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ABSTRACT
7.1 INTRODUCTION :
3
and Pasteur may be considered as the base of modern
1 2
stereochemistry. Biot and Fresnel showed that
effect).
lline state.
7.2 THEORY :
at angle of
... (7.1)
<=k ■=■
(degr)
198
light beam.
7, 25, 26.
r* degr cm^
c- L \ g. dm ... (7.2)
is expressed as
r degr.cm'
z"' ” \oo
1U decimole
1 Us
> \bo
degr.cm
... (7.4)
decimole
degr. cm
(7.5)
decimole
2.8
'
Drude expressed a relationship between
as
... (7.7)
201
at certain wavelength.
be rewritten as
(7.8
viruses
as
20/
equation.
(7.10)
\ I
..(7.11)
> (7.12)
> . QL©
/
bo (7.13)
Q.o ¥
syndicate Hyderabad.
the value.
doubt.
tion.
by Moffitt.
209
r*
404. 1.4552 141.58 140.38 137.07
o
479. 1.4530 121.36 119.38 118.84
01*901
104.51
o
508. 1.4515 104.27
92.87
o
535. 1.4504 94.41 92.70
75.16
o
589. 1.4485 76.22 74.77
59.34
o
656. 1.4400 60.11 59.05
210
T a b le 7 .2 : ORD o f B o v in e serum a lb u m in H o t PH 5 .4
1
f\l
00
R e f r a c tiv e
II
'
E
E
O
H
r--
i—i
f-
A in d e x d e g re e s -c m 2 p e rd e c im o le
00 1
O li
= 212 nm fro m
^
M o f f i t t 's e x p r e s s io i
o o
X 00
oo• (30
nm
•n*
<H
= 2 1 1 .8 5 nm fro m N .D . r e l a t i o n
i
i
i
i
ii
ii
ii
ii
ii
i
i
i
ii
t
i
i
i
i
i
i
i
31
i
i
i
ii
1
1
11
1
11
oo 1
1
o 1
1
1
1
II 1
1
1 1
43 Dl
1
11
From e q . From e q . E x p e ri
(7 .1 3 ) (7 .1 0 ) , m e n ta l
1
CM
rH
r^
rH
—
i—1
4 0 4 .7 .5 3 5 0 -1 7 2 .9 3 1 8 3 . 05
CO
1—1
o
00
in•
so
rH
r-*
00
sr
.4 9 6 0 -1 0 9 .5 4 -1 2 6 . 24
CTii
00
in
5 0 8 .5 .4 7 8 1 -8 6 .1 7 -8 5 .2 1
00
rH
5 4 6 .1 .4 6 5 0 -7 0 .3 6 -7 0 .0 9 -7 5 .
1
o
o
to
rH
5 7 9 .0 .4 5 5 6 -6 0 .0 7 -6 6 . 45
H
5 8 9 .3 .4 5 3 0 -5 7 .9 1 -5 7 .9 3 -6 3 . 72
rH
6 4 3 .8 .4 4 1 1 -4 6 .1 9 -4 5 .9 3 -5 9 . 97
211
Table 7.3 : ORD of Insulin PH 8.5, 8M Urea
Refractive
00
-2 2
t
II
pH
<
o
u
e
0*
CM
X
co
00
cj
index . [m 13 degrees -
-cm perdecimole
nm
e
u
0
a
a = -692 = 212 nm Moffitt's expression
'
Ao
o
fl
II
Q
e
•
C
it
M
0
CM
rH
co
£
A
o
relation
r-
rH
404.7 1.5545 -262.56 -261. -269.53
00
to
467.8 1.5099 -180.70 -178. -187.82
'
i
o
rH
in
in
CO
«A
to
H*
to
Table 7.4 : ORD of Insulin PH 3.5.8M Urea
Refractive
t
00
2
1
-2
II
X
o
—i
oo
C\
CO
00
<J\
QJ
A
index cm [in'K degrees -cm. per decimole
c
e
ii
212 nm f.*om Moffitt's expression
d
= -510
o
o
u
.
D relation
1
1
1
1
1
1
I1
1
1
1
z 1
1
1
1
1
1
1
1
tfc-4 1]
0 1
e 1
1
1
1
c 1
E 11
r—I 11
CM• 11
it 1
CN 1
1
l
Dl
CO 1
1
1
1
1
1
l
l
1
XI 1
31
II 11
1
1 1
From eq. From eq . Experi
(7.13) (7.10) mental
CM
i—1
r-'
i£>
*
589.3 -77.34 -77.14 -85.12
ZOt) ~
0 Expt.lT
* Eqn. 7.13
„/ Eqn. 7.10
i9>
o
£
‘3
0-
IS
VJ
t
wv
<S>
5,
If
"G
j,
5-0
REFERENCES
1 _ (n-x)
“ <?#■ A substitution of eqn.(6) in Loventz-
Ti- ' Lorenz relation yields
TABLE II - MORD
Compound aM aM aM
ABSTRACT
: l
THE METHOD
The Lippincott — 8—function potential mode! is based on the Quantum
mechanical approach to the study of eigenstate of the system and polarizability
forms one of the fine critertion for testing suitability of such wave functions. It
gives an easy and faitly reliable method for the polarizability detcimir.ation.
Relevant equations to calculate the mean polarizability in terms of the parallel
bond component (v or,f erpcndicnlar bond contribution (H 2 and non-bond /-i-/
N
region electron conttibution {t oc,, „) are given as
where
A/
(X,-X2)]' /£* f>/
oc„ p = 4n A Ra + . ... (2)
A X ?j
a„ . 4 2Cr2 4 J
-2
•-A Xia
A} oc,-.
W-i-i
i i
Here n is the number of degrees of freedom given by the equation nd( = (3N-2t^k,) 6/
/iTtz *y where N is the number of atoms and ns is/thet^umber of bonds in the coenzyme.
Though various emperical methods <Guy <?t a!. 1954, Bandit, 1961, Habberditzl,
J964) have been developed to calculate the diamagneti. susceptibility, they were not
found>^o have universal application and hence Rao and Murthy (1979) have suggested
a relation which states that
hi where/g|/i$ the saturation factor explained in last section. This formula (eq. 6}
is applied to obtain the ‘Q’ values of the coenzymes. The values are given in Tabled.
The oxidation potential taken from Ref. (Fasman, G. D. 1952} of these eoenzymes lav
also given in Table 2 for comparison.
Results and discussion:
Frdm Tables l and 2, it is seen that the molecular polarizability as well as
diamagnetic susceptibility obey additive property as in any other type of simple
/ as/- molecules as well/jbiomolecules. Also the molar polarizability show an Increase with
increass in effective electro-negative character of the group transferied by the
ltd hi //enzyme. VA graph^rdrawn between electron ionization cross section as well aa-
oxidation potential of the, enzyme show a regular variation thereby showing that the
/ :)h/
ionization ability as well as oxidation, potential are well related tbroq^ the number
/to/ ^ree c^ectrons (available for reaction) present in th^fenzymes.
The relatively low values-of* molecular electron ionization cross-section in
/tj FMN or FAD is reflected in its/^ase to oxit^se or reduce a biomolecul^In Lipoid
HI
A
•J'
tfcid the val\ie is large. Tliis suggests tUc necessary foie it plays-in oxidative-
decarboxylation, A'lso Eipoic add acts as acyl transferring as well as hydrogen-
transferring agent. Similarly the multiple ways of reactivity of adenosine methiorine-
in /(l)/the transfer of sulphur to the t/^borr chain (in serine) as well as (ii)‘
/{O/ /cl/
transmethylation is indicated by the high value of Q as well as^-E Investigations-
in this field requiring' more confirmative approach to the enzyme kinetics are in
progress.
TABLE—f
POLARIZABILITIES ( X !D»* am? )
TABLE-2
^’OLARIZAMLFfrEs/(10a»)/ DIAMAGNETIC SUSCEPTIBILITIES (X10*) AND
MOLECULAR ELECTRON IONIZATION CROSS SECTION AND
OXIDATION POTENTIAL
/W “Zm q
*V(V>
; . Mot. Wl
Coenzyme tfXlp^cc)
rtSS) (xl0,*c“*>
Beran, J. A., and Kevan, L., J. I'hys. Chem. 73, 3860, (1969).
CRC Hand Book of physics and Chemistry, 59th ed. (1979),
Fasman, G. D., Hand Book of Biochemistry & Molecular Biology (ed), (1952);
Guy, J., Tillieu, J., Compt. Rend, 239, 1203, (1954).
Habbarditzl, U., Sitzchev. Deut, Akad Wiss. Berlin Ke Chem. Geol. Biol.
No. 2. (1964).
Murthy, V. R , In<f.*l?IhClSem. & Biophys. 16, 32, (1979).
Rao, B. P., Murthy, V, R., Subbaiah, D. V., Naidu, S. V., Acta Cienica Indies,
5 (p), 118, (1978).
Lippineot, E. R., Stutman, J. M., J, Phy. Chem. 68, 2465, (1965).
Sanyal, N. K„ Dixit, Paridey., A. N., J. Phys. Chem. 77. 2552, (1973).