Studies on the Structural and Colloidal Behavior of Polyvinyl Alcohol-Acetate Copolymers and of Egg Albumin

233 Pages·8.618 MB·English

by  Timasheff, Serge N

FORDHAM UNIVERSITY
GRADUATE SCHOOL
January... 15*.............19.51
This dissertation prepared under my direction by
.............Serge N. Timashef f........................................
entit[ecl STUDIES; ON T H E . J T R U C T ^ ...............
BEHAVIOR OF POLYVINYL ALCOHOL-ACETATE
................................COPOLYMERS AND OF EGG ALBUMIN..........................
has been accepted in partial fulfilment of the requirements for the
Degree of Doctor of Philosophy
Dr.....Friedr^
(Faculty Adviser)

STUDIES OH THE STRUCTURAL *AND COLLOIDAL
BEHAVIOR OF POLYVINYL ALCOHOL-ACETATE
COPOLYMERS AND OF EGG ALBUMIN.
By
Serge N. Timasheff
B .S ., Fordham College 1946
M .S., Fordham U niversity 194V
DISSERTATION
•SUBMITTED 111 PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY IN THE DEPARTMENT OF CHEMISTRY
AT FORDHAM UNIVERSITY"'1
NEW to rn
195*
L
ProQuest Number: 10992997
All rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is dependent upon the quality of the copy submitted.
In the unlikely event that the author did not send a complete manuscript
and there are missing pages, these will be noted. Also, if material had to be removed,
a note will indicate the deletion.
uest
ProQuest 10992997
Published by ProQuest LLC(2018). Copyright of the Dissertation is held by the Author.
All rights reserved.
This work is protected against unauthorized copying under Title 17, United States Code
Microform Edition © ProQuest LLC.
ProQuest LLC.
789 East Eisenhower Parkway
P.O. Box 1346
Ann Arbor, Ml 48106- 1346
i i i
r
TABLE OF CONTESTS i
page
L ist ©f Tables
v
L ist of Figures
v i i
Acknowledgments x
I. A. General Introduction 1
B. Theory of Light Scattering 5
0* Methods and Instruments 26
C.
II. C ritical Phenomena in Polyvinyl A lcohol-
-A cetate Copolymers
1. Aggregation Studies in PVA-A Fractions
A. Introduction 44
B. Experimental 53
C. R esults 60
D. D iscussion 8 7
2. Coagulation Studies in PVA-A and Sulfur
Solutions
A* Experimental and R esults 101
B. D iscussion 116
III. Studies on the Chemical M odification of
Egg Alhumin
1. Introduction 134
2. The Interaction of Egg Albumin with a
Thiophene-2-Azlactone
A. Introduction 136
B. Experimental 137
C. R esults and D iscussion 140
3. The Interaction of Egg Albumin with
Dodecylamine Hydrochloride
A. Introduction 155
B. Experimental 159
C. R esults 162
D. D iscussion 189
IV. General D iscussion 195
L
a
iv
r page n
V. Summary 199
VI. Appendices
1. A nalysis of PVA-A Bata in Terms of Pox-
-Flory Thermodynamics 202
2. Trans-Aeylation in Azlactone Synthesis 205
3. Typical Light Scattering C alculations 208
Bibliography 212
LIST OF TABLES
TABLE
I Angular D istribution of Scattered Light as
a Function of P article Size in the Case of
a Random Coil
II Dependence of Correction Factor on
In trin sic Dissymmetry
III Degree of Coagulation of PVA-A Solutions
at 45 C*
IT Turbidity Values of CoagulatingFVA-A
Solutions of Various Concentrations
V Light Scattering Data of 23-35°C.
Fraction
VI Light Scattering Data of 35-45°C.
Fraction
VII lig h t Scattering Bata of 45-53°C.
Fraction
VIII Light Scattering Data of 50-74°C.
Fraction
IX Light Scattering Data of PVA-A Fractions
X A cetyl Content of PVA-A Fractions
XI Dimensions of Polymer Chains for Various
Models
XII R eversib ility of Aggregation in PVA-A
Fractions
* V< ••'K.
XIII E ffect of Concentration on Turbidity
of PVA-A
XIV Thermodynamic Data on PVA-A Fractions
XV E ffect of Salt Addition on PVA-A Turbidity
XVI E ffect of Prefreezing on Heat Coagulation
of PVA-A
XVII U.V. Absorption Maxima of Thiophene
Azlactone Compounds
vi
rTABLE PAGE 1
XVIII Extent of Interaction between Egg Albumin
and Thiophene-2-Azlactone 146
XIX A nalytical la ta on Egg Albumin-Thiophene
Azlactone Interaction 148
XX R elative Change in Turbidity of Egg
Albumin-lodeeylamine Hydrochioride
Solutions of Various R atios 176
XXI M obilites of E lectrophoretic Boundaries
of Egg Albumin-lodeeylamine Hydrochloride
Systems 18©
XXII M ob ilities of E lectrophoretic Boundaries
of Egg AlbuminlodecylamineHydrochloride
Systems 182
XXIII Change of O ptical Rotation of Egg Albumin-
-lodeeylam ine Hydrochloride with Time 184
XXIV Combining R atios of Egg Albumin and
lodecylam ine Hydrochloride 193
XXV A pplication of Plory-Pox Theory to PVA-A
Aggregation 204
_j
v ii
n
LIST OF FIGURES
FIGURE PAGE
1 . Angular Scattering Diagram for Small
Isotropic P article 9
.
2 Lateral Scattering of Light "by a P article
the Dimensions of which are Comparable
with the Wave Length of Light 11
3. Angular D istribution of Scattered Light
as a Function of P article Size for the
Case of a Random Coil 17
4. Dissymmetry as a Function of l/* for
Spheres, C oils, and Rods of low R elative
Index of R efraction 19
5. Dependence of In trin sic Dissymmetry on
Length of P article 20
.
6 Scattering Dissymmetry Correction for
Large P a rticles 22
7. View of Light Beam at Various Angles 28
.
8 E ffect of Focusing Lens on P arallel Light 33
9. U ltra V iolet Absorption Spectrum of
KoCr0, ’ 41
2 4
.
10 Absorption Spectrum of Azobenzene 42
.
11 Change of Turbidity of a 3% PVA-A Solution
with Time 45
.
12 Aggregation of Ron-Fractionated PVA-A 47
13. Light Scattering Data of 23-35°C. PVA-A
Fraction 62
14. Dissymmetry Data of 23-35°C. PVA-A Fraction 63
15. Light Scattering Data of 35-45°C. PVA-A
Fraction 65
16. Dissymmetry Data of 35-45°C. PVA-A Fraction 66
17. Light Scattering Data of 45-53°C. PVA-A
Fraction 68
v iii
FIGURE' PAGE n
18. Dissymmetry Data of 45-53°C. PVA-A Fraction 69
19. Light Scattering Data ©f 50-74°C. PVA-A
Fraction 71
20. Dissymmetry Data of 50-74°c. Fraction 72
.
21 P article Weights of PVA-A Fractions at
Various Temperatures 74
.
22 Light Scattering Data of PVA-A 23-35°0.
Fraction Hydrolyzed 77
23. Light Scattering Data of Hydrolyzed PVA-A 78
24. P article Weights of PVA-A Fractions 81
25. Light Scattering Data Obtained in the
Aggregation Studies on Hon-Fractionated
PVA-A, Grade 52-22 96
26. Approach to Phase Separation 50-74°c.
PVA-A Fraction 99
27. Coagulation of PVA-A at Various Tem­
peratures 103
28. R eversib ility of PVA-A Coagulation upon
Cooling 105
29. R eversib ility of PVA-A Coagulation 106
30. E ffect of pH on PVA-A Coagulation 107
31. Influence of HaCl.on PVA-A Coagulation at
50 C. 109
32. Influence of HaCl on Thermal Coagulation
of PVA-A 112
33. T hiosulfate Sulfur Coagulation 118
34. Coagulation of Sulfur Sols 119
35. Coagulation of Sulfur Sols (lo g . relation ) 122
36. Coagulation of Sulfur (alcohol-w ater) 129
37. Coagulation of T hiosulfate Sulfur 130
38. PVA-A Coagulation 131