Biochemical Characterization and Fuel Properties of Endemic Taurus Flowering Ash (Fraxinus ornus subsp. cilicica) Bark from Turkey
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Summative Chemical Composition
2.3. Inorganic Elemental Composition
2.4. FT-IR Analysis
2.5. Phenolic Content
2.6. In Vitro and Ex Vivo Antioxidant Activity
2.7. Composition of Lipophilic Extractives
2.8. Suberin Monomeric Composition
2.9. Thermogravimetric Analysis
2.10. Kinetic Analysis of Combustion
3. Results
3.1. Chemical Composition
3.2. FT-IR Analysis
Signal (cm−1) | Functional Group | Assignment to Chemical Components | Reference |
---|---|---|---|
512 | O-C-O | CaOxa | - |
780 | O-C-O | CaOxa | [32] |
1016 | C-O | Cellulose or lignin | [36] |
1316 | O-C-O | CaOxa | [32] |
1419 | C-H | Lignin | [36] |
1609 | C=O | CaOxa | [32] |
2934 | C-H | Suberin | - |
3227 | O-H | Moisture or phenolic structures | - |
3.3. Phenolic Content and Antioxidant Properties
3.4. Lipophilic Extractives
3.5. Suberin Composition
3.6. Thermogravimetric Analysis
4. Discussion
5. Conclusions
- Fraxinus ornus subsp. cilicica bark contains a notable amount of extractives (39%) that are predominantly polar compounds;
- The inorganic content of the bark is elevated (17%), comprising primarily calcium;
- The polar bark extractives contain a moderate phenolic content as well as moderate in vitro and ex vivo antioxidant properties;
- The lipophilic extractives are rich in fatty acids and abietane diterpenoids;
- Suberin content is low and primarily composed of ω-hydroxy acids. The current study contributes to the ongoing research to enlarge the data on the monomeric composition of suberins of different barks;
- The ignition temperature of the bark is 190 °C, and the burnout temperature is 653 °C;
- A biorefinery concept was developed for the fractionation and valorization of F. ornus bark to produce fatty acids, terpenoids, hydrophilic extracts, suberin monomers, cellulose nanocrystals, and cement-replacement materials.
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Component | % Dry Weight | % Ash-Free Weight |
---|---|---|
Ash | 17.1 ± 3.2 | - |
Extractives-DCM | 2.5 ± 0.3 | 3.0 |
Extractives-EtOH | 29.4 ± 3.4 | 35.5 |
Extractives-H2O | 7.0 ± 0.3 | 8.5 |
Total extractives | 38.9 ± 3.3 | 46.9 |
Suberin | 1.0 ± 0.2 | 1.2 |
Klason lignin | 6.7 ± 1.1 | 8.1 |
Acid-soluble lignin | 3.1 ± 0.7 | 3.8 |
Total lignin | 9.8 ± 1.8 | 11.8 |
* Polysaccharides | 33.2 ± 9.2 | 40.1 |
Major elements | mg kg−1 bark | % Elements |
Na | 25.3 | 0.1 |
K | 2448.8 | 5.1 |
Ca | 43,356.7 | 90.7 |
Mg | 813.6 | 1.7 |
P | 274.3 | 0.6 |
S | 636.6 | 1.3 |
Fe | 228.9 | 0.5 |
Oligoelements | mg kg−1 bark | % Oligoelements |
Cu | 6.1 | 15.2 |
Zn | 7.6 | 18.9 |
Mn | 13.8 | 34.3 |
B | 12.7 | 31.6 |
Total | 47,824.4 | 100.0 |
Extract Yield (%) | TPC (mg GAE/g Extract) | Flavonoids (mg CE/g Extract) | Condensed Tannins (mg CE/g Extract) | DPPH (mg TE/g Extract) | DPPH IC50 (μg/mL) | FRAP (mM) |
---|---|---|---|---|---|---|
35.5 ± 2.1 | 241.8 ± 3.2 | 171.6 ± 13.6 | 106.6 ± 3.8 | 113.4 ± 44.5 | 40.0 ± 20.9 | 0.3 ± 0.0 |
Extract yield (%) | 24.9 |
EC50 (μg/mL) | 230 ± 10 |
Trolox (μg/mL) | 5.4 ± 0.3 |
Compound Families | Compounds | % Total Peak Area |
---|---|---|
Alcohols | Total | 1.43 |
Dodecanol | 0.12 | |
Hexadecanol | 0.07 | |
Docosanol | 0.48 | |
Hexacosanol | 0.11 | |
Octacosanol | 0.65 | |
Fatty acids | Total | 42.99 |
Octanoic acid | 2.55 | |
Nonanoic acid | 0.46 | |
Decanoic acid | 0.16 | |
2-Ethyl hexanoic acid | 6.86 | |
Tetradecanoic acid | 0.14 | |
Pentadecanoic acid | 0.17 | |
Hexadecanoic acid | 15.13 | |
Heptadecanoic acid | 0.69 | |
9,12-Octadecadienoic acid | 0.32 | |
9-Octadecenoic acid | 2.46 | |
Octadecanoic acid | 1.99 | |
Eicosanoic acid | 1.85 | |
Heneicosanoic acid | 0.98 | |
Docosanoic acid | 3.63 | |
Tricosanoic acid | 0.43 | |
Tetracosanoic acid | 1.42 | |
Pentacosanoic acid | 0.10 | |
Hexacosanoic acid | 1.32 | |
Octacosanoic acid | 1.79 | |
Triacontanoic acid | 0.54 | |
Diacids | Total | 7.45 |
Oct-2-ene-1,8 dioc acid | 2.13 | |
Nonanedioic acid | 3.56 | |
Octadecanedioic acid | 1.79 | |
ω-hydroxy fatty acids | Total | 8.79 |
9,10-Epoxy-18 hydroxy octadecanoic acid | 8.79 | |
Phenolics | Total | 0.49 |
Homovanillyl alcohol | 0.49 | |
Steroids | Total | 0.79 |
β-sitosterol | 0.67 | |
Stigmast-4-en-3-one | 0.11 | |
Terpenoids | Total | 20.89 |
Dehydroabietic acid | 4.53 | |
Abietic acid | 16.18 | |
Betulinic acid | 0.18 | |
Sugars | Total | 0.15 |
Sitosteryl-3β-D-glucopyranoside | 0.15 |
Compound Families | Compounds | % Total Peak Area |
---|---|---|
Alcohols | Total | 0.46 |
Octadecanol | 0.17 | |
Eicosanol | 0.22 | |
1,22-Docosanediol | 0.07 | |
Fatty acids | Total | 14.93 |
Hexadecanoic acid, methyl ester | 0.14 | |
Octadecanoic acid, TMS | 0.05 | |
Octadecanoic acid, 9,10-dihydroxy-, methyl ester | 5.37 | |
Methyl 2-hydroxytetradecanoate, TMS | 0.19 | |
15-Tetracosenoic acid, TMS | 9.19 | |
α-ω-dicarboxylic acids | Total | 19.37 |
Hexadecanedioic acid, dimethyl ester, | 0.54 | |
Octadec-9-enedioic acid, dimethyl ester | 1.19 | |
Octadecanedioic acid, dimethyl ester | 0.39 | |
Eicosanedioic acid, dimethyl ester | 14.16 | |
Docosanedioic acid, dimethyl ester | 0.69 | |
Hexadecanedioic acid, 2TMS | 0.05 | |
Octadec-9-enedioic acid, (18-trimethylsiloxy)-, methyl ester | 0.23 | |
Octadecanedioic acid 9,10-dihydroxy(di-TMS), 1,18-(dimethylsilyl) | 2.12 | |
ω-hydroxy acids | Total | 47.52 |
Hexadecanoic acid, (16-trimetilsiloxy)-, methyl ester | 0.30 | |
Methyl 18-hydroxy-9-octadecenoate, TMS | 12.83 | |
Octadecanoic acid, 9,10-epoxy-18-trimethylsiloxy)-, methyl ester cis | 12.84 | |
Eicosanoic acid, (20-trimethylsiloxy)-, methyl ester | 0.41 | |
9,10,18 Trihydroxyoctadecanoic acid, methyl ester, threo, 3TMS | 14.60 | |
Docosanoic acid, (22-trimethylsiloxy)-, methyl ester | 5.84 | |
22-hydroxy docosanoic acid, (bis-methylsilyl)-, derivative | 0.12 | |
Tetracosanoic acid, (24-trimethylsiloxy)-, methyl ester | 0.52 | |
Hexacosanoic acid, (26--trimethylsiloxy)-, methyl ester | 0.06 | |
Phenolics | Total | 3.94 |
Vanillin | 0.10 | |
Methyl p-coumarate, TMS derivative | 0.22 | |
Methyl isoferulate, TMS | 0.31 | |
Methyl ferulate, TMS | 3.29 | |
Ferulate Ac.C25:0, TMS | 0.02 | |
Ferulate Ac.C27:0, TMS | 0.01 | |
Glycerol derivatives | Total | 3.63 |
Docosyl glycerol (C22:0) | 3.63 | |
Diacids | Total | 0.08 |
Octanedioic acid, dimethyl ester | 0.02 | |
Nonanedioic acid, dimethyl ester | 0.06 |
Moisture Mass Loss Region (40–120 °C) | Low-Temperature Mass Loss Region (40–200 °C) | Main Mass Loss Region (200–450 °C) | Residual Char (%) | |
---|---|---|---|---|
Mass loss (%) | 4.2 ± 0.7 | 8.2 ± 1.5 | 51.7 ± 1.4 | 17.3 ± 0.4 |
Tmax (°C) | 76.9 ± 11.7 | 148.5 ± 8.1 | 345.3 ± 21.4 | - |
Onset (°C) | - | 121.9 ± 9.6 | 197.1 ± 4.2 | - |
Biomass | Extract Yield (%) | TPC (mg GAE/g Extract) | Flavonoids (mg CE/g Extract) | Tannins (mg CE/g Extract) | TEAC (mg TE/g Extract) | IC50 (μg/mL) | FRAP (mM) | Reference |
---|---|---|---|---|---|---|---|---|
F. ornus bark | 35.5 | 241.8 | 171.6 | 106.6 | 113.4 | 40 | 0.3 | This work |
Eucalypt bark | 12.6 | 332.5 | 141.6 | 138.3 | 338.4 | 39.7 | 9.6 | [43] |
Douglas fir bark | 11 | 674 | 429 | 141 | 2554 | 2 | 12 | [44] |
Waste oak cork | 6.9 | 733.8 | 306.6 | 419.4 | 729.5 | 8.8 | 3.3 | [45] |
Waste oak phloem | 4.9 | 255.2 | 190.0 | 131.4 | 435.8 | 7.3 | 1.8 | [45] |
Pine phloem | - | 439.8 | 86.6 | 101.6 | - | 1.5 | 3.5 | [46] |
Pine nutshell (Turkey) | - | 455 | - | - | 825 | - | 9.5 | [47] |
Pine nutshell (Portugal) | 3.9 | 303.1 | 114.6 | 30.4 | 934.9 | 8.2 | 5.2 | [48] |
Almond shell | 3.4 | 188.6 | 99.4 | 34.6 | 646.0 | 7.9 | 3.1 | [48] |
Walnut shell | 7.3 | 317.9 | 197.6 | 60.1 | 188.6 | 15.2 | 5.1 | [48] |
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Şen, A.U.; Simões, R.; Yücedağ, C.; Miranda, I.; Fernandes, Â.; Pereira, H. Biochemical Characterization and Fuel Properties of Endemic Taurus Flowering Ash (Fraxinus ornus subsp. cilicica) Bark from Turkey. Processes 2023, 11, 2774. https://doi.org/10.3390/pr11092774
Şen AU, Simões R, Yücedağ C, Miranda I, Fernandes Â, Pereira H. Biochemical Characterization and Fuel Properties of Endemic Taurus Flowering Ash (Fraxinus ornus subsp. cilicica) Bark from Turkey. Processes. 2023; 11(9):2774. https://doi.org/10.3390/pr11092774
Chicago/Turabian StyleŞen, Ali Umut, Rita Simões, Cengiz Yücedağ, Isabel Miranda, Ângela Fernandes, and Helena Pereira. 2023. "Biochemical Characterization and Fuel Properties of Endemic Taurus Flowering Ash (Fraxinus ornus subsp. cilicica) Bark from Turkey" Processes 11, no. 9: 2774. https://doi.org/10.3390/pr11092774