EFFECTS OF SIDE CHAINS ON THE CONFORMATION OF

POLYPEPTIDES

DISSERTATION

Submitted in partial fulfillment

of the requirements for

the degree of

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DOCTOR OF PHILOSOPHY (CHEMISTRY)

at the
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POLYTECHNIC INSTITUTE OF BROOKLYN
EV

Arthur M. Felix
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June 1964

Approved :

1964

Copy No. 1 Head, Department of^hemistry

Approved by the Guidance Committee :

Major: Organic Chemistry

Murray Goodman
Associate Professor of Chemistry

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F. Marshall Beringer /
Professor of Organic Chemistry

Minor: Polymer Chemistry

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Charles rberger
Professor of Chemistry
Head, Department of Chemistry
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Additional member:

Rudolph A. Marcus
Professor of Physical Chemistry

11
Microfilm or other copies of this

dissertation

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are obtainable from the firm of

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University Microfilms

313 North First Street

Ann Arbor, Michigan

PR

iii
 VITA

The author was born on June 15, 1938 in New York City.

His primary education was obtained in the public schools

of the Bronx. In 1955 he graduated from William Howard Taft

High School in the Bronx. After receiving his Bachelor of

Arts degree in Chemistry from the University College of

Arts and Science at New York University, graduate studies

were immediately taken up at the Polytechnic Institute of

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Brooklyn. He was appointed a Teaching Fellow in the

Chemistry Department for the academic year 1959-1960,

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after which he received a Research Fellowship sponsored

by the National Institutes of Health (1960-1962). In 1963

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he was awarded a National Health Institutes predoctoral

fellowship.

Preliminary reports describing this work have been

PR

published in the Journal of the American Chemical Society,

Vol. 84, pp. 3773-3774, October 1962, and Biopolymers,

Vol. 1, pp. 371-400, October 1963.

iv
 DEDICATION

This thesis is dedicated to the memory of

an inspiring American president,

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JOHN FITZGERALD KENNEDY
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PR

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 ACKNOWLEDGEMENT

The author wishes to express his deepest gratitude

to Professor Murray Goodman. Without his inspiration,

guidance and ceaseless encouragement this dissertation

would not have been possible.

The author also wishes to express his acknowledge­

ments to Mr. Charles M. Deber and Mr. Allan R. Brause,

whose efforts and contributions opened many new areas of

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research.

A sincere expression of gratitude goes to the

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author’s friend and colleague, Mr. Ira G. Rosen. His

advice and suggestions were extremely helpful and greatly

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appreciated.

A special vote of thanks goes to Mr. Axel Palmer

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of the Bendix Ericsson Corp, for his assistance in taking

many of the ultraviolet rotatory dispersion measurements.

The author wishes to express his gratitude to

Dr. Leon Levine, Miss Marija Stake, Mr. Aaron Kossoy,

Mr. Max Safdy, Miss Joan Sshulman, Dr. Franklin Boardman,

and Mr. Mishael Langsam for their suggestions and

assistance during the course of this work.

The assistance offered by Mr. Gerald Schwartz in the

form of his superb technical drawings and skillful

geometrical calculations were of incalculable value.

A final note of gratitude goes to Miss Joan Lazar for

her technical assistance in taking numerous measurements.

 ABSTRACT

The effect of amino acid composition on the conforma­

tion of synthetic polypeptides and proteins has been

investigated extensively_in recent years. It was suggest­

ed^^ that there are two classes of «-amino acids, those

which form helical structures, and those which form either

random or associated structures. Since helices are

dissymmetric, helical polypeptides can be either right­

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handed or left-handed; those derived from L-amino acids

generally form right-handed helices. However, it was

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shown recently that certain esters of poly-a-L-aspartic

acid form left-handed helices. Furthermore, this type of

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helix from poly-£-benzy1-L-aspartate is weaker than the

right-handed helix of poly-Y-benzyl-L-glutamate.

We attempted to prepare a high molecular weight, water­

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soluble, nonionic helical polypeptide composed of only one

optical isomer since such polymers can serve as more

effective model compounds for use in physico-chemical

studies relating to proteins. To this end, poly-5-hydroxy-

L-a-aminovaleric acid was synthesized. Although the pre-

a-
cursor, poly-fl-O-acetyl-L-aminovaleric acid, was>shown to

be helical in dimethylformamide and trifluoroethanol, the

unblocked polypeptide, poly-ç-hydroxy-L-a-aminovaleric acid,

was non-helical in water, dichloroacetic acid, and 8M aqueous

lithium bromide. Evidence for stable helices was obtained

in aqueous solutions containing IM lithium bromide or less.

vii
 Another important objective of this dissertation was
to study the effect of bulky groups such as (2-methyl-l-

butyl) on the conformation of poly-p-alkyl-aspartates and

poly-Y-alkyl-glutamates. We also studied the effects of

side-chain optically active groups on the rotatory

properties of aspartate and glutamate polymers. In order

to carry out such studies a series of new polymers and co­

polymers of aspartic and glutamic acid were prepared. We

observed that although poly-alkyl-glutamates are un­

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affected by the presence of bulky or optically active side

chains, the corresponding poly-alkyl-aspartates show

dramatic effects.
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Bulky side chains were shown to force

the left-handed aspartate into a partially right-handed

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helical conformation.

A third objective of this dissertation was the prep­

aration of an optically active polyester that could serve

PR

as the oxygen analog of a polypeptide. Low molecular

weight poly-2-hydroxy-4-methyl-L-valeric acid was

synthesized. Its conformation was shown to be independent

of solvent. A new Cotton effect (positive) was observed in

dioxane. The existence of secondary structure of.a differ­

ent nature from that present in polypeptides is suggested.

We were also interested in examining the effect of a

jd-nitro group on the conformation of poly-p-benzyl-L-

aspartate.

viii
 We demonstrated that in chloroform the left-handed

helical sense of poly-^-benzyl-L-aspartate is converted

to a right-handed sense for poly-^-p-nitrobenzyl-L-

aspartate. This transition occurs at 26-32 mole# nltro-

benzyl-L-aspartate content in the copolymers prepared from

these L-aspartate esters. A new conformationally dependent

Cotton effect was uncovered for these copolymers with a

trough at 370 my,.

From a study of the above copolymers in dimethylform­

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amide we showed that the conformation of poly-p-p-nltro-

benzyl-L-aspartate is helical while the conformation of

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poly-p-benzyl-L-aspartate is random.

We propose the formation of a four-stranded side chain

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helix to explain the enhanced rotatory properties for the

nitrated poly-L-aspartates. Each strand is held together

by non-bonded interactions of nitroaromatic groups four

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residues removed from each other. It was established in our

laboratory that poly-v-benzyl-L-glutamate is unaffected by

the introduction of jD-nitro groups. We suggest an explana­

tion for the anomalous behavior of poly-L-aspartates involv­

ing competitive hydrogen bonding. Barring electronic or

steric effects as noted above, the L-aspartate polymers do

not form right-handed helices because of geometrically

favored intrachain hydrogen bonding between main chain amides

and side chain esters.

lx
 TABLE OF CONTENTS

Page

I. INTRODUCTION 1

II. HISTORICAL 3

III. RESULTS AND DISCUSSION 19

A. Synthesis and conformational studies of

poly- Ô-hydroxy-L-ex-aminovaleric acid 19

B. Syntheses and conformational studies of

poly-Y-(2-methyl-l-butyl)-glutamates and
poly-p-(2-methyl-l-butyl)-aspartates 32

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C. Syntheses and conformational studies of
poly-2-hydroxy-4-methyl-L-valeric acid
and poly-p-hydroxybutyric acid
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D. Conformational studies of copolymers of

poly-p-jo-nitrobenzyl-L-aspartate with
poly-p-benzyl-L-aspartate 54
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1. in chloroform 56
2. in dimethylformamide 67
3. in trifluoroacetic acid 73
4. geometrical considerations 77
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IV. CONCLUSIONS 92

A. Poly-6-O-acetyl-L-a-aminovaleric acid and

poly-6-hydroxy-L-a-aminovaleric acid 92

B. Poly-Y-(2-methyl-l-butyl)-glutamates and
poly-p-(2-methyl-l-butyl)-aspartates 93

C. Poly-2-hydroxy-4-methyl-L-valeric acid
and poly-p-hydroxybutyric acid 94

D. Poly-p-jo-nltrobenzyl-L-aspartate 95

V. EXPERIMENTAL 97

A. Materials 97

B. Preparation of compounds 98

N-^-Toluenesulfonyl-L-glutamlc acid (IV) 98

Anhydrous 1-jo-toluene sulf on

5-one-2-carboxyllc acid (V) 98
 TABLE OF CONTENTS(contd.)

Page

Li thlum-l-jo-toluene sulf onyl-L-pyrrolld-5-

one-2-carboxylate (VI ). Method A. 99

Li thium-l-jD-toluene sulf onyl-L-pyrrolid-5-

one-2-carboxylate (VI ). Method B. 99

ô-Hydroxy-L-a-tosylaminovaleric acid (VII ) 99

6-Hydroxy-L-a-aminovaleric acid (VIII) 100

a-Amino-L- ô-valerolactone hydrochloride

(Villa) 102

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Copper chelate of O-carbobenzoxy-DL-
serlne (Xa) 102

Copper chelate of O-carbobenzoxy-L-

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serine (Xa1) 103

Copper chelate of 0-jo - ni t r oc arb obe nz oxy-

L-serine (Xb) 103
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ô-0-Acetyl-L-a-aminovaleric acid hydro­

chloride (XI) 104

ô-0-Acetyl-L-a-aminovaleric acid (Xia) 105

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Ô-0-Acetyl-L-a~aminovaleric acid-N-
carboxyanhydride (XII) 105

Poly-6-0-acetyl-L-a~aminovalerlc acid
(HI;n=3,R=COCH3). Method A. 106

Poly-Ô-0-acetyl-L-a-aminovaleric acid
(III,n=3,R=C0CH3). Method B. 10?

Poly-Ô-hydroxy-L-a-aminovaleric acid
(III,n=3,R=H). Method A. 10?

Poly-ô-hydroxy-L-a-aminovaleric acid
(III,n=3,R=H). Method B. 108

Y-Isoamyl-DL-glutamate (XIV) 109

Y-RS~(2-Methyl-l-butyl)-L-glutamate (XV) 110

 TABLE OF CONTENTS(contd.)

Pa&e
Y-S_(2-Methyl-l-butyl)-L-glutamate (XVI) ill

y_S-(2-Methyl~1-buty1)-D-glutamate (XVII) 111

Y-S-(2-#ethyl~l-butyl)-L-glutamate-N-
carboxyanhydride (XVIII) 112

Y-S-(2-Methyl-l-butyl)-D-glutamate-N-
carboxyanhydride (XIX) 113

Poly-Y-S-(2-methyl-l-butyl)-L-glutamate
(XIII;n=2,*=L,$=S) 113

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Poly-y-S-(2~methyl~l~butyl)-D-glutamate
(XIII;n=2,*=D,*=S). 114

Poly-Y-5-(2-methyl-l-butyl)-DL-glutamate
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(XIII;n=2, *=DL, *=S) 114

p-RS-(2-Methyl-l-butyl)-L-aspartate (XX) 115

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p-S-(2-methyl-l-butyl)-L-aspartate (XXI) 116

6-S-(2-Methyl-l-butyl)-D-aspartate XXII) 117

6-RS-(2-^ethyl-l-butyl)-L-aspartate-N-
carboxyanhydride (XXIII) 117
PR

6-5-(2-Methyl-l-butyl)-L-aspartate-N-
c arb oxyanhyd ride (XXIV) 117

6-S-(2-Methyl-l-butyl)-D-aspartate-N-
carboxyanhydride (XXV) 118

Poly-p-RS-(2-methyl-l-butyl )-L-aspartate
(XIII;n=l,*=L,$=RS) 118

Poly-6-S-(2-methyl-l-butyl)-L-aspartate
(XIII; n=l,*=L, *=S) 119

Poly-6-5-(2-methyl-l-butyl)-D-aspartate
(XIII;n=l,*=D>*=S 119

Poly-6-S-(2-methyl-l-butyl)-DL-aspartate
(XIII;n=l,*=DL,+=S) 120

6-phenyl-L-lactic acid (XXVI). Method A. 120

xM
 TABLE OF CONTENTS(contd.)

Page

£-phenyl-L-lactlc acid (XXVI). Method B. 121

Attempted preparation of g-phenyl-L-

lactic acid anhydrosulfite 121
2-Hydroxy-4-methyl-L-valeric acid (XXIX) 122

2-Hydroxy-4-methyl-L-valeric acid anhydro-

sulflie(XXVII;R1=H, Rg= -CH2-CH(CH3)2) 122

Poly-2-hydroxy-4-methyl-L-valeric acid
(XXVIIIjR^H, R2= -CH2-CH(CH3ÿ 123

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Copper chelate of ^-benzyl-DL-malate (XXX) 124

^-benzyl-DL-malate (XXXI) 124

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Y-Carb oxy-L-Y-butyrolac tone (XXXII) 125

Reaction of Y-ethyl-L-glutamate with

nitrous acid 126
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Reaction of Y-benzyl-L-glutamate with nitrous
acid 12?

Reaction of L-glutamine with nitrous acid 127

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p-^p-Nitrobenzyl-L-aspartate (XXXIV) 12?

^-^-Nitrobenzyl-L-aspartate-N-carboxy-
anhydride (XXXV) 128

Poly-0-p-nltrobenzyl-L-aspartate (XXXVI) 128

Preparation of copolymers of p-^-nitrobenzyl-

L-aspartate with p-benzyl-L-aspartate 128

Formation of poly-L-succinimide (XXXVII)

from poly-^-p-nltrobenzyl-L-aspartate 129

C. Apparatus and Measurements 132

Optical rotations 132

Infrared spectra 133
Molecular weight determinations 133
Ultraviolet spectra 134
Circular dichroism 134

VI. BIBLIOGRAPHY 181

xiH
 FIGURES AND TABLES

Figures Page

1. The left-handed and right-handed conformations

of the a-helix 4

2. Ultraviolet rotatory dispersion of poly-7-

benzyl-L-glutamate and poly-L-methionine 14

3. Far ultraviolet rotatory dispersion of the

helical and random, coil forms of poly-a, L-
glutamic acid 16

4. Ultraviolet rotatory dispersion of polywô-O-

acetyl-L-a-aminovaleric acid in trifluoroethanol

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and poly-ô-hydroxy-L-a-aminovaleric acid in
aqueous lithium bromide 31

5.
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Ultraviolet rotatory dispersion of poly-y-(2-
methyl-l-butyl)-glutamates in dioxane 37

6. Ultraviolet rotatory dispersion of poly-p-(2-

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methyl-1-butyl)-aspartates in dioxane 43

?. Ultraviolet rotatory dispersion of poly-2-

hydroxy-4-methyl-L-valeric acid in dioxane and
poly-6-hydroxybutyric acid in trifluoroethanol 53
PR

8. The specific rotations at 546 my, in chloroform

at 25.0°C for copolymers of LNBA with LBA 58

9. Values of bo and Xc in chloroform at 25.0°C. for

copolymers of LNBA with LBA 59

10. Ultraviolet rotatory dispersion of copolymers of

LNBA with LBA in chloroform at 25.0°C having
various nitro residue contents : 15.O mole-0,
26.0 mole-0, and 32.0 mole-0 60

11. Optical rotatory dispersion of P-LBA and a co­

polymer of LNBA with LBA in chloroform at 25.0°C
having 66.0 mole-0 nitro residue content 61

xlv
 FIGURES AND TABLES (contd.)

Figures Page

12. Optical rotatory dispersion of P-LBA and co­

polymers of LNBA with LBA in chloroform at
25.0
0.
* having various nitro residue contents :
8.5 mole-0 and 15.0 mole-0 64

13. Optical rotatory dispersion of copolymers of LNBA

with LBA in chloroform at *0°C.
25 having various
nitro residue contents : 26.0 mole-0, 32.0 mole-0,
50.0 mole-0, and 58.5 mole-0 65

14. Residue rotations in chloroform at *

0°C.
25 at the
trough of the 370 mu Cotton effect for copolymers

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of LNBA with LBA 66

15 * Optical rotatory dispersion, circular dichroism

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and ultraviolet absorption curves in chloroform
for the copolymer of LNBA with LBA having 58.5
mole-0 nitro residue content 68
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16. Values of b0 and in dimethylformamide at
25
0
* . for copolymers of LNBA with LBA 70

17. Values of Xc in dimethylformamide at 25.0°C.

for copolymers of LNBA with LBA 71
PR

18. Observed rotation in dimethylformamide at 25.0°C.

at 546 mu as a function of time for poly-p-^-
nitrobenzyl-L-aspartate catalyzed with diethyl­
amine . 74
546
19. Values of bo and [«125 in trifluoroacetic acid
at 25.0oC. for copolymers of LNBA with LBA 75

20. Optical rotatory dispersion of poly-£-£-nitro-

benzyl-L-aspartate in dimethylformamide 78

21. The suggested structure for poly-L-aspartate

esters in the left-handed conformation with
minimum carbonyl interactions 78

22. The suggested perturbed structure for poly-L-

aspartate esters in the right-handed conformation 79

xv.
 FIGURES AND TABLES (contd.)

Figures Page

23. The suggested structure for poly-L-aspartate

esters in the left-handed conformation with
maximum carbonyl interactions 82

24. The suggested structure of poly-^-p-nitro-

benzyl-L-aspartate in the right-handed conform­
ation showing interactions of alternate side
chains 84

25. The suggested structure of poly-^-p-nitrobenzyl-

L-aspartate in the right-handed conformation
showing the proposed 4-stranded interactions of

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the side chains 86

26. Schematic representation of the proposed 4-

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stranded P-LNBA side-chain helix 87
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PR

xyi '
 FIGURES AND TABLES (contd.)

Tables Page

I Specific rotations and derived constants for

poly-ô-0-acetyl-L-a-aminovaleric acid at 25.0°C. 26

II Specific rotations and derived constants for poly-

ô-hydroxy-L-a-aminovaleric acid at 25.0°C. 29

III Specific rotations and derived constants for poly-

Y-(2-methy1-1-butyl)-glutamates in dioxane 36

IV Specific rotations and derived constants for

poly-p-(2-methyl-l-butyl)-aspartates 41

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V Specific rotations and derived constants of poly-
2-hydroxy-4-methyl-L-valeric acid and poly-p-
hydroxy-butyric acid 52

VI
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Values of bo and [a] for homopolymers of L-
glutamic and L-aspartic acid esters at 25.0°C. 56
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VII Specific rotations and derived constants for 57
copolymers of LNBA with LBA in chloroform at 25. 0°C

VIII Summary of the 370 my, Cotton effect and the

233 my. Cotton effect trend of copolymers of
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LNBA with LBA in chloroform 63

IX Summary of the ultraviolet absorption spectra of

copolymers of LNBA with LBA 63

X Optical rotatory dispersion data for copolymers

of LNBA with LBA in dimethylformamide at
25.0°C. 69

XI Optical rotatory dispersion data for copolymers

of LNBA with LBA in trifluoroacetic acid at
25.0*C 73

XII Geometrical calculations for poly-L-aspartate

in the proposed perturbated right-handed
(18-5) helix 80

xvii-
 FIGURES AND TABLES (contd.)

Tables Page

XIII Geometrical calculations for poly-L-aspar­

tate in the left-handed (18-5) helix with
minimum side-chain:main-chain interactions 81

XIV Geometrical calculations for poly-L-aspar-

tate in the left-handed (18-5) helix with
maximum side-chain:maln-chain interactions 83

XV Geometrical calculations for P-LNBA in the

four-stranded side-chain right-handed helix 88

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XVI Quantities used and yields obtained for co­
polymers of LNBA with IBA 130

XVII Elemental analyses of copolymers of

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LNBA with IBA 131

XVIII Optical rotatory dispersion data for poly-

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ô-0-acetyl-L-a-aminovaleric acid in di­
methylformamide at 25
0°C.
* 135

XIX Optical rotatory dispersion data for poly-

ô-0-acetyl-L-a-aminovaleric acid in tri­
fluoroethanol at 25-0°C.
PR

135

XX Optical rotatory dispersion data for poly-

Ô-0-acetyl-L-a-aminovaleric acid in dichloro­
0°C.
*
acetic acid at 25 136

XXI Ultraviolet rotatory dispersion data for

poly- 6-0-acetyl-L-ct-aminovaleric acid in
tri fluoroethanol 136

XXII Optical rotatory dispersion data for poly-

Ô-hydr oxy- L- a-aminovaleric acid in dichloro­
acetic acid at 25-0°C, 137

XXIII Optical rotatory dispersion data for poly-

Ô-hydroxy-L-a-aminovaleric acid in water
at 25.0°C. 137

xvMi
 FIGURES AND TABLES (contd.)

Tables Page

XXIV Rotatory dispersion data for poly-Ô-hydroxy-

L-a-aminovaleric acid in 8M aqueous lithium
bromide. 138
XXV Rotatory dispersion data for poly-Ô-hydroxy-
L-a-aminovaleric acid in 2M aqueous lithium
bromide. 139
XXVI Ultraviolet rotatory dispersion data for poly-
ô-hydroxy- L-a-aminovaleric acid in IM aqueous
lithium bromide. 140

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XXVII Optical rotatory dispersion data for poly-y-
S-(2-methyl-l-butyl)-L-glutamate in dioxane
0.
*
at 25-0 140

XXVIII
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Ultraviolet rotatory dispersion data for poly-
Y-S-(2-methyl-l-butyl)-L-glutamate in dioxane. 141

XXIX Optical rotatory dispersion data for poly-Y-

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S-(2-methyl-l-butyl)-D-glutamate in dioxane
at 25-0°C. 141

XXX Ultraviolet rotatory dispersion data for poly-

Y-S-(2-methyl-l-butyl)-D-glutamate in dioxane. 142
PR

XXXI Optical rotatory dispersion data for poly-y-S-

(2-methyl-l-butyl)-DL-glutamate in dioxane
0.
*
at 25-0 142

XXXII Ultraviolet rotatory dispersion data for poly-

Y-S-(2-methyl-l-butyl)-DL-glutamate in dioxane. 143

XXXIII Optical rotatory dispersion data for poly-£-

RS-(2-methyl-l-butyl)-L-aspartate in dioxane
at 25-0
0.
* 143

XXXIV Optical rotatory dispersion data for poly-p-

RS-(2-methyl-l-butyl)-L-aspartate in trifluoro­
acetic acid at 25.0
0.
* 144

XXXV Ultraviolet rotatory dispersion data for poly-

p-RS-(2-methyl-l-butyl)-L-aspartate in dioxane 144

XXXVI Optical rotatory dispersion data for poly-p-

5-(2-methyl-l-butyl)-L-aspartate in dioxane
at 25-0
0.
* 145

xix
 FIGURES AND TABLES (contd.)

Tables Page

XXXVII Optical rotatory dispersion data for poly-p-

S- (2-methyl-l-butyl)-L-aspartate in tri-
fluoroacetlc acid at 25.0^0. 14$

XXXVIII Ultraviolet rotatory dispersion data for

poly-p-S-(2-methyl-l-butyl)-L-aspartate in
dioxane. 146

XXXIX Optical rotatory dispersion data for poly-p-

S-(2-methyl-l-buty1)-D-aspartate in dioxane
at 25-0*0. 146

XL Optical rotatory dispersion data for poly-p-

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S-(2-methy1-1-butyl)-D-aspartate in trlfluoro-
acetic acid at 25.0&C. 147

XII Ultraviolet rotatory dispersion data for poly-

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p-S-(2-methyl-l-butyl)-D-aspartate in
dioxane. 147

XIII Optical rotatory dispersion data for poly-p-

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S-(2-methyl-l-butyl)-DL-aspartate in dioxane
at 25.0°C. 148

XIIII Optical rotatory dispersion data for poly-p-

S-(2-methyl-l-butyl)-DL-aspartate in tri­
fluoroacetic acid at 25.0°C. 148
PR

XIIV Ultraviolet rotatory dispersion data for poly-

p—S—(2—methyl—1—butyl)—DL—aspartate in dioxane. 149

XLV Optical rotatory dispersion data for poly-2-

hydroxy-4-methyl-L-valeric acid in benzene at
25.0*0. 149

XLVI Optical rotatory dispersion data for poly-2-

hydroxy-4-methyl-L-valeric acid in dichloro­
acetic acid at 25.0*0. 150

XLVII Optical rotatory dispersion data for poly-2-

hydroxy-4-methyl-L-valeric acid in chloroform
at 25.0*0. 150

XLVIII Ultraviolet rotatory dispersion data for poly-

2-hydroxy-4-methyl-L-valeric acid in dioxane 151

xx
 FIGURES AND TABLES (contd.)

Tables page

XLIX Ultraviolet rotatory dispersion data for

poly-hydroxybutyric acid in trifluoro­
ethanol. 152

L Ultraviolet absorption spectra data for poly­

p-hydroxy-butyric acid in trifluoroethanol. 153

U Optical rotatory dispersion data for poly-p-

hydroxy-butyric acid in trifluoroethanol. 153

UI Ultraviolet absorption spectra data for poly-

£-benzyl-L-aspartate in chloroform. 154

UII Ultraviolet absorption spectra data for poly-

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p-benzyl-L-aspartate in trifluoroacetic acid. 154

UV Ultraviolet rotatory dispersion data for poly-

p-benzyl-L-aspartate in chloroform (243­
IE
455 mil) . 155

LV Ultraviolet rotatory dispersion data for poly-

^-benzyl-L-aspartate in chloroform (290-589 m$i). 155
EV

LVI Ultraviolet absorption spectra data for 8.5^

P-LNBA:91.5^ P-LBA in chloroform. 156

LVII Ultraviolet absorption spectra data for 8.50

PR

P-LNBA:91.5% P-LBA in trifluoroacetic acid. 156

LVIII Optical rotatory dispersion data for 8.5%

P-LNBA:91.5% P-LBA in chloroform at 25-0°C. 156

LIX Ultraviolet rotatory dispersion data for 8.5%

P-LNBA:91.5% P-LBA in chloroform(240-455 mil). 157

LX Ultraviolet rotatory dispersion data for 8.5%

P-LNBA:91.5% P-LBA in chloroform at 25-0°C
(330589 mix). 157

LXI Optical rotatory dispersion data for 8.50

P-LNBA:91.50 P-LBA in trifluoroacetic acid
at 25.0°0. 158

LXII Ultraviolet absorption spectra data for 15-0%

P-LNBA:85.0% P-LBA in chloroform. 158

LXIII Ultraviolet absorption spectra data for 15

00
*
P-LNBA:85 *
00 P-LBA in trifluoroace tic acid. 159

lxtv Optical rotatory dispersion data for 15

00
*
P-LNBA:85.00 P-LBA in chloroform at *
0
25 C. 159
 FIGURES AND TABLES (contd.)

Tables Page

LXV Ultraviolet rotatory dispersion data for 15.0^

P-LNBA:85-O^ P-LBA in chloroform (243-455 mp.). 160

LXVT Ultraviolet rotatory dispersion data for 15.00

P-LNBA:85*00 P-LBA in chloroform (330-589 mp.). 160

LXVII Optical rotatory dispersion data for 15-00

P-LNBA:85-O0 P-LBA in dimethylformamide at
25-0*0. 161

LXVTII Optical rotatory dispersion data for 15.00

P-LNBA:85-O0 P-LBA in trifluoroacetic acid
at 25.0*0. 161

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LXIX Ultraviolet absorption spectra data for
26.Q0 P-LNBA:?4.O0 P-LBA in chloroform. 162

LXX Ultraviolet absorption spectra data for 26.00

IE
P-LNBA:y4.O0 P-LBA in trifluoroacetic acid.162

LXXI Optical rotatory dispersion data for 26.00

P-LNBA:74.O0 P-LBA in chloform at 25.0*0. 163
EV
LXXII Ultraviolet rotatory dispersion data for
26.00 P-LNBA:74.O0 P-LBA in chloroform (244­
455 mp.). 163

LXXIII Ultraviolet rotatory dispersion data for

PR

26.00 P-LNBA:74.00 P-LBA in chloroform

(330589 mu). 164

LXXIV Optical rotatory dispersion data for 26.00

P-LNBA:740 P-LBA in dimethylformamide at
25-0*0. 165

LXXV Optical rotatory dispersion data for 26.00

P-LNBA:74.O0 P-LBA in trifluoroacetic acid at
25.0*0. 165

LXXVI Ultraviolet absorption spectra data for 32.00

P-LNBA;68.00 P-LBA in chloroform. 166

LXXVII Ultraviolet absorption spectra data for 32.00

P-LNBA:680 P-LBA in trifluoroacetic acid. 166

LXXVIII Optical rotatory dispersion data for 32.00

P-LNBA:68.00 P-LBA in chloroform at 25.0*0. 167

LXXIX Ultraviolet rotatory dispersion data for 32.00

P-LNBA:68.00 P-LBA in chloroform (244-455 my.). 16$

xxil
 FISURES AND TABLES (contd.)

Tables Page

LXXX Ultraviolet rotatory dispersion data for 32.0^

P-LNBA;68^ P-LBA in chloroform (330-589 my.). 168

Lxm Optical rotatory dispersion data for 32.0$

P-LNBA:68$ P-LBA in dimethylformamide at 25.0°C. 168

LXXXII Ultraviolet absorption spectra data for 50.0$

P-LNBA:50.0$ P-LBA in chloroform. 169

LXXXEII Ultraviolet absorption spectra data for 50.0$

P~LNBA:5O.O$ P-LBA in trifluoroacetic acid. 169

LXXXEV Ultraviolet rotatory dispersion data for

W
50.0$ P-LNBA:50.0$ P-LBA in chloroform at
25.0°C. 170

LXXXV Ultraviolet rotatory dispersion data for

IE
50.0$ P-LNBA:50.0$ P-LBA in chloroform (250­
455 mu). 170

LXXXVI Ultraviolet rotatory dispersion data for

EV
50.0# P-LNBA:50.0% P-LBA in chloroform (330­
589 my.). 171

LXXXVII Optical rotatory dispersion data for 50.0$

P-LUBA:50.0$ P-LBA in dimethylformamide at 25
0°
* C.171
PR

LXXXVIII Optical rotatory dispersion data for 50.0$

P-LNBA:50.0$ P-LBA in trifluoroacetic acid
at 25.0
0.
* 172

LXXXIX Ultraviolet absorption spectra data for 58.50

P-LNBA:41.5$ P-LBA in chloroform. 172

xc Ultraviolet absorption spectra data for 58.5$

P-LNBAî41.5$ P-LBA in trifluoroacetic acid. 173

XCI Optical rotatory dispersion data for 58.50

P-LNBA:41.50 P-LBA in chloroform at 25.0°C. 173

XCII Ultraviolet rotatory dispersion data for

58.5$ P-LNBA:41.5$ P-LBA in chloroform (240­
455 mu). 174

XCIII Ultraviolet rotatory dispersion data for

58.50 P-LNBA:41.50 P-LBA in chlofoform at
25.0°C (33O-589mu). 174

xxiii
 TABLES AND FIGURES (contd.)

Tables Page

XCIV Circular dichroism data for 58.50 P-LNBA:

41.50 P-LBA in chloroform. 175

XCV Optical rotatory dispersion data for 58.50

P-LNBA:41-50 P-LBA in dimethylformamide at
25.0°C. 176

XCVI Ultraviolet absorption spectra data for 66.00

P-LMBA:34.00 P-LBA in chloroform. 176

XCVII Ultraviolet absorption spectra data for 66.0$

P-LNBA:34.O$ P-LBA in trifluoroace tic acid. 177

W
XCVIII Optical rotatory dispersion data for 66.00
P-LNBA:34.O$ P-LBA in chloroform at *
25-0
0 . 177

XCIX Ultraviolet rotatory dispersion data for

IE
66.0$ P-LNBA:34.O$ P-LBA in chloroform
(238-455 mp.). 178

c Ultraviolet absorption spectra data for 72.0$

EV
P-LNBA:28.0$ P-LBA in 95-00 trifluoroacetic
acid;5.0$ chloroform (by volume). 178

CI Optical rotatory dispersion data for poly-p-

o-nitrobenzyl-L-aspartate in dimethylformamide
at 25-0°C. 179
PR

on Kinetics of poly-L-succinimide formation from

poly-p-p-nitrobenzyl-L-aspartate in dimethy1-
formamide at 25-0°C. 179

cm Ultraviolet rotatory dispersion data for poly-

p-2-nïtrobenzyl-L-aspartate in dimethylformamide
at 25-0°C. 180

xxiv

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