Studies on the Lignins of Bark and Wood and the Mechanism of Oxolate Formation by Wood-Destroying Molds

100 Pages·3.305 MB·English

by  De Baun, Robert Mathew

FORDHAM UNIVERSITY
GRADUATE SCHOOL
......... -'ay 15.......... 19...51
This dissertation prepared under my direction by
Robert Matthew DeBaun
entitled STUDIES ON THE LIGNINS OF BARK AND vvOOD AND THE
MECHANISM OF OXALATE FORMATION BY WOOD-DESTROYING
MOLDS
has been accepted in partial fulfilment of the requirements for the
Degree of Pqptor...of„..l^ilosophy;_
Dr. F.F. Nord
(Faculty Adviser)

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STUDIES ON THE LIGNINS OF BARK AND WOOD AND THE
MECHANISM OF OXALATE FORMATION BY WOOD-DESTROYING
MOLDS
BY
ROBERT MATTHEW DE BAUN
B.S., Fordham College, 1947
M.S., Fordham University, 1949
DISSERTATION
SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY IN THE DEPARTMENT OF CHEMISTRY
AT FORDHAM UNIVERSITY
NEW YORK, NEW YORK
1951
ProQuest Number: 10993004
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table of contents
Page
LIST OF TABLES.......................................... v
LIST OF FIGURES......................................... vi
ACKNOWLEDGMENTS ......................................... vii
I. INTRODUCTION.................................... 1
II. GENERAL EXPERIMENTAL METHODS...................... 8
A. Microbiological •.«•••••••...... ..................... 8
B. Analytical .......... 10
C• Colorimetric and Spectroscopic ••••••••••••.......... 11
D. Synthetic ................. 15
E. Isolation and Fractionation ....... 13
1.Cor k ............ 13
2.Native Lignins ........ 13
3.Cork Alkali Lignin .............. 15
F. Analysis of Cork ........ «... 15
1 .Moisture ...... 15
2.Extractable Matter........... 15
5.Saponifiable Matter........... 15
G. Enzymatic Methods ........ 15
III. SPECIAL EXPERIMENTAL PROCEDURES .................... 17
km Determination of Lignin in Cork ........ 17
B. Phloroglucinol-HCl test...... 19
C. Reaction of Lignins with the Phenol Reagent.......... 29
l.Cork Lignins...... ...»..... 29
2.Softwood and Hardwood Lignins ..... 29
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D. Paper Chromatography of Lignins ...... .••••••• 50
E. Codetermination of Resazurin and Resorufin ......32
IV. LIGNINS OF CORK AND T/OOD...........................41
A. Cork Lignin .... 41
B. Softwood and Hardwood Lignins •••• •••• 48
V. METABOLIC STUDIES........ 53
A. Comparison of JT. cinnabarina andI ?. vaporarius •••«•••• 53
B. Conditions Governing Oxalate Accumulation
by T. cinnabarina ........................... 59
C. Oxalic Acid Metabolism of T. cinnabarina •••••••••••••• 61
D. Infection of Cork by Fungi ......... 70
VI. DISCUSSION....................................... 73
VII. SUMMARY .............. 81
BIBLIOGRAPHY........... 83
V
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LIST OF TABLES
Table Page
I• Reported Composition of Cork • • • • •......... 18
II• Determination of Lignin in Cork •••••....•••............. . 22
III, Recovery of Resazurin and Resorufin ...... 40
IV. Composition of the Fractions of Cork
Native Lignin ..... 46
V. The Phloroglucinol-HCl test on Various Lignins ••••.•••••••• 50
VI. Reaction of Various Lignins with the Phenol
Reagent, and Chromatography of the Lignins ••••.••«••••••••• 51
VII. Growth of P. vaporaria on Glucose Neopeptone
Medium....... 54
VIII. Growth of JT. cinnabarina on Glucose Neopeptone
Medium. ..... 55
IX. Growth of P. vaporarius on Glucose-Urea Medium 56
X. Growth of JT. cinnabarina on Glucose-Urea Medium........ 57
XI. Accumulation of Oxalate by JT* cinnabarina •••••.......... 60
XII. Dissimilation of ©(-Ketoglutarate by JT. cinnabarina 62
XIII. Dissimilation of L-Glutamic and L-Aspartic
Acid by T. cinnabarina .... 66
XIV. Reduction of Resazurin in the Presence of Various
Substrates by Growing Cells of T. cinnabarina ..... 67
XV. Reduction of Resazurin in the Presence of Various
Substrates by Resting Cells of JT. cinnabarina .... 68
XVI. Effect of Fungi on Lignin Content of Cork ... 71
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LIST OF FIGURES
Figure Page
I* Calibration Curve for the Determination
of <-Ketoglutaric Acid................... 12
II* Calibration Curve for the Determination
of Lignin in Cork ...... *............*....... *.... 20
III. Spectrum of the Color Produced on Reaction of
Phenols with Pho sphomolybdic-phosphotung stic Acid....... 21
IV. Fading of Lignin-Phloroglucinol-HCl Color............. 26
V. Spectrum of the Lignin-Phloroglucinol-HCl Complex ••••... 27
VI. Calibration Curve for the Quantitative Method for
the Determination of the Lignin-Phloroglucinol-HCl
Test. ....... 28
VII. Reaction of B-Naphthol with the Phenol Reagent ...... 31
VIII. Absorption Spectrum of Resazurin ...... 35
IX. Absorption Spectrum of Resorufin... ....... 56
X. Concentration-Extinction Curves for Resazurin
and Resorufin..........••••••.... 57
XI. Absorption Spectra of Resazurin and Resorufin ........ 58
XII. Absorption Spectrum of a Mixture of
Resazurin and Resorufin.................. .......••••• 39
XIII. Fractionation of the Cork Native Lignin ...... 43
XIV. Ultraviolet Spectra of Cork Lignin Fractions .... 44
XV. Infrared Spectra of Cork Lignin Fractions.......... 45
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ACKNOWLEDGMENTS
This dissertation is dedicated to ray wife*
These investigations were assisted b, y a grant from the
Office of Naval Research, and were c arried out under
the direction of Dr* F.F. Nord*
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STUDIES ON THE LIGNINS OF BARK AND HOOD AND THE
MECHANISM OF OXALATZ FORMATION BY WOOD-DESTROYING
MOLDS