date: tural differences. It was recognized fairly early on that changing the struc
d n ture of starch polysaccharides can dramatically affect the behavior of
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adati those materials. For this reason, chemically modified starches and depo-
oc
wnlubli lymerized starches have served competently over the years.
Do P Contemporary society, however, has stressed the importance of the
perception of healthfullness. To meet the demands of this perception, a
reduction in chemical modification will probably be required. To replace
those necessary functionalities, biotechnology will be called on to perform
the required structural changes. To achieve this end, however, a more
fundamental understanding of starch structures as well as
function-structure relationships of these compounds will be required.
Furthermore, enzyme systems must be understood along with the basic
biochemical and genetic mechanisms that control their production and
behavior. The purpose of this book, as well as the symposium from which
it was derived, is to focus attention on the many facets of the biotechnol
ogy of amylodextrin polysaccharides. It is hoped that not only will the
ix
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
potential usefulness of this group of substances be illuminated, but also
the broad extent of fundamental scientific information will be revealed.
This book is designed to be useful to a broad array of researchers who
might find oligosaccharide biopolymers of interest. As such, it must cover
biochemistry and enzymology as well as those unique structural charac
teristics that require novel analytical tools. New aspects of usefulness
must also be addressed. Consequently, the book has three basic parts:
• The first section deals with the basic biochemical aspects of biotech
nology of amylodextrin oligosaccharides. It includes an introduction to
genetic engineering as well as enzyme structure and enzymology.
• The second section focuses on applications of specific new analytical
tools that are essential to characterize adequately these new types of
g 1 materials. These oligosaccharides are characterized as polymeric
cs.orpr00 materials.
12 | http://pubs.a1/bk-1991-0458. • STcehvhaeerr iatdhle iysre.d a arrse aag aod, ditr ewssoeus ldsp hecaivfiec bfieeelnd sd oifff iucuseltfu tlon efsins df omr otrhee steh apno lyas faecw
02
n August 1, 21 | doi: 10.10 bicdsooi rnoeetkxcrpstiib eoocuntnte i oodsfnp setdh ceoaivfntiec l og tphaernmeee aestnsiuc bto jeofen cfog ttl.iih ngSeeosoeseraoi cnnscu ghib taw srwtiaidlinlle lch ebbasie.vo etne ecach esnsigsoanlorifgyiyc at. onF tdo eerfv feeexlcoatmp openlne t,ti hritee
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4.136 30, 19 whIi cahc kmnaodwele dthgee styhme pfionsaiunmci aplo assssibisltea:n cAell ioefd -tShieg nfaoll loCwoirnpgo roartigoann;i zAamtioenrsi ,
163.3April can Maize-Products Company; Aqualon Company; Corn Products Com
by 89.Date: Npaantyio;n Dal CSAta Frcoho da nIdn dCuhstermieisc,a lI nCc.o;r pJoarnastsieonn ; PNhoavrmo aLceaubtoicraa;to Mrieilse;s , PIfnizce.;r ,
ed on Inc.; Pioneer Hi-Bred International; U.O.P.; and Wyatt Technology Cor
oadcati poration. In addition, I would like to acknowledge the assistance and sup
wnlubli port of the officers of American Maize-Products Company, in particular
oP
D William Ziegler HI, Patric J. McLaughlin, and Frances R. Katz, for their
support and encouragement in the development of this book. The assis
tance of Sherree Jackson and Gloria Kras in the preparation of the text is
also acknowledged. I would like to thank Alfred French for the graphic
idea incorporated in the cover design. Finally, I would like to thank Ellen
and the boys for their inspiration and vast amounts of encouragement.
ROBERT B. FRIEDMAN
American Maize-Products Company
Hammond, IN 46320-1094
September 9, 1990
x
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Chapter 1
Helical and Cyclic Structures in Starch
Chemistry
J. Szejtli
Cyclodextrin Research and Development Laboratory, Cyclolab,
1026 Budapest, Endrdódi S. 38/40, Hungary
g 1
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20
n August 1, 1 | doi: 10.1 moffoonerr smmm, aaadnttiieyool nnivv eeaornrfy sd c dypifcrfuflooerprdteheerenxtrtti erpsion rbooss,ofe frc avafmaottaryil olyotnshsseee,d- h hbebeuliyltxi ccmacyoalc milnsitplzyrlieu nxocgent su e.t rnhTeze,hy e
o9 and simultaneously is the source of a new technology:
4.136 30, 19 tlohde emxtorlienc ucloamr pelnecxaaptisounl.a tTiohne osifg ndiiffifcearnecnet coofm tphoeu ndcys cbloyd ceyxtc
163.3April rbien sd iasncdu stshedei. r derivatives in commercial applications will
by 89.Date:
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oadecatio Wlhinekna get, woth eD- fgolrumceodp ydriasnaocsceh ariudnei tsi s acarlel eldi nmkaeldt osbe,y w<h*i-lle, 4a gfltu-c1o,s4 idic
wnlubli glucosidic linkage between them results in cellobiose. Inspecting a
Do P molecular model of such a diglucoside, it becomes evident, that the
rotation around the and O-C^* bond is hindered, i.e. the values
^and Y rotational angles (the so-called bond conformation, Fig.l.)
are restricted to a relatively narrow domain, because of collision of
the hydrogens and hydroxyls of the interconnected glucopyranoside
units. Maltose can exists only in the cis-configuration (Fig.2.b.)
and cellobiose only in the trans-configuration (Fig.2.c). That
configuration, in which the plane of one glucopyranose ring lies at
right angle to the other, is sterically impossible (Fig.2.a.). (1,2).
This cis-configuration (=maltose) is, however, not a planar
structure, because the bond angle of the bridge-oxygen is between
113 and 119°, depending on the steric strain of the whole structure.
(3). Constructing a long-chain from these disaccharides, the
repetition of these fundamental structural elements results in the
case of cis-type configuration (maltose) a helical turn, or in case
0097-6156/91A)458-0002$06.00/0
© 1991 American Chemical Society
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
1. SZEJTLI Helical and Cyclic Structures in Starch Chemistry 3
of the trans-type configuration a zig-zag conformation i.e.
cellulose (Fig. 3).
The amylose helix
Amylose and cellulose are the most thoroughly studied
polysaccharides, nevertheless, some properties of amylose are until
today not understood. For some time two conflicting hypotheses
existed concerning the molecular conformation of amylose in aqueous
solution. According to one hypothesis the dissolved molecule forms a
coil, (Fig.4.a.) in which helical segments are connected by
disordered segments. Adherents to the other hypothesis claim that
the molecule forms a completely random coil, without any helically
ordered segments. (Fig.4.b.). Neither the completely stretched
uncoiled structure, nor the rigid, rodlike totally helical form
g 1 (Fig.4.c.) has ever been seriously considered as a possibility, and
s.orh00 their existence can be easily disproved by viscosimetric studies.
12 | http://pubs.ac1/bk-1991-0458.c mddT(hoiiFelssi epogcur.utdAn4leeca.edrcta eou.dirr) ne di ins wnoegrho avifqce uhcr,eoatt olnoh u teds hao oitzhwnceesseon oivslle ouaerodrtc,f di t eoupnrfca aeolopdr ne,mbsr ,eais hhc.saec tvleis(eip. 4sTce) eao..ldf awsse hehxegayttm pehefonenltdrtehe sxde sihiibhatsles e li isrbtc aehacnleeo d nmos pmealv gmeimytvceleionoldiytsll ,yse
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4.136 30, 19 satsosiocchiiaotmieont ric of comdpoisfifteiroennt. Tmheo lecrualteiso ofi s thnee vecro mpoonfe ntsst riinc ttlhye
163.3April miascorloamteodl eccuolmaprl exc odlelpoeind,d s boyn mwahniyc hf aicst omrosr,e mdoirfefoivceurl t thteo apmeyrlfoorsme iasn ya
by 89.Date: wcoyrcklo detxhatnr in wiithn cluwseiolnl dceofmipnlede xcersy,s tanadl liqnuei tseu brsetcaennctelsy. tThhee isstouldayt ioofn
ed on and study of pure maltooligomers up to DP= 30 (5), clarified some
oadcati scientific problems about the amylose and cyclodextrin inclusion
ownlPubli cionmdpulsetrxieasl, buutti, lizfaitristo n of of alcl,y crleovdeeaxltedr inasn anadn ortmhoeuisr fiineclld usfioorn
D
complexes. (6)
The cyclic dextrins
The cyclodextrins are produced, by an enzymic reaction, from
starch, more exactly from amylose and from the oc-1,4 linked
segments of amylopectin. (Fig.6.) The applied enzyme is a
biocatalyst: it does nothing else, but to help to reach the
thermodynamically most stable conformation of the polyglucan: i.e.
the helical segments are converted to closed rings. The easy
formation of cyclodextrins with high yield is an indirect proof for
the existence of the helical structure of amylose in the aqueous
solution.
Three different cyclic dextrins can be produced: (Fig.7.) the 6
membered otCD, the 7 membered pCD and the 8 membered )f CD. All of
these are industrially produced crystalline products, with a purity
of over 99 %.
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
BIOTECHNOLOGY OF AMYLODEXTRIN OLIGOSACCHARIDES
g 1
s.orh00
12 | http://pubs.ac1/bk-1991-0458.c Fig.l. BCo^-nOd acnodn f0o-rCm>a tbioonn dso.f a disaccharide: rotation around the
02
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163.3April Fig.2. Only the "cis" and the "trans" conformations can exist.
by 89.Date:
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oadcati
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amylose cellulose
Fig.3. Repeating the "cis" (=maltose) conformation results in a
helical structure while the "trans" (=cellobiose) leads
to a zig-zag chain.
In Biotechnology of Amylodextrin Oligosaccharides; Friedman, R.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
