Studies on Lignins of Woods and Jute

89 Pages·3.412 MB·English

by  Kudzin, Stanely F

r
FORDHAM UNIVERSITY
GRADUATE SCHOOL
19.51.
This dissertation prepared under my direction by
Stanley F. Kudzin
entitled STUDIES ON LIGNINS OF WOODS AND JUTE
has been accepted in partial fulfilment of the requirements for the
Degree of Doctor of Philo sophy
Dr...F,F....Nqrd.....
(Faculty Adviser)

STUDIES ON DIGNINS OF WOODS AND JUTE
BY
STANDBY F* KUDZIN
B#S*f F©r&liam G©llegef 1947
M*S*, FordJaam University, 1949
DISSERTATION
SUBMITTED IN PART I AD FUDFIDDMENT OF THE REQUIRE­
MENTS FOR THE DEGREE OF DOG TOR OF PHIDOSOPHY IN
THE DEPARTMENT OF 0HE1ISTRY AT FORDHAM UNIVERSITY
NEW YORK
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ii
r TABLE OF CONTENTS i
Page
LIST OP TABLES .............. ♦ . iv
LIST OP FIGURES ..................................... v
ACKNOWLEDGEMENTS ............................. .. ♦ vii
I. INTRODUCTION *............................... 1
II* EXPERIMENTAL METHODS ........ 6
A. Microbiological •••••........ 6
B. Analytical • • 8
G. Preparative ••••.... .............. 11
B* Spectroscopic 13
III. EXPERIMENTAL RESULTS ........................ 14
A. Studies on Softwood Lignin ••....••••••...•• 14
1. Infrared Absorption Speotra «••••••••••••• 15
2. Methylation with Biazomethane 18
3. Oxidation with Alkali and Nitrobenzene .. . 21
B. Studies on Hardwood Native Lignins ........ 23
1. Elementary and Methoxyl Analyses of
Native Lignins....•••.••••••••••••••.« 25
2. Ultraviolet Absorption Speetra .... 27
3. Solubilities and Color Reactions ••••••••• 30
4* Acetate and Phenylhydrazone Derivatives .. 33
5. Maule Test and Oxidation with Alkali and
Nitrobenzene ..*••••.••••••••••••••••••• 37
6. Infrared Absorption Spectra ..•••.•••••••• 39
7* Methylation with Diazomethane ••••••..,••• 41
8. Infrared Absorption Spectra of Methylated
Lignins *......... 45
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C. Studies on Enzymatically liberated Hardwood
Lignins .... 47
1* Comparison of Native and Enzymatically
Liberated Lignins ..................... 51
D. Studies on Jute Lignin ••.••.•••.•••••••••* 63
it; discussion... ......... 66
Y. SUMMARY ...... ........ 72
REFERENCES . . ...... 74
iV
r LIS! OP CABLES 'I
I ABLE Page
I. Methylation with Biazomethane of White Scots
Pine Lignins ........... ....•• 19
II. Oxidation of White Scots Pine Lignins with
Alkali and Nitrobenzene ............. 22
III* Analysis of Sulfuric Acid Lignins •..•••.•••• 24
IV. Analysis of Native Lignins •.••«••••..••••*. • 26
V. Solubilities, Reducing Abilities and Color
Reactions of Native Lignins ♦•«.••••••••••» 31
VI. Sulfuric Acid Lignins Obtained from Native
Hardwood Lignins ...... 32
VII. Acetate and Phenylhydrazone Derivatives of
Native Lignins ....... 34
VIII. Oxidation of Native Hardwood Lignins ••••..•* 38
IX. Comparison of Calculated and Pound Methoxyl
Contents of Derivatives of Hardwood Native
Lignins ........................... 43
X. Methylation of Native Lignins with Diazome-
thane ..................................... 44
XI. Effect of the Action of Daedalea quercina on
the Composition of Oak, Birch and Maple ... 48
XII. Yields of Lignin Isolated from Sound and
Decayed Hardwoods 30
XIII. Comparison of Native and Enzymatically Libe­
rated Hardwood Lignins .... 53
XIV. Effect of Trichoderma viride and of Penicil-
lium citrinum on the Composition ofJute
S*ibre «... ..7. * * 65
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LIST OF FIGURES
FIGURE
I* Standard Curves for the Spectrophotometrie
Determination of Vanillin and Syringalde-
hyde ...... .••••••••..*••«
II. Infrared Absorption Spectra of Native and
Enzymatically liberated White Scots Pine
' lignins ..
III. Infrared Absorption Spectra of the Diazome-
thane-Methylated White Scots Pine lignins ..
IV. Ultraviolet Absorption Spectra of Oak, Birch,
Maple, White Scots Pine and Aspen Native
lignins .•«.
V. Ultraviolet Absorption Spectra of the Phenyl-
hydrazones of Oak, Birch, Maple and White
Pine Native lignins .. .......
VI. Ultraviolet Absorption Spectra of the Acetates
of Oak, Birch, Maple and White Scots Pine
Native Iignms .............................
VII. Infrared Absorption Spectra of Oak, Birch,
Maple and White Scots Pine Native lignins ..
VIII. Infrared, Absorption Spectra of Diazomethaner
Methylated Oak, Birch and Maple Native
lignins ..•
IX. Ultraviolet Absorption Spectra of Native and
Enzymatically liberated Oak, Birch and Maple
X. Ultraviolet Absorption Spectra of the Acetates
of Native and Enzymatically liberated. Oak,„
Birch and Maple lignins
XI. Ultraviolet Absorption Spectra of the Phenyl-
hydrazones of.Native and Enzymatically libe­
rated Oak, Birch and Maple lignins •••••••••
/
XII. Infrared Absorption Spectra of Native and En­
zymatically liberated Oak lignins •••••••••.
XIII. Infrared Absorption Spectra of Native and En­
zymatically liberated Birch lignins .....
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FIGURES Page n
XIV# Infrared Absorption Spectra of Native and En­
zymatically Liberated Maple Lignins #•##••## 59
XV# Infrared Absorption Spectra of the Diazometha-
ne-Methylated Native and Enzymatically Li­
berated Oak Lignins ..... • 60
XVI# Infrared Absorption Spectra of the Diazome-
thane-Methylated Native and Enzymatically
Liberated Birch Lignins 61
XVII. Infrared Absorption Spectra of the Diazome-
thane-Methylated Native and Enzymatically
Liberated Maple Lignins # • # . . « . # • 6 2
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ACK3J0WLEIXxMEM?S
This dissertation is dedicated t© my mother
and father*
These investigations were assisted hy a grant
from the Office of Uaval Research, and were earried out
under the direction ©f Dr* f*P* lord*
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