Thermodynamics of the Hydrolysis Reactions of 1,4-beta-D-xylobiose, 1,4-beta-D-xylotriose, D-cellobiose, and D-Maltose

Tewari, Yadu B.; Lang, Brian E.; Decker, Steven R.; Goldberg, Robert N.

doi:10.1016/j.jct.2008.05.015

Thermodynamics of the Hydrolysis Reactions of 1,4-beta-D-xylobiose, 1,4-beta-D-xylotriose, D-cellobiose, and D-Maltose

Journal Article · Wed Oct 01 04:00:00 EDT 2008 · Journal of Chemical Thermodynamics

DOI:https://doi.org/10.1016/j.jct.2008.05.015· OSTI ID:951021

Tewari, Yadu B.; Lang, Brian E.; ; Goldberg, Robert N.

Microcalorimetry and high-performance liquid chromatography have been used to conduct a thermodynamic investigation of the following reactions: (1) 1,4-{beta}-Dxylobiose(aq)+H{sub 2}O(I)=2D-xylose(aq); (2) 1,4-{beta}-D-xylotriose+2H{sub 2}O(I)=3D-xylose(aq); (3) D-maltose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq); and (4) D-cellobiose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq). The results of the equilibrium measurements were K = (1.46 {+-} 0.15) {center_dot} 10{sup 3} for reaction (1) and K = (551 {+-} 34) for reaction (3). Although it was not possible to measure directly a value for the equilibrium constant for reaction (4), it was possible to obtain the value K = 657 for this reaction via a thermochemical pathway calculation. The results of the calorimetric measurements were standard enthalpies of reaction {Delta}{sub r}H{sup o} = (0.12 {+-} 0.26) kJ {center_dot} mol{sup -1} for reaction (1) and {Delta}{sub r}H{sup o} = -(0.06 {+-} 0.18) kJ {center_dot} mol{sup -1} for reaction (2). It is noted that values of {Delta}{sub r}H{sup o} for reactions (1) and (2) are equal to each other within their respective experimental errors. This fact is consistent with earlier observations that, for reactions involving the making/breaking of N saccharide linkages, the assignment of characteristic values of {Delta}{sub r}H{sup o}/N or {Delta}{sub r}G{sup o}/N or {Delta}{sub r}S{sup o}/N for a specified linkage, is accurate in predicting the values of {Delta}{sub r}H{sup o}, {Delta}{sub r}G{sup o}, and {Delta}{sub r}S{sup o} for reactions involving saccharides that contain multiples or combinations of such linkages. Also, the values of the standard entropy changes {Delta}{sub r}S{sup o} for the hydrolysis reactions (3) and (4) fall into the range of values {l_brace}(32 to 48) J {center_dot} K{sup -1} {center_dot} mol{sup -1}{r_brace} previously noted for the hydrolysis of six-carbon disaccharides. In order to tie the results of this study into the thermochemical literature, a reaction catalog of related property values was created. Selected property values from this reaction catalog were then used to calculate 'best' values of the standard Gibbs free energy of formation {Delta}{sub r}G{sup o}, the standard enthalpy of formation {Delta}{sub r}H{sup o}, the standard molar entropy S{sub m}{sup o}, and the standard molar heat capacity C{sub p,m}{sup o}, for the substances of interest to this investigation.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 951021

Report Number(s):: NREL/JA-270-43083; MainId:47505; UUID:ec87c796-f0d4-e411-b769-d89d67132a6d; MainAdminId:29597

Journal Information:: Journal of Chemical Thermodynamics, Journal Name: Journal of Chemical Thermodynamics Journal Issue: 10 Vol. 40; ISSN JCTDAF; ISSN 0021-9614

Country of Publication:: United States

Language:: English

References (40)

Comparative Solubilities in Water, in Pyridine and in Aqueous Pyridine. Dehn, William M. Journal of the American Chemical Society, Vol. 39, Issue 7 https://doi.org/10.1021/ja02252a012	journal	July 1917
Saturation molalities and standard molar enthalpies of solution of adenosine(cr), guanosine·2H2O(cr), inosine(cr), and xanthosine·2H2O(cr) in H2O(l) Tewari, Yadu B.; Klein, Ralph; Vaudin, Mark D. The Journal of Chemical Thermodynamics, Vol. 35, Issue 10 https://doi.org/10.1016/S0021-9614(03)00156-3	journal	October 2003
Indirect Measurements of the Rotatory Powers of some Alpha and beta Forms of the Sugars by Means of Solubility Experiments. Hudson, C. S.; Yanovsky, E. Journal of the American Chemical Society, Vol. 39, Issue 5 https://doi.org/10.1021/ja02250a019	journal	May 1917
The water solubilities and heats of solution of short chain cellulosic oligosaccharides Taylor, J. B. Transactions of the Faraday Society, Vol. 53 https://doi.org/10.1039/tf9575301198	journal	January 1957
Equilibrium relationships in the degradation of starch by an amyloglucosidase van Benynum, G. M. A.; Roels, J. A.; van Tilburg, R. Biotechnology and Bioengineering, Vol. 22, Issue 3 https://doi.org/10.1002/bit.260220313	journal	March 1980
Partial molar heat capacities and volumes of some mono-, di- and tri-saccharides in water at 298.15, 308.15 and 318.15 K Banipal, P. K.; Banipal, T. S.; Lark, B. S. Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 1 https://doi.org/10.1039/a604656h	journal	January 1997
Kinetics of formation of maltose and isomaltose through condensation of glucose by glucoamylase Adachi, Shuji; Ueda, Yasuo; Hashimoto, Kenji Biotechnology and Bioengineering, Vol. 26, Issue 2 https://doi.org/10.1002/bit.260260203	journal	February 1984
Enthalpies and heat capacities of transfer of some sugars from water to aqueous urea solutions Jasra, Raksh V.; Ahluwalia, Jagdish C. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 79, Issue 5 https://doi.org/10.1039/f19837901303	journal	January 1983
Sugar Monomer and Oligomer Solubility: Data and Predictions for Application to Biomass Hydrolysis Gray, Matthew C.; Converse, Alvin O.; Wyman, Charles E. Applied Biochemistry and Biotechnology, Vol. 105, Issue 1-3 https://doi.org/10.1385/ABAB:105:1-3:179	journal	January 2003
An equilibrium phase diagram for the glucose-cellobiose-water system at 30.5.degree.C Mistry, Firoz R.; Barnett, Stanley M. Journal of Chemical & Engineering Data, Vol. 25, Issue 3 https://doi.org/10.1021/je60086a015	journal	July 1980
Apparent molar volumes and apparent molar heat capacities of aqueous D(+)-cellobiose, D(+)-maltose, and sucrose at temperatures from (278.15 to 393.15)K and at the pressure 0.35MPa Brown, B. R.; Ziemer, S. P.; Niederhauser, T. L. The Journal of Chemical Thermodynamics, Vol. 37, Issue 8 https://doi.org/10.1016/j.jct.2004.12.004	journal	August 2005
High Precision Microcalorimetry: Apparatus, Procedures, and Biochemical Applications Steckler, D. K.; Goldberg, R. N.; Tewari, Y. B. Journal of Research of the National Bureau of Standards, Vol. 91, Issue 3 https://doi.org/10.6028/jres.091.018	journal	May 1986
Calorimetric Studies on Hydrolysis of Glucosides Ono, Sozaburo; Hiromi, Keitaro; Takahashi, Katsutada The Journal of Biochemistry, Vol. 57, Issue 6 https://doi.org/10.1093/oxfordjournals.jbchem.a128147	journal	June 1965
Properties of Sugar, Polyol, and Polysaccharide Water−Ethanol Solutions Bouchard, Andréanne; Hofland, Gerard W.; Witkamp, Geert-Jan Journal of Chemical & Engineering Data, Vol. 52, Issue 5 https://doi.org/10.1021/je700190m	journal	July 2007
The Heat Capacities and Entropies of Three Disaccharides Anderson, Adolph G.; Stegeman, Gebhard Journal of the American Chemical Society, Vol. 63, Issue 8 https://doi.org/10.1021/ja01853a026	journal	August 1941
Thermodynamics of the disproportionation of adenosine 5′-diphosphate to adenosine 5′-triphosphate and adenosine 5′-monophosphate Goldberg, Robert N.; Tewari, Yadu B. Biophysical Chemistry, Vol. 40, Issue 3 https://doi.org/10.1016/0301-4622(91)80024-L	journal	July 1991
Phosphorolysis of Maltose by Enzyme Preparations from Neisseria Meningitidis Fitting, Charlotte; Doudoroff, Michael Journal of Biological Chemistry, Vol. 199, Issue 1 https://doi.org/10.1016/S0021-9258(18)44822-3	journal	November 1952
Ueber die Verbrennungswärme organischer Verbindungen. Ein Beitrag für die Thermochemie und für die physiologische Chemie v. Rechenberg, C. Journal für Praktische Chemie, Vol. 22, Issue 1 https://doi.org/10.1002/prac.18800220101	journal	November 1880
Apparent molar volumes of aqueous cellobiose solutions Herrington, Thelma M.; Pethybridge, Alan D.; Parkin, Brian A. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 79, Issue 4 https://doi.org/10.1039/f19837900845	journal	January 1983
Selected Values of Heats of Combustion and Heats of Formation of Organic Compounds Containing the Elements C, H, N, O, P, and S. Domalski, Eugene S. Journal of Physical and Chemical Reference Data, Vol. 1, Issue 2 https://doi.org/10.1063/1.3253099	journal	April 1972
Polysaccharide XIX. Die Verbrennungswärmen der Kohlenhydrate Karrer, P.; Fioroni, W. Helvetica Chimica Acta, Vol. 6, Issue 1 https://doi.org/10.1002/hlca.19230060138	journal	January 1923
Thermodynamics of hydrolysis of disaccharides Tewari, Yadu B.; Goldberg, Robert N. Biophysical Chemistry, Vol. 40, Issue 1 https://doi.org/10.1016/0301-4622(91)85029-P	journal	April 1991
Thermodynamics of hydrolysis of oligosaccharides Goldberg, Robert N.; Bell, Donna; Tewari, Yadu B. Biophysical Chemistry, Vol. 40, Issue 1 https://doi.org/10.1016/0301-4622(91)85030-T	journal	April 1991
Characteristics of Cellobiose Phosphorylase Alexander, James K. Journal of Bacteriology, Vol. 81, Issue 6 https://doi.org/10.1128/JB.81.6.903-910.1961	journal	January 1961
Heats of Combustion of Some Mono- and Disaccharides Clarke, Theodore H.; Stegeman, Gebhard. Journal of the American Chemical Society, Vol. 61, Issue 7 https://doi.org/10.1021/ja01876a028	journal	July 1939
Thermodynamic quantities for the dissociation equilibria of biologically important compounds. 4. The second acid dissociation of glucose 1-phosphoric acid Ashby, J. H.; Clarke, H. B.; Crook, E. M. Biochemical Journal, Vol. 59, Issue 2 https://doi.org/10.1042/bj0590203	journal	February 1955
Heterologous Expression of Aspergillus niger β-d-Xylosidase (XlnD): Characterization on Lignocellulosic Substrates Selig, Michael J.; Knoshaug, Eric P.; Decker, Stephen R. Applied Biochemistry and Biotechnology, Vol. 146, Issue 1-3 https://doi.org/10.1007/s12010-007-8069-z	journal	November 2007
Calorimetric Solution Properties of Simple Saccharides and Their Significance for the Stabilization of Biological Structure and Function Miller, Danforth P.; de Pablo, Juan J. The Journal of Physical Chemistry B, Vol. 104, Issue 37 https://doi.org/10.1021/jp000807d	journal	September 2000
Recommendations for nomenclature and tables in biochemical thermodynamics (IUPAC Recommendations 1994) Alberty, Robert A. Pure and Applied Chemistry, Vol. 66, Issue 8 https://doi.org/10.1351/pac199466081641	journal	January 1994
Kalorimetrische Untersuchungen. Über den Wärmewert von Kohlehydraten, mehrsäurigen Alkoholen und Phenolen Stohmann, F.; Langbein, H. Journal für Praktische Chemie, Vol. 45, Issue 1 https://doi.org/10.1002/prac.18920450134	journal	January 1892
Thermodynamic Quantities for the Ionization Reactions of Buffers Goldberg, Robert N.; Kishore, Nand; Lennen, Rebecca M. Journal of Physical and Chemical Reference Data, Vol. 31, Issue 2 https://doi.org/10.1063/1.1416902	journal	June 2002
Thermodynamic and Transport Properties of Carbohydrates and their Monophosphates: The Pentoses and Hexoses Goldberg, Robert N.; Tewari, Yadu B. Journal of Physical and Chemical Reference Data, Vol. 18, Issue 2 https://doi.org/10.1063/1.555831	journal	April 1989
LXXIII.—Thermal phenomena attending the change in rotatory power of freshly prepared solutions of certain carbohydrates, with some remarks on the cause of multirotation Brown, Horace T.; Pickering, Spencer U. J. Chem. Soc., Trans., Vol. 71, Issue 0 https://doi.org/10.1039/CT8977100756	journal	January 1897
Heat-capacity measurements of aqueous solutions of mono-, di-, and tri-saccharides using an isoperibol twin calorimeter Kawaizumi, F.; Nishio, N.; Nomura, H. The Journal of Chemical Thermodynamics, Vol. 13, Issue 1 https://doi.org/10.1016/S0021-9614(81)80013-4	journal	January 1981
Thermodynamics of hydrolysis of disaccharides Tewari, Y. B.; Goldberg, R. N. Journal of Biological Chemistry, Vol. 264, Issue 7 https://doi.org/10.1016/S0021-9258(19)84947-5	journal	March 1989
Guidelines for evaluating and expressing the uncertainty of NIST measurement results Taylor, B. N. NIST Technical Note 1297 1994 Edition https://doi.org/10.6028/NIST.TN.1297	report	January 1994
Thermochemistry of the reaction { phospho enol pyruvate(aq)+d -erythrose 4-phosphate(aq) + H2 O(l) = 2-dehydro-3-deoxy- d - arabino -heptonate 7-phosphate(aq) + phosphate(aq) } Tewari, Yadu B.; Kishore, Nand; Bauerle, Ronald The Journal of Chemical Thermodynamics, Vol. 33, Issue 12 https://doi.org/10.1006/jcht.2001.0862	journal	December 2001
Heat capacities of maltose, maltotriose, maltotetrose and α-, β-, and γ-cyclodextrin in the solid state and in dilute aqueous solution Briggner, Lars-Erik; Wadsö, Ingemar The Journal of Chemical Thermodynamics, Vol. 22, Issue 11 https://doi.org/10.1016/0021-9614(90)90156-K	journal	November 1990
Enthalpies and heat capacities of dissolution, apparent molar heat capacities, and apparent molar volumes of some mono-, di-, tri-, and tetra-saccharides in water Jasra, R. V.; Ahluwalia, J. C. The Journal of Chemical Thermodynamics, Vol. 16, Issue 6 https://doi.org/10.1016/0021-9614(84)90010-7	journal	June 1984
Apparent molar heat capacities and apparent molar volumes of aqueous glucose at temperatures from 298.15 K to 327.01 K Kishore, N.; Goldberg, R. N.; Tewari, Y. B. The Journal of Chemical Thermodynamics, Vol. 25, Issue 7 https://doi.org/10.1006/jcht.1993.1082	journal	July 1993

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Related Subjects

BASIC BIOLOGICAL SCIENCES
BIOMASS FUELS
D-cellobiose
D-glucose
D-maltose
DISACCHARIDES
ENTROPY
FORMATION HEAT
FREE ENTHALPY
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY
HYDROLYSIS
PROPERTY VALUES
SACCHARIDES
SPECIFIC HEAT
THERMODYNAMICS
calorimetry
entropy
equilibrium constants
heat capacity

Thermodynamics of the Hydrolysis Reactions of 1,4-beta-D-xylobiose, 1,4-beta-D-xylotriose, D-cellobiose, and D-Maltose

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