%0 Journal Article %1 STOKKE1992 %A STOKKE, B. T. %A CHRISTENSEN, B. E. %A SMIDSROD, O. %C 1155 16TH ST, NW, WASHINGTON, DC 20036 %D 1992 %I AMER CHEMICAL SOC %J Macromolecules %K ;; [ISI:] aqueous behavior; conformational dilute-solution; double-stranded helix; light-scattering; polysaccharide pyruvate schizophyllan; sodium-chloride; substituents; temperature thermal-stability; transition; %N 8 %P 2209 -- 2214 %T DEGRADATION OF MULTISTRANDED POLYMERS - EFFECTS OF INTERSTRAND STABILIZATION IN XANTHAN AND SCLEROGLUCAN STUDIED BY A MONTE-CARLO METHOD %V 25 %X The depolymerization of double-stranded xanthan and triple-stranded scleroglucan is simulated using a Monte Carlo method. Chain scissions are introduced randomly in each strand to simulate chemical degradation. The cooperative single- to double- or single- to triple-stranded conformational change requires that the chain length exceeds a lower critical value which is incorporated in the model. The simulations show that degradation of such polymers deviates significantly from that of single-stranded polymers. There is initially an apparently enhanced stability where scission of the glycosidic linkages is effectively masked because of interstrand stabilization. This period is followed by a power law region, M(w) approximately t(-nu), where the exponent nu for a monodisperse starting material is observed to be 1.0, 1.66 +/- 0.06, and 2.3 +/- 0.1 for the single-, double-, and triple-stranded cases, respectively. Exponents larger than 1 originate from the unmasking of preexisting broken glycosidic linkages when additional scissions are introduced. Analysis of the data reported for the acid-catalyzed degradation of xanthan in the ordered conformation yielded nu = 1.5 +/- 0.1, in good agreement with the prediction for a double-stranded model.

@article{STOKKE1992, __markedentry = {[phpts:6]}, abstract = {The depolymerization of double-stranded xanthan and triple-stranded scleroglucan is simulated using a Monte Carlo method. Chain scissions are introduced randomly in each strand to simulate chemical degradation. The cooperative single- to double- or single- to triple-stranded conformational change requires that the chain length exceeds a lower critical value which is incorporated in the model. The simulations show that degradation of such polymers deviates significantly from that of single-stranded polymers. There is initially an apparently enhanced stability where scission of the glycosidic linkages is effectively masked because of interstrand stabilization. This period is followed by a power law region, M(w) approximately t(-nu), where the exponent nu for a monodisperse starting material is observed to be 1.0, 1.66 +/- 0.06, and 2.3 +/- 0.1 for the single-, double-, and triple-stranded cases, respectively. Exponents larger than 1 originate from the unmasking of preexisting broken glycosidic linkages when additional scissions are introduced. Analysis of the data reported for the acid-catalyzed degradation of xanthan in the ordered conformation yielded nu = 1.5 +/- 0.1, in good agreement with the prediction for a double-stranded model.}, added-at = {2011-11-04T13:47:04.000+0100}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036}, author = {STOKKE, B. T. and CHRISTENSEN, B. E. and SMIDSROD, O.}, authoraddress = {UNIV TRONDHEIM,DIV BIOTECHNOL,N-7034 TRONDHEIM,NORWAY.}, biburl = {https://www.bibsonomy.org/bibtex/2959b7d0e53c10106d477571e49f97954/pawelsikorski}, citedref = {APPLEQUIST J, 1965, J AM CHEM SOC, V87, P1450 ; ASH SG, 1983, 58TH ANN C EXH SOC P ; BRAGG JR, 1983, 58TH ANN C EXH SOC P ; CHEN CSH, 1979, J MACROMOL SCI CHEM, V13, P239 ; CHRISTENSEN BE, 1991, CARBOHYD RES, V214, P55 ; COVIELLO T, 1986, MACROMOLECULES, V19, P2826 ; DAVISON P, 1982, SOC PET ENG J JUN, P353 ; FOSS P, 1987, CARBOHYD POLYM, V7, P421 ; HACCHE LS, 1987, MACROMOLECULES, V20, P2179 ; HAGEN U, 1967, BIOCHIM BIOPHYS ACTA, V134, P45 ; HATAKENAKA K, 1987, INT J BIOL MACROMOL, V9, P346 ; HIGGS PG, 1989, J PHYS-PARIS, V50, P3285 ; HOLZWARTH G, 1979, CARBOHYD RES, V76, P277 ; JANSSON PE, 1975, CARBOHYD RES, V45, P275 ; JOHNSON J, 1963, CHEM IND-LONDON, P820 ; KIERULF C, 1988, CARBOHYD POLYM, V9, P185 ; KITAMURA S, 1989, BIOPOLYMERS, V28, P639 ; LAMBERT F, 1985, POLYMER, V26, P1549 ; LANGE EA, 1988, WATERSOLUBLE POLYM P, P231 ; LECOURTIER J, 1986, INT J BIOL MACROMOL, V8, P306 ; LIU W, 1987, CARBOHYD RES, V160, P267 ; LIU W, 1988, INT J BIOL MACROMOL, V10, P44 ; LUND T, 1990, POLYM DEGRAD STABIL, V27, P211 ; MILAS M, 1986, CARBOHYD RES, V158, P191 ; MILAS M, 1988, J APPL POLYM SCI, V35, P1115 ; MULLER G, 1988, CARBOHYD POLYM, V9, P213 ; NORTON IT, 1984, J MOL BIOL, V175, P371 ; OLEARY WB, 1987, SPE RESERVOIR EN NOV, P647 ; PAOLETTI S, 1983, CARBOHYD RES, V123, P173 ; PARADOSSI G, 1982, MACROMOLECULES, V15, P874 ; RYLES RG, 1988, SPE RESERVOIR EN FEB ; SATO T, 1984, MACROMOLECULES, V17, P2696 ; SATO T, 1984, POLYM J, V16, P341 ; SATO T, 1984, POLYM J, V16, P423 ; SERIGHT RS, 1986, 5TH SPE DOE S ENH OI ; SHATWELL KP, 1990, CARBOHYD RES, V206, P87 ; SHATWELL KP, 1990, INT J BIOL MACROMOL, V12, P71 ; SHIBATA JH, 1981, BIOPOLYMERS, V20, P525 ; SINSHEIMER RL, 1953, J BIOL CHEM, V208, P445 ; STOKKE BT, 1986, INT J BIOL MACROMOL, V8, P217 ; STOKKE BT, 1989, ACS SYM SER, V396, P145 ; TANFORD C, 1961, PHYSICAL CHEM MACROM ; THOMAS CA, 1956, J AM CHEM SOC, V78, P1861 ; WELLINGTON SL, 1980, 4218327, US ; WELLINGTON SL, 1983, SOC PET ENG J DEC, P901 ; YANAKI T, 1960, J CHEM PHYS, V33, P1349 ; YANAKI T, 1983, BIOPHYS CHEM, V17, P337 ; YANAKI T, 1985, CARBOHYD POLYM, V5, P275 ; ZAMNHOF S, 1985, APR INT S OILF GEOTH ; ZHANG L, 1987, BIOPOLYMERS, V26, P333 ; ZIMM BH, 1959, J CHEM PHYS, V31, P526}, interhash = {1156eef9ba6c443da29bcbe707c6c124}, intrahash = {959b7d0e53c10106d477571e49f97954}, isifile-dt = {Article}, isifile-ga = {HN935}, isifile-j9 = {MACROMOLECULES}, isifile-nr = {51}, isifile-pi = {WASHINGTON}, isifile-rp = {STOKKE, BT, UNIV TRONDHEIM,DEPT PHYS & MATH,NORWEGIAN BIOPOLYMER ; LAB,N-7034 TRONDHEIM,NORWAY.}, isifile-sc = {Polymer Science}, isifile-tc = {15}, issn = {0024-9297}, journal = {Macromolecules}, keywords = {;; [ISI:] aqueous behavior; conformational dilute-solution; double-stranded helix; light-scattering; polysaccharide pyruvate schizophyllan; sodium-chloride; substituents; temperature thermal-stability; transition;}, language = {English}, month = {APR 13}, number = 8, owner = {phpts}, pages = {2209 -- 2214}, publisher = {AMER CHEMICAL SOC}, size = {6 p.}, sourceid = {ISI:A1992HN93500023}, timestamp = {2011-11-04T13:47:24.000+0100}, title = {DEGRADATION OF MULTISTRANDED POLYMERS - EFFECTS OF INTERSTRAND STABILIZATION IN XANTHAN AND SCLEROGLUCAN STUDIED BY A MONTE-CARLO METHOD}, volume = 25, year = 1992 }