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ISSN 2049-954X
Research Paper
Abstract
The linear equation of a general view Y = i f (N - g), where Y can be a free energy or heat of combustion orformation,
entropy and the heat of capacity, parameters, i and f are correlation factors, describing the interdependence between
thermodynamic functions of sugars and their numbers (N) of valence electrons except the numbers of lone electron pairs (g)
of heteroatoms in them, has been applied for calculation of sugars of a various structure. The obtained results can be used
for an estimation of the energy transfer in living systems by the means of phosphorus containing sugars like adenosinetriphosphate (ATP).
Keywords: Sugar, Carbohydrate, Combustion, Formation, Free Energy, Heat, Entropy, Heat Capacity
1. Introduction
The interest of biochemists to the definition and analysis of
thermodynamic functions of carbohydrates a various structure does not weaken during many tens years till this time
(Corbridge, 1980 and Haynie, 2008). It is established, that
metabolism processes of carbohydrates are carried out via
the formation of phosphorus-containing esters. The significance of phosphorus-containing sugars in biochemical
processes it is possible to explain from the energetic and
structural positions (Stepanenko, 1977). Nucleoside-diphosphosugars (NDFS) are good donors of the sugar rests
from the thermodynamic points of view. According to
Kochetkov and co-authors (Kochetkov et al, 1967) the
hydrogen bonds formation inside NDFS leads to the twist
conformation, which promotes its interaction with enzyme
and help to conduct biochemical reaction. Taking into
account the presented results only it is possible to make
some analysis of the thermochemical properties of sugars
of the different structure.
aHbNcOdPVe + nO2
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Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
ISSN 2049-954X
co = foproducts - foreagents..9
It is necessary to add, that the heats of combustion and
formation for the carbohydrates, containing the phosphate
cycles and adenine fragments (XX-XXVIII), were calculated previously (Ovchinnikov & Lapteva, 2011). The values
for the same parameters calculated in this work good
correspond to the mentioned earlier in the frames of
uncertainties (0.5 %) for calculations.
60
Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
ISSN 2049-954X
Table 1a. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase
No
Comp.
Compound,
Formula, (N-g)
-cGo (calc.
0.5%)
So (calc.
0.5%)
Cp (calc. 0.5%)
2865.9
923.5
2804.5
1271.5
205.4
217.0
2872.2
917.2
2803.3
1272.8
209.2
219.2
5826.5
1515.2
5652.1
2214.2
(395.7
2.0)
417.6
5789.9
1551.8
5643.4
2221.2
392.4
424.3
2874.1
915.4
2810.4
1265.6
(201.3
1.0)
208.0
(2403.3
12.0)
(815.9 4.1)
2347.6
1049.1
(168.9
0.8)
187.0
(2403.3
12.0)
(815.9 4.1)
2338.8
1057.9
(168.9
0.8)
184.0
(2403.3
12.0)
(815.9 4.1)
2340.0
1057.8
(168.9
0.8)
6126 , 24
II
6126, 24
III
122211, 48
IV
122211, 48
V
6126, 24
VI
C5H10O5, 20
VII
C5H10O5, 20
VIII
C5H10O5, 20
heat capacity for sugars (III, VI, XI, XII) and not
applicable for calculation for sugars including phosphorus
-atom.
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Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
ISSN 2049-954X
Table 1b. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase
IX
(2403.3
12.0)
(815.9
4.1)
2345.3
1051.4
143.5
184.0
(2889.5
14.4)
(918.3
4.6)
2799.1
1276.9
220.9
228.6
(2889.5
14.4)
(918.3
4.6)
2812.7
1263.4
(201.3
1.0)
214.2
(2888.9
14.4)
(918.3
4.6)
2820.4
1255.7
(201.3
1.0)
1944.1
1439.1
(1940.9
9.7)
(1769.6
8.8)
(10.7
0.05)
C5H10O5, 20
X
6126, 24
XI
6126, 24
XII
O
H
|
O|
2
H
O
|
O|P
O
6126, 24
(
XIII
C4H9O7P, 16
H
|O
|
O
H
2
H
O
|P
O|
O
H
O|
|
O|
XIV
Phosphor-Containing Sugars
(
2414.9
1599.9
(2413.2
12.0)
(1976.7
9.9)
(5.7
0.03)
2888.1
1758.3
(2885.5
14.4)
(2183.7
10.9)
(8.7
0.04)
2902.5
2600.8
(2960.8
14.8)
(3530.4
17.6)
(-195.5
1.0)
3364.6
1913.3
(3357.8
16.8)
(2390.8
11.9)
(22.8
0.1)
3379.0
2755.8
(3433.1
17.2)
(3308.7
16.5)
(-181.4
0.9)
2886.0
1760.3
(2885.5
14.4)
(2183.7
14.4)
(1.7
0.01)
(3617.3
18.1)
(1995.1
10.0)
(3594.0
18.0)
(1868.8
9.3)
(78.1
0.4)
H
|O
|
O
H
XV
2
H
O
|P
O|
O
H
O|
O
H
|
O|
5118P, 20
(
XVI
2
H
O
|P
O|
O
H
|O
|
O
H
H
O|
|
O|
|O
O|P2
O
H
6139P, 24
O
H
4
H
C|O
- H
|O|
2
H
O
|P
O|
O
61412P2, 24
(
XVII
XVIII
2
H
O
|P
O|
O
4
H
C|O
- H
|O|
O
H
|O
O|P2
C7H15O10P, 28
(
_ (
O
H
H
C
O
H
XIX
2
H
O H
|
O| P O
O
C7H16O13P2, 28
6139P, 24
O
XX
P
HO
OMe
OH
O
OH
7138P, 30
The analysis of entropic data for phosphor-containing
carbohydrates allows tomake some conclusion. A small
positive magnitude of So values (compounds XIII-XVII,
XIX-XXVII) can characterize the fact that in these compo-
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Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
ISSN 2049-954X
Table 1c. Thermodynamic Functions (kJ mol-1, J mol-1 K-1) of Carbohydrates at 298.15 K; all Compounds are in The Condensed Phase
e
M
O
HO
O
O
/
XXI
O P
HO
OH
(3617.3
18.1)
(1995.1
10.0)
(3594.0
18.0)
(1868.8
9.3)
(78.1
0.4)
(3617.3
18.1)
(1995.1
10.0)
(3594.0
18.0)
(1868.8
9.3)
(78.1
0.4)
(4831.3
24.1)
(2391.3
11.9)
(4774.7
23.9)
(1760.9
8.8)
(189.8
0.9)
(6045.3
30.2)
(2787.3
13.9)
(5955.4
29.8)
(544.9
2.7)
(301.5
1.5)
(6045.3
30.2)
(2787.3
13.9)
(5930.3
29.6)
(570.0
2.8)
(385.7
1.9)
(6045.3
30.2)
(2787.3
13.9)
(5955.4
29.8)
(544.9
2.7)
(301.5
1.5)
(6045.3
30.2)
(2787.3
13.9)
(6030.7
30.1)
(1748.7
8.7)
(49.0
0.2)
(6045.3
30.2)
(2787.3
13.9)
(6106.0
30.5)
(2666.6
13.3)
(-203.6
1.0)
7138P, 30
OH
O OH
OMe
O
XXII
O
P
HO
C7H13O8P, 30
HO
O
P
HO
XXIII
O
O
Me2
C9H15O8P, 40
O
O
XXIV
Ade
P
O
HO
OH
1012N56P, 50
O
HO
Ade
XXV
P
O
OH
1012N56P, 50
O
O
( HO)2P O
Ade
XXVI
HO
OH
1014N57P, 50
O
XXVII
| |
|
O
[
|P
O|
O
H
(
Ade
n=
HO
HO
OH
XXVIII
)
2
HO
| |
|
O
|[
P
O|
O
H
1015N510P2, 50
O
Ade
n= 2
HO
OH
1016N513P3, 50
workers (Kochetkov et al, 1967).
2.4. The Application of P-Sugars for Energy Transmission
The obtained thermodynamic data can be possible use for
the calculation of the heat of reaction (ro) between the
compressed glucose (II) and 1-adenine-ribofuranoside-5triphosphate (XXVII, ATP) (Eq. 14) for reception D-
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Ovchinnikov / Chemistry Journal (2013), Vol. 02, Issue 02, pp. 59-65
ISSN 2049-954X
3. Conclusion
We have shown the application of the equation Y = i f
(N - g) for the calculation of the free energy, of the heat of
combustion and formation, of entropy and heat capacity
for the big row of known sugars with a numbers valence
electrons N, from which the numbers of lone electron pair
g are excluded. The calculated equations give a possibility
to calculate the same thermodynamic parameters for phosphor-containing carbohydrates with the important biochemical function. The presented results can be used for an
estimation of the energy transfer in living systems by the
means of P-sugars like adenosine-triphosphate (ATP) too.
Acknowledgement
References
Boerio-Goates, J. (1991) Heat-capacity measurements and
thermodynamic functions of crystalline -D-glucose at
temperatures from 10K to 340K. J. Chem. Thermodynam., 23, pp. 403-409.
Clarke, T.H., and Stegeman, G. (1939) Heats of combustion of some mono- and disaccharides. J. Am. Chem. Soc.,
61(7), pp. 1726-1730.
Corbridge, D.E.C. (1980) Phosphorus. An Outline of its
Chemistry, Biochemistry and Technology. 2nd ed.
Amsterdam-Oxford-New York, Elsevier Scientific Publishing Company.
Cox, J.D., and Pilcher, G. (1970) Thermochemistry of
Organic and Organometallic Compounds. London-New
York, Academic Press.
Desai, P., and Wilhoit, R.C. (1970) Heats of combustion
and enthalpies of formation of D-ribose, D-arabinose, and
L-ascorbic acid. Thermochim. Acta, 1, pp. 61-64.
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ISSN 2049-954X
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