Ligninsimilar Components From Algae
LIGNINSIMILAR COMPONENTS FROM ALGAE
I.V. Dovgan
Odessa State Academy of Civil Engineering and Architecture, Ukraine
INTRODUCTION
Consistency and properties of nonhydrolysed components from sea algae have been studied by us with the purpose of scientific control of the complex use and all-round utilization.
Red and brown sea-algae Cystoseira barbata, Fucus vesiculosus, Zostera noltii, Phyllophora nervosa, Gracilaria verrucosa /of natural planting and mагуculture/ are used as the object of the scientific investigation.
The result of this research allow to arrive to conclusion, that algae as higher plants, synthesize ligninsimilar components. (LSC), which contain the main part of the residual after acid hydrolysis. LSC from algae are high-molecular combinations with the molecular mass morе than 9000 o.u.
LSC from algae, extraction with dioxane for Papper methods, differ from birch-wood and spruce-wood lignins according to the, elementary and functional compositions (table 1,2).
Table 1. The elemental composition of dioxane lignins (in per cents)
Subject of inquiry
C
H
O
N
Br
Cystoseira barbata
Fucus vesiculosus
Zostera noltii
Spruce wood
Birch wood
61.19
57.76
59.18
61.32
58.85
4.92
6.03
6.71
6.10
6.29
30.21
34.84
32.97
32.58
34.86
2.10
1.37
1.68
–
–
1.58
trace
–
–
–
LSC from algae contains carboxylic, carbonylic and hydroxylic groups. Dioxane-lignins from algae differ from birch-wood and spruce-wood lignins, they are characterized by comparatively low content by methoxylic groups (table 2).
Table 2. The functional composition of dioxane-lignins and the presence of carbohydrates in them (in per cents)
Subject of inquiry
OCH3-gr.
OH-gr. phenol
COOH-gr.
CO-gr.
Carbohydrates
Cystoseira barbata
Fucus vesiculosus
Zostera noltii
Spruce wood
Birch, wood
7.24
3.41
4.61
15.90
21.70
5.28
9.03
3.83
3.20
1.40
2.08
3.63
1.62
0.53
0.75
8.70
8.36
6.43
3.25
3.20
1.81
1.76
2.06
0.71
2.40
They differ also according to the character of the products of alkaline nitrobenzene oxidation (table 3), degradation of the metallic sodium in liquid ammonia and thioacetic acid (table 4).
Table 3. Output of the nitrobenzene oxidation products of the dioxane lignins (in per cents)
Subject of inquiry
p-Oxy-benzal-dehyde
Vanilin
Syringic aldehyde
p-Oxy-benzenic acid
Vanilinic acid
Syringic acid
Cystoseira barbata
Fucus vesiculosus
Zosters noltii
Spruce wood
Birch wood
1.64
0.43
0.82
trace
–
6.53
3.33
3.71
22.11
7.52
–
1.05
0.34
–
22.24
0.91
0.11
0.10
trace
–
3.43
1.16
1.32
9.32
0.91
–
0.06
–
–
2.01
In carbolic fraction of the products received as a result of degradation LSC from algae by means of metallic sodium in liquid, ammonia and destruction with thioacetic acid phenol, guaiacol, p-oxyphenylpropane, p-oxyphenylpropanol and as well as bimolecular compound similar B-coniferyl ether guaiacylglycerine, which have been identified.
It has been established, that macromolecules of LSC from algae contain low-methoxylar compounds p-cumaric and guaiacylic series. Near 1/3 bondings between structural units of LZS from algae have been represented by arylalkyl ether bondings.
Unlike of lignin from wood, in LSC from algae phenylcumaric structures which predominate, but there are not any syringylpropane structure units. This results have been confirmed with the data UV-, IR - and NMR-spectroscopy.
Table 4. The composition and output of the phenol products received as a result of degradation of the lignin from Cystoseira barbata (in per cents of mixture)
Phenol products
Metal. Na in liquid NH3
CS3COOH + ВF3
LSC
Algae
LSC
Algae
p-Oxyphenilpropane
p-Oxyphenilpropanol
Phenol
Guaiacol
Guaiacylpropane
Vanilin
Guaiacylpropanol-1
Guaiacylprepanol-3
0.81
-
-
47.21
31.03
0.22
6.49
–
3.55
–
0.40
–
67.02
–
11.55
6.37
1.29
4.49
15.69
5.14
4.09
29.95
0.31
–
14.47
–
5.45
9.93
1.84
13.79
7.72
–
It has been stated that LSC from algae of the natural planting differ from LSC algae maryculture. Thus, LSC maryculture of algae Gracilaria verrucosa are different from comparatively low molecular mass, the consistency methoxyl group being 5.6%, and consistency carboxyl groups - 9.2%.
Taking into consideration the result of investigation and the representation of structure LSC from а1gaе, we propose the ways for complex use of ligninsimilar compounds from algae after their processing for the recovery of high quality building materials, etc.
References
1. Dovgan I.V., Kreycberg Z.N., Medvedeva E.I. 1982. Investigation of lignin isolated from brown algae Cystoseira barbata. Khimiya Drevesini, №. 5, p.67-71.
2. Dovgan I.V., Medvedeva E.I., Janishevskaya E.N. 1983. Decomposition of lignin isolated from algae Cystoseira barbata by thioacetic acid. Khimiya priroda. soedinen., №. 1, p.88-91.
3. Dovgan I.V. 1983. NMR-spectrum of lignins isolated from brown algae Cystoseira barbata in different age. Khimiya prirodn., soedinen., № 1, p.9I-94.
4. Medvedeva E.I., Dovgan I.V. 1985. Modification and the ways for use the lignin components of the sea-algae. In: Procedings of the V-th International Symp. "Modyfikacia drewna 85". Poland, Poznan, p.252-259.
5. Medvedeva E.I., Dovgan I.V. 1987. The investigation of lignin algae structure with the purpose of biostability prediction of the extracted building materials. In: Procedings of the VI-th International Symp. "Modyfikacia drewna 87", Poland, Poznan, p.217-221.
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