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11 pages, 607 KiB  
Article
Evaluating the Susceptibility of Different Crops to Smoke Taint
by Julie Culbert, Renata Ristic and Kerry Wilkinson
Horticulturae 2024, 10(7), 713; https://doi.org/10.3390/horticulturae10070713 - 5 Jul 2024
Viewed by 777
Abstract
The potential for grapes and wine to be tainted following vineyard exposure to wildfire smoke is well established, with recent studies suggesting hops and apples (and thus beer and cider) can be similarly affected. However, the susceptibility of other crops to ‘smoke taint’ [...] Read more.
The potential for grapes and wine to be tainted following vineyard exposure to wildfire smoke is well established, with recent studies suggesting hops and apples (and thus beer and cider) can be similarly affected. However, the susceptibility of other crops to ‘smoke taint’ has not yet been investigated. Smoke was applied to a selection of fruits and vegetables, as well as potted lavender plants, and their volatile phenol composition determined by gas chromatography–mass spectrometry to evaluate their susceptibility to contamination by smoke. Volatile phenols were observed in control (unsmoked) capsicum, cherry, lavender, lemon, spinach and tomato samples, typically at ≤18 µg/kg, but 52 µg/kg of guaiacol and 83–416 µg/kg of o- and m-cresol and 4-methylsyringol were detected in tomato and lavender samples, respectively. However, significant increases in volatile phenol concentrations were observed as a consequence of smoke exposure; with the highest volatile phenol levels occurring in smoke-exposed strawberry and lavender samples. Variation in the uptake of volatile phenols by different crops was attributed to differences in their physical properties, i.e., their surface area, texture and/or cuticle composition, while the peel of banana, lemon, and to a lesser extent apple samples, mitigated the permeation of smoke-derived volatile phenols into pulp. Results provide valuable insight into the susceptibility of different crops to smoke contamination. Full article
(This article belongs to the Section Biotic and Abiotic Stress)
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Figure 1

Figure 1
<p>Principal component analysis biplot of volatile phenol concentrations measured in different crops, following exposure to smoke.</p>
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16 pages, 3009 KiB  
Article
Unraveling the Lignin Structural Variation in Different Bamboo Species
by Ling-Ping Xiao, Yi-Hui Lv, Yue-Qin Yang, Shuang-Lin Zou, Zheng-Jun Shi and Run-Cang Sun
Int. J. Mol. Sci. 2023, 24(12), 10304; https://doi.org/10.3390/ijms241210304 - 18 Jun 2023
Viewed by 1886
Abstract
The structure of cellulolytic enzyme lignin (CEL) prepared from three bamboo species (Neosinocalamus affinis, Bambusa lapidea, and Dendrocalamus brandisii) has been characterized by different analytical methods. The chemical composition analysis revealed a higher lignin content, up to 32.6% of [...] Read more.
The structure of cellulolytic enzyme lignin (CEL) prepared from three bamboo species (Neosinocalamus affinis, Bambusa lapidea, and Dendrocalamus brandisii) has been characterized by different analytical methods. The chemical composition analysis revealed a higher lignin content, up to 32.6% of B. lapidea as compared to that of N. affinis (20.7%) and D. brandisii (23.8%). The results indicated that bamboo lignin was a p-hydroxyphenyl-guaiacyl-syringyl (H-G-S) lignin associated with p-coumarates and ferulates. Advanced NMR analyses displayed that the isolated CELs were extensively acylated at the γ-carbon of the lignin side chain (with either acetate and/or p-coumarate groups). Moreover, a predominance of S over G lignin moieties was found in CELs of N. affinis and B. lapidea, with the lowest S/G ratio observed in D. brandisii lignin. Catalytic hydrogenolysis of lignin demonstrated that 4-propyl-substituted syringol/guaiacol and propanol guaiacol/syringol derived from β-O-4′ moieties, and methyl coumarate/ferulate derived from hydroxycinnamic units were identified as the six major monomeric products. We anticipate that the insights of this work could shed light on the sufficient understanding of lignin, which could open a new avenue to facilitate the efficient utilization of bamboo. Full article
(This article belongs to the Special Issue Bio-Polymer Materials and Bio-Refinery 2.0)
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Figure 1

Figure 1
<p>FT-IR spectra of (a) CEL<sub>N</sub>, (b) CEL<sub>B</sub>, and (c) CEL<sub>D</sub>. CEL<sub>N</sub>, CEL<sub>B</sub>, and CEL<sub>D</sub> were isolated from <span class="html-italic">N. affinis</span>, <span class="html-italic">B. lapidea</span>, and <span class="html-italic">D. brandisii</span>, respectively.</p>
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<p>GPC of (a) CEL<sub>N</sub>, (b) CEL<sub>B</sub>, (c) CEL<sub>D</sub> and lignin oil obtained from the catalytic hydrogenolysis of (d) CEL<sub>N</sub>, (e) CEL<sub>B</sub>, (f) CEL<sub>D</sub> over a Ru@NC catalyst.</p>
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<p>TG and DTG curves of (a) CEL<sub>N</sub>, (b) CEL<sub>B</sub>, and (c) CEL<sub>D</sub>.</p>
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<p>Quantitative <sup>13</sup>C NMR spectra of (<b>a</b>) CEL<sub>N</sub>, (<b>b</b>) CEL<sub>B</sub>, and (<b>c</b>) CEL<sub>D</sub>.</p>
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<p>2D HSQC NMR spectra of the prepared (<b>a</b>,<b>d</b>) CEL<sub>N</sub>, (<b>b</b>,<b>e</b>) CEL<sub>B</sub>, and (<b>c</b>,<b>f</b>) CEL<sub>D</sub> isolated from ball-milled bamboo. The colors of the contours correspond to the structures drawn. (<b>g</b>) The main structures and lignin-derived monomers found are as follows: (A) β-<span class="html-italic">O</span>-4′ alkyl-aryl ether; (A′) γ-OH with <span class="html-italic">p</span>-coumaroylated β-<span class="html-italic">O</span>-4′ alkyl-aryl ethers; (B) phenylcoumarans; (C) resinols; (D) spirodienones; (T) tricin; (S) syringyl units; (S′) oxidized syringyl units bearing a carbonyl at C<sub>α</sub>; (G) guaiacyl units; (H) <span class="html-italic">p</span>-hydroxyphenyl unites; (<span class="html-italic">p</span>CA) <span class="html-italic">p</span>-coumarates; and (FA) ferulates.</p>
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<p>2D HSQC NMR spectra (in DMSO-<span class="html-italic">d</span><sub>6</sub>) of the lignin oily product (<b>a</b>–<b>c</b>) obtained from the Ru@NC-catalytic hydrogenolysis of CEL<sub>N</sub> (in DMSO-<span class="html-italic">d</span><sub>6</sub>); (<b>d</b>) three-dimensional version of the 2D HSQC end-chain region; (<b>e</b>) detected lignin monomers. Reaction conditions: CEL<sub>N</sub> (50 mg), Ru@NC catalyst (5 mg, 10 wt%), MeOH (10 mL), 240 °C, H<sub>2</sub> (3 MPa at 25 °C, 12 MPa at 240 °C), and 4 h.</p>
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<p>Catalytic hydrogenolysis of the lignin β-<span class="html-italic">O</span>-4′ model compounds over a Ru@NC catalyst.</p>
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<p>Atomic H/C versus O/C ratios (van Krevelen diagram) of bamboo, bamboo CELs, and lignin oil obtained from the Ru@NC-catalytic hydrogenolysis of CELs. The lines represent demethanation, dehydration, and decarboxylation pathways. Bamboo<sub>N</sub>, Bamboo<sub>B</sub>, and Bamboo<sub>D</sub> refer to <span class="html-italic">N. affinis</span>, <span class="html-italic">B. lapidea</span>, and <span class="html-italic">D. brandisii</span>, respectively.</p>
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15 pages, 2541 KiB  
Article
Physicochemical Properties, Thermal Stability, and Pyrolysis Behavior of Antioxidative Lignin from Water Chestnut Shell Obtained with Ternary Deep Eutectic Solvents
by Feng Li, Wenzhi Lv, Dena Huang, Chenglu Zeng and Runping Wang
Molecules 2023, 28(10), 4088; https://doi.org/10.3390/molecules28104088 - 15 May 2023
Cited by 5 | Viewed by 1752
Abstract
The molecular weight of lignin extracted from lignocellulosic biomass is an important factor in determining its valorization in industrial processes. Herein, this work aims to explore the extraction of high molecular weight and bioactive lignin from water chestnut shells under mild conditions. Five [...] Read more.
The molecular weight of lignin extracted from lignocellulosic biomass is an important factor in determining its valorization in industrial processes. Herein, this work aims to explore the extraction of high molecular weight and bioactive lignin from water chestnut shells under mild conditions. Five kinds of deep eutectic solvents were prepared and applied to isolate lignin from water chestnut shells. The extracted lignin was further characterized with element analysis, gel permeation chromatography, and Ultraviolet-visible and Fourier-transform infrared spectroscopy. The distribution of pyrolysis products was identified and quantified with thermogravimetric analysis—Fourier-transform infrared spectroscopy and pyrolysis-gas chromatograph-mass spectrometry. The results showed that choline chloride/ethylene glycol/p-toluenesulfonic acid (1:1.8:0.2 molar ratio) exhibited the highest fractionation efficiency for lignin (84.17% yield) at 100 °C for 2 h. Simultaneously, the lignin showed high purity (90.4%), high relative molecular weight (37,077 g/mol), and excellent uniformity. Furthermore, the aromatic ring structure of lignin remained intact, consisting mainly of p-hydroxyphenyl, syringl, and guaiacyl subunits. The lignin generated a large number of volatile organic compounds during the depolymerization process, mainly composed of ketones, phenols, syringols, guaiacols, esters, and aromatic compounds. Finally, the antioxidant activity of the lignin sample was evaluated with the 1,1-diphenyl-2-picrylhydrazyl radical scavenging assay; the lignin from water chestnut shells showed excellent antioxidant activity. These findings confirm that lignin from water chestnut shells has a broad application prospect in valuable chemicals, biofuels and bio-functional materials. Full article
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Figure 1
<p>DPPH radical scavenging activity of the different types of DES-isolated lignin.</p>
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<p>UV−Vis (<b>a</b>) and FTIR (<b>b</b>) spectra of the lignin isolated with ChCl/EG/<span class="html-italic">p</span>−TsOH DES.</p>
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<p>TG and DTG curves of the lignin isolated with ChCl/EG/<span class="html-italic">p</span>−TsOH DES.</p>
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<p>The 3D−FTIR spectra of ChCl/EG/<span class="html-italic">p</span>−TsOH−isolated lignin with a heating rate of 10 °C/min, where red, yellow, green, blue and purple represent very strong, strong, medium, weak and very weak infrared absorbance, respectively.</p>
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<p>FTIR spectra of the volatile components in the vapor phase of the lignin isolated with ChCl/EG/<span class="html-italic">p</span>−TsOH DES.</p>
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<p>Total ion chromatograph of lignin extracted using ChCl/EG/<span class="html-italic">p</span>-TsOH.</p>
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<p>Schematic diagram showing lignin extraction with DES.</p>
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17 pages, 2273 KiB  
Article
Characterization of the Aroma Profile of Food Smoke at Controllable Pyrolysis Temperatures
by Marina Rigling, Laura Höckmeier, Malte Leible, Kurt Herrmann, Monika Gibis, Jochen Weiss and Yanyan Zhang
Separations 2023, 10(3), 176; https://doi.org/10.3390/separations10030176 - 6 Mar 2023
Cited by 5 | Viewed by 2341
Abstract
Smoking is used to give food its typical aroma and to obtain the desired techno-functional properties of the product. To gain a deeper knowledge of the whole process of food smoking, a controllable smoking process was developed, and the influence of wood pyrolysis [...] Read more.
Smoking is used to give food its typical aroma and to obtain the desired techno-functional properties of the product. To gain a deeper knowledge of the whole process of food smoking, a controllable smoking process was developed, and the influence of wood pyrolysis temperature (150–900 °C) on the volatile compounds in the smoking chamber atmosphere was investigated. The aroma profile of smoke was decoded by headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS). Subsequently, the correlations in the most important substance classes, as well as in individual target components, were investigated by the Pearson test. Phenols and lactones showed an increase over the entire applied temperature range (rT = 0.94 and rT = 0.90), whereas furans and carbonyls showed no strict temperature dependence (rT < 0.6). Investigations on single aroma compounds showed that not all compounds of one substance class showed the same behavior, e.g., guaiacol showed no significant increase over the applied pyrolysis temperature, whereas syringol and hydoxyacetone showed a plateau after 450 °C, and phenol and cyclotene increased linear over the applied temperature range. These findings will help to better understand the production of aroma-active compounds during smoke generation in order to meet consumers preferences. Full article
(This article belongs to the Special Issue Application of Chromatography in Analytical Chemistry)
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Graphical abstract

Graphical abstract
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<p>Absolute peak areas with standard deviation of the substance classes carbonyls, furans and lactones in food smoke depending on pyrolysis temperature. Different letters indicate a significant difference in absolute peak area of a substance class between different pyrolysis temperatures (<span class="html-italic">p</span> &lt; 0.05, <span class="html-italic">n</span> = 3).</p>
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<p>Food smoke composition at different wood pyrolysis temperatures (<span class="html-italic">T<sub>P</sub></span>) represented as relative peak areas [%] from individual substance classes. (1) <span class="html-italic">T<sub>P</sub></span> = 150 °C, (2) <span class="html-italic">T<sub>P</sub></span> = 300 °C, (3) <span class="html-italic">T<sub>P</sub></span> = 450 °C, (4) <span class="html-italic">T<sub>P</sub></span> = 600 °C, (5) <span class="html-italic">T<sub>P</sub> =</span> 750 °C, (6) <span class="html-italic">T<sub>P</sub> =</span> 900 °C.</p>
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<p>Correlation matrix between pyrolysis temperature and substance classes obtained via Pearson’s linear correlation analysis; total = sum of all target aroma compounds. Significance levels: * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01, *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>Absolute peak areas with standard deviation of individual phenols in food smoke depending on pyrolysis temperature. (<b>a</b>) Guaiacol, (<b>b</b>) syringol, (<b>c</b>) phenol, (<b>d</b>) creosol, (<b>e</b>) 4-ethyl-guaiacol, (<b>f</b>) <span class="html-italic">p</span>-cresol, (<b>g</b>) eugenol, (<b>h</b>) <span class="html-italic">o</span>-cresol, (<b>i</b>) vanillin and (<b>j</b>) <span class="html-italic">trans</span>-isoeugenol. Different letters indicate a significant difference in absolute peak area of a substance between different pyrolysis temperatures (<span class="html-italic">p</span> &lt; 0.05, <span class="html-italic">n</span> = 3).</p>
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<p>Absolute peak areas with standard deviation of individual lactones in food smoke depending on pyrolysis temperature. (<b>a</b>) 2-(5H)-furanone and (<b>b</b>) butyrolactone. Different letters indicate a significant difference in absolute peak area of a substance between different pyrolysis temperatures (<span class="html-italic">p</span> &lt; 0.05, <span class="html-italic">n</span> = 3).</p>
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<p>Absolute peak areas with standard deviation of individual carbonyls in food smoke depending on pyrolysis temperature. (<b>a</b>) cyclotene, (<b>b</b>) hydroxyacetone, (<b>c</b>) 2-methyl-2-cyclopenten-1-one and (<b>d</b>) diacetyl. Different letters indicate a significant difference in absolute peak area of a substance between different pyrolysis temperatures (<span class="html-italic">p</span> &lt; 0.05, <span class="html-italic">n</span> = 3).</p>
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<p>Absolute peak areas with standard deviation of individual furans in food smoke depending on pyrolysis temperature. (<b>a</b>) Furfural and (<b>b</b>) 5-methyl-furfural.</p>
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22 pages, 4554 KiB  
Article
Foliar Application of Oil Palm Wood Vinegar Enhances Pandanus amaryllifolius Tolerance under Drought Stress
by Muhammad Asyraf Mohd Amnan, Wee Fei Aaron Teo, Wan Mohd Aizat, Fiqri Dizar Khaidizar and Boon Chin Tan
Plants 2023, 12(4), 785; https://doi.org/10.3390/plants12040785 - 9 Feb 2023
Cited by 6 | Viewed by 3047
Abstract
Drought stress severely threatens plant growth, yield and survivability. Wood vinegar, formed by the condensation of smoke produced during biochar production, has been shown to promote plant growth and enhance stress tolerance. They have now been recognized as a sustainable alternative and are [...] Read more.
Drought stress severely threatens plant growth, yield and survivability. Wood vinegar, formed by the condensation of smoke produced during biochar production, has been shown to promote plant growth and enhance stress tolerance. They have now been recognized as a sustainable alternative and are frequently used exogenously to support plants coping with environmental stress. This study aimed to evaluate the efficacy of oil palm wood vinegar (OPWV) in mitigating the adverse effects of drought stress on Pandanus amaryllifolius. The optimal concentrations and frequencies of OPWV application were determined before the drought treatment. The results showed that the imposed drought stress negatively affected the plant growth parameters but applying OPWV at 1:500 dilution at 3-day intervals for 12 days increased its tolerance. These include increased leaf relative water content, root-to-shoot ratio, relative stem circumference, chlorophyll pigments and antioxidant enzyme activities. In contrast, the drought-stressed plants treated with OPWV showed decreased relative electrolyte leakage, hydrogen peroxide, proline, malondialdehyde, and enhanced drought-responsive gene expressions, such as HSP70, GAPDH, and Thau, while ENO and β-Fruc were reduced. These biostimulatory effects of OPWV might be due to several antioxidant compounds, such as anthranilic acid, tetrasiloxane, syringol, guaiacol, and catechol. Altogether, our results showed the effectiveness of OPWV in alleviating the adverse effects of drought stress, and as such, OPWV could be potentially applied in agriculture. Full article
(This article belongs to the Special Issue Regulation of Crop Quality and Stress Responses)
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Figure 1
<p>The plant morphological and pigment analyses of the <span class="html-italic">Pandanus amaryllifolius</span> treated with different dilution factors of oil palm wood vinegar (OPWV). (<b>A</b>) Relative stem circumference. (<b>B</b>) Root dry weight (DW). (<b>C</b>) Shoot DW. (<b>D</b>) The root-to-shoot ratio. (<b>E</b>) Chlorophyll <span class="html-italic">a</span> (µg mg<sup>−1</sup> DW). (<b>F</b>) Chlorophyll <span class="html-italic">b</span> (µg mg<sup>−1</sup> DW). (<b>G</b>) Total chlorophyll (µg mg<sup>−1</sup> DW). (<b>H</b>) Carotenoids (µg mg<sup>−1</sup> DW). The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ above the bars indicates the highest value, followed by ‘ab’ and ‘b’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
Full article ">Figure 2
<p>The plant morphological and pigment analyses of the <span class="html-italic">Pandanus amaryllifolius</span> were subjected to different application frequencies. F1: applied once at 6-day intervals, F2: applied once at 3-day intervals, and F3: applied once at 1-day intervals. (<b>A</b>) Relative stem circumference. (<b>B</b>) Shoot dry weight (DW). (<b>C</b>) Root DW. (<b>D</b>) The root-to-shoot ratio (<b>E</b>) Chlorophyll <span class="html-italic">a</span> (µg mg<sup>−1</sup> DW). (<b>F</b>) Chlorophyll <span class="html-italic">b</span> (µg mg<sup>−1</sup> DW). (<b>G</b>) Total chlorophyll (µg mg<sup>−1</sup> DW). (<b>H</b>) Carotenoids (µg mg<sup>−1</sup> DW). The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ above the bars indicates the highest value, followed by ‘ab’, ‘b’, and ‘c’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The morphological analysis of the well-watered and drought-stressed <span class="html-italic">Pandanus amaryllifolius</span> plants treated with or without OPWV for 7 and 10 days. (<b>A</b>) Representative photographs of <span class="html-italic">P. amaryllifolius</span> under different conditions. Bar = 10 cm. (<b>B</b>) Leaf relative water content (LRWC). (<b>C</b>) Leaf relative electrolyte leakage (REL). (<b>D</b>) The shoot dry weight (DW). (<b>E</b>) Root DW. (<b>F</b>) Root-to-shoot mass ratio. The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ above the bars indicates the highest value, followed by ‘ab’, ‘b’, and ‘c’. The (<b>×</b>) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The stem and leaf morphological analyses of the <span class="html-italic">Pandanus amaryllifolius</span> treated with 1:500 diluted OPWV at 3-day intervals under well-watered and drought stress conditions for 7 and 10 days. (<b>A</b>) The relative stem circumference. (<b>B</b>) The percentage of yellowing leaves. (<b>C</b>) The percentage of Stage 1 leaf folding. (<b>D</b>) The percentage of Stage 2 leaf folding. The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ above the bars indicates the highest value, followed by ‘b’, ‘c’, and ‘d’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The pigmentation constituents of the well-watered and drought-stressed plants with or without OPWV for 7 and 10 days. (<b>A</b>) Chlorophyll <span class="html-italic">a</span> (µg mg<sup>−1</sup> DW). (<b>B</b>) Chlorophyll <span class="html-italic">b</span> (µg mg<sup>−1</sup> DW). (<b>C</b>) Total chlorophyll (µg mg<sup>−1</sup> DW). (<b>D</b>) Carotenoids (µg mg<sup>−1</sup> DW). The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ indicates the highest value, followed by ‘ab’, ‘b’, and ‘c’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), proline and malondialdehyde (MDA) contents in the well-watered and drought-stressed <span class="html-italic">Pandanus amaryllifolius</span> plants with or without OPWV for 7 and 10 days. (<b>A</b>) H<sub>2</sub>O<sub>2</sub>. (<b>B</b>) Proline. (<b>C</b>) MDA. The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ above the bars indicates the highest value, followed by ‘b’, ‘c’, and ‘d’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The antioxidant enzyme activities of the well-watered and drought-stressed <span class="html-italic">Pandanus amaryllifolius</span> plants with or without OPWV for 7 and 10 days. (<b>A</b>) Superoxide dismutase (SOD). (<b>B</b>) Catalase (CAT). (<b>C</b>) Peroxidase (POD). (<b>D</b>) Ascorbate peroxidase (APX). (<b>E</b>) Glutathione reductase (GR). The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ indicates the highest value, followed by ‘b’, ‘bc’, ‘c’ and ‘d’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
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<p>The drought-responsive gene expression of the well-watered or drought-stressed <span class="html-italic">Pandanus amaryllifolius</span> treated with or without OPWV for 7 days. (<b>A</b>) <span class="html-italic">Heat shock protein 70</span> (<span class="html-italic">PaHSP70</span>). (<b>B</b>) <span class="html-italic">Glyceraldehyde-3-phosphate dehydrogenase</span> (<span class="html-italic">PaGAPDH</span>). (<b>C</b>) <span class="html-italic">Enolase</span> (<span class="html-italic">PaENO</span>). (<b>D</b>) <span class="html-italic">Thaumatin</span> (<span class="html-italic">PaThau</span>). (<b>E</b>) β-fructofuranosidase (Paβ-Fruc). Actin and elongation factor-1 of <span class="html-italic">P. amaryllifolius</span> were reference genes for gene expression normalization. The letter labelled on the mean value indicates a significant level between treatments based on the one-way ANOVA, followed by the post hoc Tukey test when its <span class="html-italic">p</span>-value &lt; 0.05. The letter ‘a’ indicates the highest value, followed by ‘b’, ‘c’, and ‘d’. The (×) labelled in the box plot indicates the mean value of the treatment, while the (•) refers to the outlier value of the replicates.</p>
Full article ">Figure 9
<p>The schematic diagram of the experimental setup. (<b>A</b>) <span class="html-italic">Pandanus amaryllifolius</span> plants were sprayed with oil palm wood vinegar (OPWV) at 1:100, 1:250, 1:500, and 1:1000 dilutions in 3-day intervals until 12 days. The plants were allowed to grow for an additional 7 days before harvesting. (<b>B</b>) <span class="html-italic">P. amaryllifolius</span> plants were sprayed with OPWV at 1:500 dilution at 6-day intervals (F1), 3-day intervals (F2), and 1-day intervals (F3). Well-watered plants served as control. (<b>C</b>) The optimized concentration and application frequency of OPWV was used to determine its potential to mitigate the drought stress effects. <span class="html-italic">P. amaryllifolius</span> plants were well-watered or treated with 7- or 10-day drought stress with or without OPWV.</p>
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15 pages, 4176 KiB  
Article
Recovery and Reuse of Valuable Chemicals Derived from Hydrothermal Carbonization Process Liquid
by Abu-Taher Jamal-Uddin, M. Toufiq Reza, Omid Norouzi, Shakirudeen A. Salaudeen, Animesh Dutta and Richard G. Zytner
Energies 2023, 16(2), 732; https://doi.org/10.3390/en16020732 - 8 Jan 2023
Cited by 2 | Viewed by 1580
Abstract
Recovery and reuse of valuable chemicals from hydrothermal carbonization process liquid (HTC-PL) from tomato plant biomass (TPB) was conducted. Different HTC-PLs were characterized with FTIR and Py-GC-MS analyses revealing the presence of low molecular weight linear, cyclic, and aromatics compounds in the HTC-PL. [...] Read more.
Recovery and reuse of valuable chemicals from hydrothermal carbonization process liquid (HTC-PL) from tomato plant biomass (TPB) was conducted. Different HTC-PLs were characterized with FTIR and Py-GC-MS analyses revealing the presence of low molecular weight linear, cyclic, and aromatics compounds in the HTC-PL. Separation of these valuable chemicals by fractional distillation resulted in eutectic constrains. Solvent extraction separation followed by solvent recovery and reuse provided encouraging results. The non-polar portion of HTC-PLs were extracted by using n-hexane (C6H14), and diethyl ether (C2H5)2O solvents with 8.5 and 4.3% recoveries, respectively. Characterization by FTIR and Py-GC-MS revealed petrol fuel like materials in the extracts of C6H14 and (C2H5)2O, irrespective of higher boiling components. Blends of both non-polar extracts were flame tested revealing good burning characteristics with minimal smoke and residue. Bench scale spirit lamp tests showed the blend would be very useful for greenhouse winter heating. The polar extracts using methylene chloride (CH2Cl2) resulted in about 55% recovery. Py-GC-MS analysis revealed acetic acid and 5-Hydroxymethyl furfural (5HMF) majors in the extract along with related derivatives. 5HMF is a valued chemical and demonstrated to be a useful building block for many industrial applications, and flatform chemical for various synthesis. Other identified minor components of HTC-PL were vanillin, divinyl terephthalate, and syringol. After the extractions of polar and non-polar components in three steps, the HTC-PL residue was applied as nutrient source after maintaining pH (5.6) and concentration (TOC, 100–200 mg/L) to typical greenhouse plants. Plant growth was encouraging. The paper discusses all the potential valued reuse applications of HTC-PL in greenhouses without discharges, which contributes to environmental protection and economic benefits. Full article
(This article belongs to the Section A4: Bio-Energy)
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<p>FTIR micrographs from HTC-PLs at different HTC conditions.</p>
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<p>Selectivity of major compounds in HTC-PL.</p>
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<p>(<b>a</b>). Cellulose degradation steps producing furfural, 5HMF and other products during HTC process. (<b>b</b>). Lignin transformation into syringol and guaicol. (<b>c</b>) Transformation of caffeic acid into vanillin via ferulic acid. (<b>d</b>). Condensation of Phthalic acid with vinyl alcohol into divinyl-tetephthalate.</p>
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<p>Proposed TPB components transformation model producing chemicals as identified in HTC-PL.</p>
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<p>Major chemicals in methylene chloride extracts from HTC-PL as identified by GC-MS.</p>
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<p>Crystalized separation of 5HMF through oxidation-conversion into FDCA.</p>
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<p>GC-MS TICs of (<b>a</b>) petroleum fuel, (<b>b</b>) ether extract, and (<b>c</b>) hexane extract.</p>
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<p>Comparative FTIR micrographs of (<b>a</b>) petrol, along with (<b>b</b>) ether, and (<b>c</b>) hexane extracts (ext.) from HTC-PL.</p>
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<p>Tomato planting nursery pots substituted with and without HTC-PL residue. (<b>a</b>) With HTC-PL residue addition; (<b>b</b>) Without HTC-PL residue addition.</p>
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17 pages, 3713 KiB  
Article
Zeolitic Imidazolate Framework Decorated Molybdenum Carbide Catalysts for Hydrodeoxygenation of Guaiacol to Phenol
by Jintu Francis Kurisingal, Shinjae Lee, Jun Gyeong Lee and Kwangjin An
Catalysts 2022, 12(12), 1605; https://doi.org/10.3390/catal12121605 - 7 Dec 2022
Cited by 3 | Viewed by 1793
Abstract
Bimetallic zeolitic imidazolate framework (BMZIF)-decorated Mo carbide catalysts were designed for the catalytic hydrodeoxygenation of guaiacol to produce phenol with high selectivity. A uniform layer of BMZIF was systematically coated onto the surface of the MoO3 nanorods. During carbonization at 700 °C [...] Read more.
Bimetallic zeolitic imidazolate framework (BMZIF)-decorated Mo carbide catalysts were designed for the catalytic hydrodeoxygenation of guaiacol to produce phenol with high selectivity. A uniform layer of BMZIF was systematically coated onto the surface of the MoO3 nanorods. During carbonization at 700 °C for 4 h, BMZIF generated active species (ZnO, CoO) on highly dispersed N-doped carbons, creating a porous shell structure. Simultaneously, the MoO3 nanorod was transformed into the Mo2C phase. The resulting core@shell type Mo2C@BMZIF-700 °C (4 h) catalyst promoted a 97% guaiacol conversion and 70% phenol selectivity under 4 MPa of H2 at 330 °C for 4 h, which was not achieved by other supported catalysts. The catalyst also showed excellent selective cleavage of the methoxy group of lignin derivatives (syringol and vanillin), which makes it suitable for selective demethoxylation in future biomass catalysis. Moreover, it exhibits excellent recyclability and stability without changing the structure or active species. Full article
(This article belongs to the Special Issue Catalytic Conversion of Biomass to Added Value Chemicals)
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<p>Structural change in ZIF-decorated Mo carbide nanorods. (<b>a</b>–<b>c</b>) FE-SEM and (<b>d</b>–<b>f</b>) TEM images of (<b>a</b>,<b>d</b>) as-prepared MoO<sub>3</sub> nanorods, (<b>b</b>,<b>e</b>) MoO<sub>3</sub>@BMZIF composite, and (<b>c</b>,<b>f</b>) Mo<sub>2</sub>C@BMZIF-700 °C (4 h) core@shell structure after carbonization under an N<sub>2</sub> atmosphere at 700 °C for 4 h.</p>
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<p>XRD patterns of (<b>a</b>) as-prepared MoO<sub>3</sub> nanorods and MoO<sub>3</sub>@BMZIF catalysts obtained at different reaction times (0.25–24 h), and (<b>b</b>) Mo<sub>2</sub>C@BMZIF-700 °C (4 h).</p>
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<p>(<b>a</b>–<b>d</b>) HR-TEM images of Mo<sub>2</sub>C@BMZIF-700 °C (4 h) showing Mo<sub>2</sub>C, ZnO, and CoO phases and (<b>e</b>) corresponding elemental EDS maps of Mo<sub>2</sub>C@BMZIF-700 °C (4 h).</p>
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<p>(<b>a</b>) XPS profiles of Mo<sub>2</sub>C@BMZIF-700 °C (4 h). (<b>b</b>) XPS Mo 3d spectra compared to a pure Mo<sub>2</sub>C-700 °C (4 h) nanorod and the Mo<sub>2</sub>C@BMZIF-700 °C (4 h) core@shell structure. XPS (<b>c</b>) Mo 3d and (<b>d</b>) N 1s spectra of Mo<sub>2</sub>C@BMZIF-700 °C (4 h).</p>
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<p>Conversion and product selectivity of catalytic HDO of guaiacol over Mo<sub>2</sub>C@BMZIF catalysts as a function of (<b>a</b>) carbonization condition of the catalyst, (<b>b</b>) reaction pressure, (<b>c</b>) temperature, and (<b>d</b>) time (a standard reaction condition: catalyst 60 mg, guaiacol 0.12 g, <span class="html-italic">n</span>-decane 20 mL, 330 °C, 4 h, 4 MPa). Mo<sub>2</sub>C@BMZIF-700 °C (4 h) catalyst was used for <b>b</b>–<b>d</b>.</p>
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<p>Comparison of conversion and product selectivity of catalytic HDO of guaiacol over various catalysts (reaction condition: catalyst 60 mg, guaiacol 0.12 g, <span class="html-italic">n</span>-decane 20 mL, 330 °C, 4 h, 4 MPa).</p>
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<p>(<b>a</b>) Catalytic recyclability test for 4 runs (catalyst 60 mg, guaiacol 0.12 g, <span class="html-italic">n</span>-decane 20 mL, 330 °C, 4 h, 4 MPa), (<b>b</b>) XRD, (<b>c</b>) TEM, and (<b>d</b>) FE-SEM results of the spent Mo<sub>2</sub>C@BMZIF-700 °C (4 h) catalyst after 4 runs.</p>
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<p>(<b>a</b>) Schematic representation of the possible reaction pathways and products by catalytic HDO of guaiacol. (<b>b</b>) Schematic illustration of the synthesis of ZIF-decorated Mo carbide nanorods with a core@shell structure.</p>
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10 pages, 1829 KiB  
Article
Extraction and Depolymerization of Lignin from Pine Sawdust and Pistachio Shells
by Balawanthrao Jadhav, Ranen Roy, Md Sajjadur Rahman and Douglas E. Raynie
Biomass 2022, 2(4), 348-357; https://doi.org/10.3390/biomass2040023 - 28 Nov 2022
Cited by 4 | Viewed by 2754
Abstract
Lignocellulosic biomass is a renewable resource that contains three major constituents: cellulose, hemicellulose, and lignin. Lignin is a potential source of aromatic phenols. The extraction and subsequent depolymerization of lignin was studied using pine sawdust and pistachio shells. Lignin extraction used 70:30 methyl [...] Read more.
Lignocellulosic biomass is a renewable resource that contains three major constituents: cellulose, hemicellulose, and lignin. Lignin is a potential source of aromatic phenols. The extraction and subsequent depolymerization of lignin was studied using pine sawdust and pistachio shells. Lignin extraction used 70:30 methyl isobutyl ketone:ethanol followed by 0.1M H2SO4. The extraction yield of lignin was 15.78 ± 3.38% from pistachio shells and 18.86 ± 1.52% from pine sawdust. The extracted lignin was characterized using Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and 1H-NMR spectroscopy. The extracted lignin was depolymerized using subcritical water and a Ni-Graphene catalyst at 240 °C for 10 min. The depolymerization products were identified as phenolic monomers, such as phenol, guaiacol, vanillin, syringol, guaiacylpropane, syringaldehyde, coniferaldehyde, synapyl alcohol, and synapyl aldehyde, using GC-MS. Full article
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<p>Extraction of lignin from the biomass using accelerated solvent extraction (ASE).</p>
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<p>Extraction of lignin from the pine sawdust biomass at different temperatures.</p>
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<p>FTIR spectrum of extracted lignin from the pistachio shell and pine sawdust biomass and compared with commercial lignin.</p>
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<p><sup>1</sup>H-NMR spectrum of extracted lignin from pine sawdust and pistachio shells compared with commercial lignin.</p>
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<p>TGA plots of lignin from pistachio shells, pine sawdust, and commercial lignin obtained under nitrogen atmosphere at 10 °C/min.</p>
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<p>GC-MS total ion chromatogram of phenolic monomers from pine sawdust lignin.</p>
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<p>Relative abundance of phenolic monomers from pine sawdust lignin.</p>
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18 pages, 3209 KiB  
Article
Integrating Torrefaction of Pulp Industry Sludge with Anaerobic Digestion to Produce Biomethane and Volatile Fatty Acids: An Example of Industrial Symbiosis for Circular Bioeconomy
by Tharaka Rama Krishna C. Doddapaneni, Margareta Novian Cahyanti, Kaja Orupõld and Timo Kikas
Fermentation 2022, 8(9), 453; https://doi.org/10.3390/fermentation8090453 - 11 Sep 2022
Cited by 7 | Viewed by 2304
Abstract
Industrial symbiosis, which allows the sharing of resources between different industries, could help to improve the overall feasibility of bio-based chemicals production. In that regard, this study focused on integrating the torrefaction of pulp industry sludge with anaerobic digestion. More specifically, anaerobic digestion [...] Read more.
Industrial symbiosis, which allows the sharing of resources between different industries, could help to improve the overall feasibility of bio-based chemicals production. In that regard, this study focused on integrating the torrefaction of pulp industry sludge with anaerobic digestion. More specifically, anaerobic digestion (AD) of pulp sludge-derived torrefaction condensate (TC) was studied to evaluate the biomethane and volatile fatty acid (VFA) potential. The torrefaction condensate produced at 275 and 300 °C was used in AD. The volatile solid content (VS) was 6.69 and 9.01% for the condensate produced at 275 and 300 °C, respectively. The organic fraction of TC mainly contained acetic acid, 2-furanmethanol, and syringol. The methane yield was in the range of 481–772 mL/g VS for the mesophilic and 401–746 mL/g VS for the thermophilic process, respectively. The VFA yield was in the range of 1.1 to 3.4 g/g VS for mesophilic and from 1.5 to 4.7 g/g VS in thermophilic conditions, when methanogenesis was inhibited. Finally, pulp sludge TC is a feasible feedstock to produce platform chemicals like VFA. However, at higher substrate loading, signs of process inhibition were observed because of the relatively increasing concentration of microbial inhibitors Full article
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<p>Innovative process integration approach to produce bioenergy and biochemicals from pulp industry sludge.</p>
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<p>The cumulative methane yield at various substrate loadings for torrefaction condensate (TC) produced at 275 and 300 °C (<b>a</b>,<b>b</b>) mesophilic and (<b>c</b>,<b>d</b>) thermophilic conditions, respectively. The 2, 4, 6, represent substrate loadings (g VS/L); M and T represent mesophilic and thermophilic processes, respectively; RS represents raw sludge. For example, 275−2M−BES is for condensate produced at 275 °C, mesophilic conditions, 2 g VS/L loading and methanogenesis inhibition.</p>
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<p>Volatile fatty acids production for the mesophilic process at various substrate loading for torrefaction condensate produced at 275 and 300 °C; (<b>a</b>,<b>b</b>) without methanogenesis inhibition and (<b>c</b>,<b>d</b>) with methanogenesis inhibition. The 2, 4, 6 represent substrate loading (g VS/L). For example, 275−2M−BES is for condensate produced at 275 °C, mesophilic conditions, 2 g VS/L loading and methanogenesis inhibition.</p>
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<p>Volatile fatty acids production for the thermophilic process at various substrate loading for torrefaction condensate produced at 275 and 300 °C; (<b>a</b>,<b>b</b>) without methanogenesis inhibition and (<b>c</b>,<b>d</b>) with methanogenesis inhibition. The 2, 4, 6 represent substrate loading (g VS/L); RS represents raw sludge. For example, 275−2T−BES is for condensate produced at 275 °C, thermophilic conditions, 2 g VS/L loading and methanogenesis inhibition.</p>
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<p>The industrial symbiosis between different biomass and/or organic residues valorization industries under the concept of anaerobic digestion of pulp sludge derived torrefaction condensate.</p>
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21 pages, 4038 KiB  
Article
The Consistency of Yields and Chemical Composition of HTL Bio-Oils from Lignins Produced by Different Preprocessing Technologies
by Hilde Vik Halleraker, Konstantinos Kalogiannis, Angelos Lappas, Rafael C. A. Castro, Ines C. Roberto, Solange I. Mussatto and Tanja Barth
Energies 2022, 15(13), 4707; https://doi.org/10.3390/en15134707 - 27 Jun 2022
Cited by 4 | Viewed by 1546
Abstract
This work evaluates the effect of feedstock type and composition on the conversion of lignin to liquid by solvolysis with formic acid as hydrogen donor (LtL), by analyzing the yields and molecular composition of the liquid products and interpreting them in terms of [...] Read more.
This work evaluates the effect of feedstock type and composition on the conversion of lignin to liquid by solvolysis with formic acid as hydrogen donor (LtL), by analyzing the yields and molecular composition of the liquid products and interpreting them in terms of both the type and the preprocessing of the lignocellulosic biomass using chemometric data analysis. Lignin samples of different types and purities from softwood, hardwood, and grasses (rice straw and corn stover) have been converted to bio-oil, and the molecular composition analyzed and quantified using GC-MS. LtL solvolysis was found to be a robust method for lignin conversion in terms of converting all samples into bio-oils rich in phenolic compounds regardless of the purity of the lignin sample. The bio-oil yields ranged from 24–94 wt.% relative to lignin input and could be modelled well as a function of the elemental composition of the feedstock. On a molecular basis, the softwood-derived bio-oil contained the most guaiacol-derivatives, and syringol was correlated to hardwood. However, the connection between compounds in the bio-oil and lignin origin was less pronounced than the effects of the methods for biomass fractionation, showing that the pretreatment of the biomass dominates both the yield and molecular composition of the bio-oil and must be addressed as a primary concern when utilization of lignin in a biorefinery is planned. Full article
(This article belongs to the Special Issue Bioenergy and Biobased Technologies to Support a Green Transition)
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<p>Chromatogram of the oil from experiment SW1-kraft-360. Peaks from impurities in the solvent are in grey. Internal standard (IS) is hexadecane.</p>
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<p>Chromatogram of the oil from experiment HW1-wetox-360. Peaks from impurities in the solvent are in grey. Internal standard (IS) is hexadecane.</p>
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<p>Chromatogram of the oil from experiment G3-deac-360. Internal standard (IS) is hexadecane.</p>
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<p>Quantification of guaiacol and selected substituted guaiacols in the produced bio-oils, given as wt.% in the obtained bio-oil. Sample names are specified in the experimental section.</p>
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<p>Quantification of catechol and selected substituted catechols in the produced bio-oils, given as wt.% in the obtained bio-oil.</p>
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<p>Quantification of phenol, selected substituted phenols and 2-(4-hydroxyphenyl) ethanol in the produced bio-oils, given as wt.% in the obtained bio-oil.</p>
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<p>Quantification of syringol, 3-methoxy catechol, and 2-naphthol, given as wt.% in the obtained bio-oil.</p>
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<p>Van Krevelen plot displaying the oxygen to carbon ratio (<span class="html-italic">x</span>-axis) and hydrogen to carbon ratio (<span class="html-italic">y</span>-axis) of samples of lignin feedstock and LtL-oils. The ratios are based on mol% (all samples were analyzed in duplicates and presented in this plot as an average of the two analyses. Where replicate experiments were performed, the average of the experiments in question is presented in this plot).</p>
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<p>Multivariate regression model of predicted vs. measured oil yield based on the elemental analysis of lignin as specified in Equation (4). The regression coefficient is 0.87.</p>
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<p>LtL-oil yield and solid yield presented as the weight percent of lignin input. SW3 experiments are included for comparison. The gas yields are given as a continuous line. Gas yields larger than 100% imply a significant contribution of gas-phase products from lignin feedstock reactions. All results regarding SW3 have previously been published in Løhre et al. [<a href="#B36-energies-15-04707" class="html-bibr">36</a>].</p>
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<p>Biplot containing all variables and all experiments from this work. Experiments done with kraft-lignin are marked in green, the blue experiments are done with lignin from oxidative preprocessing, and the red experiments are performed with lignin from a deacetylation preprocessing.</p>
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15 pages, 2012 KiB  
Article
PLS-R Calibration Models for Wine Spirit Volatile Phenols Prediction by Near-Infrared Spectroscopy
by Ofélia Anjos, Ilda Caldeira, Tiago A. Fernandes, Soraia Inês Pedro, Cláudia Vitória, Sheila Oliveira-Alves, Sofia Catarino and Sara Canas
Sensors 2022, 22(1), 286; https://doi.org/10.3390/s22010286 - 31 Dec 2021
Cited by 14 | Viewed by 3271
Abstract
Near-infrared spectroscopic (NIR) technique was used, for the first time, to predict volatile phenols content, namely guaiacol, 4-methyl-guaiacol, eugenol, syringol, 4-methyl-syringol and 4-allyl-syringol, of aged wine spirits (AWS). This study aimed to develop calibration models for the volatile phenol’s quantification in AWS, by [...] Read more.
Near-infrared spectroscopic (NIR) technique was used, for the first time, to predict volatile phenols content, namely guaiacol, 4-methyl-guaiacol, eugenol, syringol, 4-methyl-syringol and 4-allyl-syringol, of aged wine spirits (AWS). This study aimed to develop calibration models for the volatile phenol’s quantification in AWS, by NIR, faster and without sample preparation. Partial least square regression (PLS-R) models were developed with NIR spectra in the near-IR region (12,500–4000 cm−1) and those obtained from GC-FID quantification after liquid-liquid extraction. In the PLS-R developed method, cross-validation with 50% of the samples along a validation test set with 50% of the remaining samples. The final calibration was performed with 100% of the data. PLS-R models with a good accuracy were obtained for guaiacol (r2 = 96.34; RPD = 5.23), 4-methyl-guaiacol (r2 = 96.1; RPD = 5.07), eugenol (r2 = 96.06; RPD = 5.04), syringol (r2 = 97.32; RPD = 6.11), 4-methyl-syringol (r2 = 95.79; RPD = 4.88) and 4-allyl-syringol (r2 = 95.97; RPD = 4.98). These results reveal that NIR is a valuable technique for the quality control of wine spirits and to predict the volatile phenols content, which contributes to the sensory quality of the spirit beverages. Full article
(This article belongs to the Special Issue Using Vis-NIR Spectroscopy for Predicting Quality Compounds in Foods)
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<p>Chemical structure of volatile phenols studied in the AWS and their associated sensory descriptors (SD) [<a href="#B5-sensors-22-00286" class="html-bibr">5</a>].</p>
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<p>PCA representation of loadings and scores of all AWS samples and all volatile phenols analysed. Legend: C and L stand for the wood used in the ageing process, Chestnut and Limousin respectively; O15, 30 and 60 are the different micro-oxygenation modalities used in the alternative system; N—without micro-oxygenation; B—Barrel; 0—0 months in bottle; 6—6 months in bottle.</p>
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<p>PCA was performed with spectral information of the AWS with chestnut (C) and with Limousin wood, acquired in NIR. Legend: C and L stand for the wood used in the ageing process, Chestnut and Limousin respectively; 15, 30 and 60 the different levels of micro-oxygenation used in the alternative system; N—no micro-oxygenation used in the alternative system; B—Barrel; 0—0 months in a bottle; 6—6 months in bottle.</p>
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<p>Representative absorption spectra of all AWS samples acquired in the NIR region measured against a background of air.</p>
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<p>True value−Prediction value of each volatile compound analysed compared to the difference between the minimum and maximum a value.</p>
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16 pages, 1189 KiB  
Article
Evaluating the Potential for Smoke from Stubble Burning to Taint Grapes and Wine
by Kerry Wilkinson, Renata Ristic, Imogen McNamara, Beth Loveys, WenWen Jiang and Mark Krstic
Molecules 2021, 26(24), 7540; https://doi.org/10.3390/molecules26247540 - 13 Dec 2021
Cited by 7 | Viewed by 2541
Abstract
It has been well established that bushfire/wildfire smoke can taint grapes (and therefore wine), depending on the timing and duration of exposure, but the risk of smoke contamination from stubble burning (a practice employed by some grain growers to prepare farmland for sowing) [...] Read more.
It has been well established that bushfire/wildfire smoke can taint grapes (and therefore wine), depending on the timing and duration of exposure, but the risk of smoke contamination from stubble burning (a practice employed by some grain growers to prepare farmland for sowing) has not yet been established. This study exposed excised bunches of grapes to smoke from combustion of barley straw and pea stubble windrows to investigate the potential for stubble burning to elicit smoke taint. Increased levels of volatile phenols (i.e., chemical markers of smoke taint) were detected in grapes exposed to barley straw smoke (relative to control grapes), with smoke density and the duration of smoke exposure influencing grape volatile phenols. However, the sensory panel did not perceive wine made from grapes exposed to low-density smoke to be tainted, despite the presence of low levels of syringol providing compositional evidence of smoke exposure. During the pea stubble burn, grapes positioned amongst the burning windrows or on the edge of the pea paddock were exposed to smoke for ~15–20 and 30–45 min, respectively, but this only resulted in 1 µg/kg differences in the cresol and/or syringol concentrations of smoke-affected grapes (and 1 µg/L differences for wine), relative to controls. A small, but significant increase in the intensity of smoke aroma and burnt rubber flavor of wine made from the grapes positioned amongst the burning pea stubble windrows provided the only sensory evidence of any smoke taint. As such, had vineyards been located immediately downwind from the pea stubble burn, it is unlikely that there would have been any smoke contamination of unharvested grapes. Full article
(This article belongs to the Special Issue Smoke Taint in Grapes and Wine)
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<p>Environmental conditions before, during and after exposure of excised bunches of Shiraz grapes to barley straw smoke (i.e., −30 to 0, 0 to 300 and 300 to 330 min, respectively): (<b>a</b>) wind and gust speed, and temperature; and (<b>b</b>) particulate matter (PM) concentrations.</p>
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<p>Concentrations of (<b>a</b>) guaiacol, (<b>b</b>) 4-methylguaiacol, (<b>c</b>) cresols and (<b>d</b>) syringol in control (C) and smoke-affected (S) Shiraz grapes (µg/kg) sampled at hourly time points (i.e., t = 1, 2, 3, 4 and 5 h) and wines (µg/L, denoted by an asterisk). Data are the means of three replicates ± standard error (where available). Different letters indicate statistical significance (<span class="html-italic">p</span> ≤ 0.05, one-way ANOVA) amongst grape and wine samples; nd = not detected.</p>
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<p>Sensory profiles of control and smoke-affected Shiraz wines; A = aroma, F = flavor, and AT = aftertaste. Data are the mean intensity ratings for one blended wine per treatment, presented to 62 panelists; ratings for all attributes were statistically significant (<span class="html-italic">p</span> ≤ 0.05, two-way ANOVA).</p>
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<p>Environmental conditions before, during (shaded) and after pea stubble burn: (<b>a</b>) wind and gust speed, and air temperature, measured amongst the stubble windrows; and particulate matter (PM) concentrations, measured (<b>b</b>) amongst stubble windrows in a pea field, (<b>c</b>) on the edge of the pea field (downwind) and (<b>d</b>) in an adjacent field (approximately 500 m downwind).</p>
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<p>Environmental conditions before, during (shaded) and after pea stubble burn: (<b>a</b>) wind and gust speed, and air temperature, measured amongst the stubble windrows; and particulate matter (PM) concentrations, measured (<b>b</b>) amongst stubble windrows in a pea field, (<b>c</b>) on the edge of the pea field (downwind) and (<b>d</b>) in an adjacent field (approximately 500 m downwind).</p>
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<p>Sensory profiles of control and smoke-affected Cabernet Sauvignon wines; A = aroma, F = flavor, AT = aftertaste. Data are the mean intensity ratings for one blended wine per treatment, presented to 52 panelists; ratings for starred attributes were statistically significant (*** = <span class="html-italic">p</span> ≤ 0.05; ** = <span class="html-italic">p</span> ≤ 0.01; two-way ANOVA).</p>
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24 pages, 7343 KiB  
Article
Lignin-Derived Syringol and Acetosyringone from Palm Bunch Using Heterogeneous Oxidative Depolymerization over Mixed Metal Oxide Catalysts under Microwave Heating
by Rangsalid Panyadee, Aphinan Saengsrichan, Pattaraporn Posoknistakul, Navadol Laosiripojana, Sakhon Ratchahat, Babasaheb M. Matsagar, Kevin C.-W. Wu and Chularat Sakdaronnarong
Molecules 2021, 26(24), 7444; https://doi.org/10.3390/molecules26247444 - 8 Dec 2021
Cited by 11 | Viewed by 3302
Abstract
Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, [...] Read more.
Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO2 catalyst (63.87 wt%), Cu-Fe/Al2O3 catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min. Full article
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<p>Co-impregnation of Cu-Fe catalysts on SiO<sub>2</sub> or Al<sub>2</sub>O<sub>3</sub> supports.</p>
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<p>Experimental diagram of EFB depolymerization process in a microwave reactor with mixed metal oxides complex heterogeneous catalysts.</p>
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<p>FT-IR spectroscopic analysis of NaOH-lignin and K<sub>2</sub>CO<sub>3</sub>–lignin compared with the control (H<sub>2</sub>O-lignin) from the alkali hydrothermal lignin extraction with solid:liquid ratio of 1:5 at 200 °C for 20 min under 2 MPa nitrogen pressure.</p>
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<p>XRD patterns of heterogeneously Cu-Fe/SiO<sub>2</sub> and Cu-Fe/Al<sub>2</sub>O<sub>3</sub> mixed metal oxides catalysts.</p>
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<p>XPS spectra recorded for (<b>A</b>) overall spectrum, (<b>B</b>) Fe 2p, (<b>C</b>) Cu 2p of Cu-Fe/Al<sub>2</sub>O<sub>3</sub> catalyst, and (<b>D</b>) overall spectrum, (<b>E</b>) Fe 2p and (<b>F</b>) Cu 2p of Cu-Fe/SiO<sub>2</sub> catalyst.</p>
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<p>XPS spectra recorded for (<b>A</b>) overall spectrum, (<b>B</b>) Fe 2p, (<b>C</b>) Cu 2p of Cu-Fe/Al<sub>2</sub>O<sub>3</sub> catalyst, and (<b>D</b>) overall spectrum, (<b>E</b>) Fe 2p and (<b>F</b>) Cu 2p of Cu-Fe/SiO<sub>2</sub> catalyst.</p>
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<p>FESEM-EDX elemental mapping of (<b>A</b>) Cu-Fe/Al<sub>2</sub>O<sub>3</sub> and (<b>B</b>) Cu-Fe/SiO<sub>2</sub> catalysts.</p>
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<p>FESEM-EDX elemental mapping of (<b>A</b>) Cu-Fe/Al<sub>2</sub>O<sub>3</sub> and (<b>B</b>) Cu-Fe/SiO<sub>2</sub> catalysts.</p>
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<p>Lignin monomer yield in liquid product from depolymerization of K<sub>2</sub>CO<sub>3</sub>-lignin and NaOH-lignin under microwave heating at 300 W for (<b>A</b>) 15 min, and (<b>B</b>) 30 min over heterogeneous catalysts namely Cu-Fe/Al<sub>2</sub>O<sub>3</sub>, Cu-Fe/SiO<sub>2</sub> and without catalyst; S1 = Syringol, S2 = Syringaldehyde, S3 = Acetosyringone, G1 = Vanillin, G2 = Acetovanilone, and H1 = 2,4-Di-tert butylphenol.</p>
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<p>Lignin monomer yield in liquid product from depolymerization of K<sub>2</sub>CO<sub>3</sub>-lignin and NaOH-lignin under microwave heating at 300 W for (<b>A</b>) 15 min, and (<b>B</b>) 30 min over heterogeneous catalysts namely Cu-Fe/Al<sub>2</sub>O<sub>3</sub>, Cu-Fe/SiO<sub>2</sub> and without catalyst; S1 = Syringol, S2 = Syringaldehyde, S3 = Acetosyringone, G1 = Vanillin, G2 = Acetovanilone, and H1 = 2,4-Di-tert butylphenol.</p>
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<p>Yield and selectivity from the depolymerization of EFB derived alkaline lignin (K<sub>2</sub>CO<sub>3</sub>-lignin and NaOH-lignin) to (<b>A</b>) syringol, (<b>B</b>) acetosyringone and (<b>C</b>) 2,4-di-tert butylphenol using 300 W microwave reaction for 15 and 30 min over different catalysts.</p>
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<p>Product yield from the recyclability study of (<b>A</b>) CuFe/Al<sub>2</sub>O<sub>3,</sub> and (<b>B</b>) CuFe/SiO<sub>2</sub> catalysts on depolymerization of NaOH-lignin under microwave at 300 W for 30 min.</p>
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<p>Atomic concentration of fresh and spent catalysts (<b>A</b>) CuFe/Al<sub>2</sub>O<sub>3</sub> and (<b>B</b>) CuFe/SiO<sub>2</sub> from recyclability study of heterogeneous catalyst on NaOH-lignin depolymerization under microwave heating at 300 W for 30 min.</p>
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17 pages, 2756 KiB  
Article
Synthesis of Ce/MgO Catalysts for Direct Oxidation of Hibiscus cannabinus Stalks to Vanillin
by Nur Akila Syakida Idayu Khairul Anuar, Anita Ramli and Lim Jun Wei
Catalysts 2021, 11(12), 1449; https://doi.org/10.3390/catal11121449 - 28 Nov 2021
Cited by 3 | Viewed by 2228
Abstract
One possible method of producing vanillin from biomass is through controlled oxidation of lignin. Direct oxidation of kenaf stalks was chosen without having to separate the cellulose and hemicellulose components from the lignocellulosic biomass. This makes the process greener, as well as saving [...] Read more.
One possible method of producing vanillin from biomass is through controlled oxidation of lignin. Direct oxidation of kenaf stalks was chosen without having to separate the cellulose and hemicellulose components from the lignocellulosic biomass. This makes the process greener, as well as saving time. In this paper, Ce/MgO catalysts were developed for oxidation of kenaf stalks and kenaf lignin under microwave irradiation. The catalysts were characterized for their physicochemical properties using XRD and N2 adsorption–desorption isotherms. The synthesized MgO showed the presence of diffraction peaks assigned to cubic MgO while the 30Ce/MgO catalysts showed the presence of cubic fluorite of CeO2. N2 adsorption–desorption isotherms showed that all catalysts possess Type III isotherm according to IUPAC classification, indicating a nonporous structure. All catalysts were tested for direct oxidation of kenaf stalks under 300 W of microwave irradiation using H2O2 as the oxidizing agent at pH 11.5 and temperatures between 160 and 180 °C for 10–30 min with 5–15% catalyst loading. The highest vanillin yields of 3.70% and 2.90% for extracted lignin and direct biomass oxidation were achieved using 30Ce/MgO-48. In comparison, 7.80% and 4.45% were obtained using 2N of NaOH homogeneous catalyst for extracted lignin and direct biomass, respectively, at 170 °C for 20 min. The reusability test shows that 30Ce/MgO can be used up to three cycles without significant loss in catalytic activity. Other compounds detected were 4-vinylguaiacol, syringol and syringaldehyde. Full article
(This article belongs to the Section Biomass Catalysis)
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<p>Chemical structure of vanillin [<a href="#B6-catalysts-11-01449" class="html-bibr">6</a>].</p>
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<p><span class="html-italic">X</span>-ray diffraction patterns of MgO synthesized using sol-gel and hydrothermal methods at pH 12.</p>
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<p><span class="html-italic">X</span>-ray diffraction patterns of MgO-supported CeO<sub>2</sub> catalysts.</p>
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<p>N<sub>2</sub> adsorption–desorption isotherms of the catalyst.</p>
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<p>FTIR spectra of dried kenaf stalk’s lignin.</p>
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<p>HPLC chromatogram of vanillin standard.</p>
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<p>Calibration curve of the vanillin standard at five different concentrations.</p>
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<p>HPLC chromatogram of derived vanillin.</p>
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<p>Reaction condition: 2 g of dried kenaf stalks, 20 mL of 0.01 N NaOH solution, 10 wt.% of catalyst, 1 mL of H<sub>2</sub>O<sub>2</sub> at 180 °C.</p>
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<p>Reaction condition: 2 g of dried kenaf stalks, 20 mL of 0.01 N NaOH solution, 10 wt.% of catalyst, 1 mL of H<sub>2</sub>O<sub>2</sub> at 20 min.</p>
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<p>Reaction condition: 2 g of dried kenaf stalks, 20 mL of 0.01 N NaOH solution, 1 mL of H<sub>2</sub>O<sub>2</sub> at 20 min for 170 °C.</p>
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<p>Reaction condition: 2 g of dried kenaf stalks and 1.06 g of extracted lignin, 20 mL of 0.01 N NaOH solution, 15 wt.% of catalyst, 1 mL of H<sub>2</sub>O<sub>2</sub> at 20 min for 170 °C.</p>
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<p>Reaction condition: 2 g of dried kenaf stalks, 20 mL of 0.01 N NaOH solution, 15 wt.% of catalyst, 1 mL of H<sub>2</sub>O<sub>2</sub> at 20 min for 170 °C.</p>
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18 pages, 1728 KiB  
Article
Structural Transformation and Creativity Induced by Biological Agents during Fermentation of Edible Nuts from Terminalia catappa
by Oluwatofunmi E. Odutayo, Bose E. Adegboye, Emmanuel A. Omonigbehin, Tolulope D. Olawole, Olubanke O. Ogunlana and Israel S. Afolabi
Molecules 2021, 26(19), 5874; https://doi.org/10.3390/molecules26195874 - 28 Sep 2021
Cited by 5 | Viewed by 2647
Abstract
Terminalia catappa L. (tropical almond) is a nutritious fruit found mainly in the tropics. This study is aimed to establish the naturally biotransformed molecules and identify the probiotic agents facilitating the fermentation. The aqueous extracts from both the unfermented and fermented T. catappa [...] Read more.
Terminalia catappa L. (tropical almond) is a nutritious fruit found mainly in the tropics. This study is aimed to establish the naturally biotransformed molecules and identify the probiotic agents facilitating the fermentation. The aqueous extracts from both the unfermented and fermented T. catappa nuts were subjected to gas chromatography/mass spectrometry (GC/MS) analysis. Syringol (6.03%), glutamine (1.71%), methyl laurate (1.79%), methyl palmitate (1.53%), palmitic acid (5.20%), palmitoleic acid (2.80%), and methyl oleate (2.97%) were detected in the unfermented nuts of the T. catappa. Additionally, two of these natural compounds (palmitic acid (4.19%) and palmitoleic acid (1.48%)) survived the fermentation process to emerge in the fermented seeds. The other natural compounds were biotransformed into 2,3-butanediol (1.81%), butyric acid (16.20%), propane-1,3-diol (19.66%), neoheptanol (2.89%), 2-piperidinone (6.63%), palmitoleic acid (1.18%), formamide, n-(p-hydroxyphenethyl)- (2.80%), and cis-vaccenic acid (1.69%) that newly emerged in the fermented seeds. The phytochemical compounds are likely carbon sources for the organisms facilitating the biotransformed molecules and product production. Four (4) potential probiotic bacteria strains, namely, Probt B1a, Probt B2a, Probt B4a, and Probt B4b, were isolated from the fermented nut. Enterococcus faecum, and Enterococcus faecalis were the organisms identified as driving the fermentation of the seeds. All strains were gram-positive, catalase-negative, and non-hemolytic, which suggests their harmless nature. N-(p-hydroxyphenethyl)-) was associated with fermentation for the first time, and neoheptanol was discovered as the main alcoholic molecule formed during the fermentation of the seeds. This fermentation is a handy tool for bio-transforming compounds in raw food sources into compounds with nutritious and therapeutic potentials. Full article
(This article belongs to the Special Issue New Frontiers in Fermented Products)
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<p>The characterisation of the LAB isolates with 16S rRNA.</p>
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<p>The proposed mechanisms for the transformation of major molecules identified in the natural kernels of <span class="html-italic">T. catappa</span> during fermentation. Keys: <b>P1</b>: Formamide, N-(p-hydroxyphenethyl) (2.80%); <b>P2</b>: 2-Piperidinone (6.63%); <b>P3</b>: Butane-2,3-diol (1.81%); <b>P4</b>: Butyric acid (16.20%); <b>P5</b>: Propane-1,3-diol (19.66%); <b>P6</b>: Neoheptanol (2.89%); <b>P7</b>: Cis-vaccenic acid (1.69%); <b>I-1</b>: Octane; <b>I-2</b>: Dodecane; <b>I-3</b>: Methyl butanoate; <b>C1</b>: Syringol (6.03%); <b>C2</b>: Glutamine (1.71%); <b>C3</b>: Methyl laurate (1.79%); <b>C4</b>: Methyl palmitate (1.53%); <b>C5</b>: Palmitic acid (5.20%); <b>C6</b>: Palmitoleic acid (2.80%); <b>C7</b>: Methyl oleate (2.97%).</p>
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<p>Flow chart illustrating the preparation of flour, unfermented and fermented freeze-dried extracts from <span class="html-italic">T. catappa</span> nuts.</p>
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