<?xml version="1.0" encoding="utf-8" ?>
<article xml:lang="en" article-type="research-article"
    xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">
    <front>
        <journal-meta>
            <journal-id journal-id-type="publisher-id">PSJFS</journal-id>
            <journal-title-group>
                <journal-title>Potravinarstvo Slovak Journal of Food Sciences</journal-title>
                <abbrev-journal-title abbrev-type="pubmed">Potr. S. J. F.
                    Sci.</abbrev-journal-title>
            </journal-title-group>
            <issn pub-type="ppub">1338-0230</issn>
            <issn pub-type="epub">1337-0960</issn>
            <publisher>
                <publisher-name>Association HACCP Consulting</publisher-name>
            </publisher>
        </journal-meta>
        <article-meta>
            <article-id pub-id-type="publisher-id">PSJFS-14-1-682 </article-id>
            <article-id pub-id-type="doi">10.5219/1232 </article-id>
            <article-categories>
                <subj-group subj-group-type="heading">
                    <subject>ARTICLE</subject>
                </subj-group>
            </article-categories>
            <title-group>
                <article-title>FUNCTIONAL PROPERTIES OF THREE NATIVE STARCHES AND THEIR MODIFIED
                    DERIVATIVES </article-title>
            </title-group>
            <contrib-group>
                <contrib contrib-type="author">
                    <name>
                        <surname>Adewumi </surname>
                        <given-names>Funmilayo Deborah </given-names>
                    </name>
                    <xref ref-type="corresp" rid="cor1">&#x002A;</xref>
                </contrib>
                <contrib contrib-type="author">
                    <name>
                        <surname>Lajide </surname>
                        <given-names>Labunmi </given-names>
                    </name>
                    <xref ref-type="aff" rid="aff2"/>
                </contrib>
                <contrib contrib-type="author">
                    <name>
                        <surname>Adetuyi </surname>
                        <given-names>Abayomi Olagunjoye </given-names>
                    </name>
                    <xref ref-type="aff" rid="aff3"/>
                </contrib>
                <contrib contrib-type="author">
                    <name>
                        <surname>Ayodele </surname>
                        <given-names>Olajide </given-names>
                    </name>
                    <xref ref-type="aff" rid="aff4"/>
                </contrib>
                <aff id="aff2">
                    <institution>Labunmi Lajide, Federal University of Technology Akure, Faculty of
                        Sciences, Department of Chemistry, Akure, Ondo State, P.M.B. 704, Nigeria,
                        Tel. +2348034721396, E-mail: bmlajide@gmail.com </institution>
                </aff>
                <aff id="aff3">
                    <institution>Abayomi Olagunjoye Adetuyi, Federal University of Technology Akure,
                        Faculty of Sciences, Department of Chemistry, Akure, Ondo State, P.M.B. 704,
                        Nigeria, Tel. +2348033801359, E-mail: aoadetuyi@futa.edu.ng </institution>
                </aff>
                <aff id="aff4">
                    <institution>Olajide Ayodele, Ekiti State University, Department of Industrial
                        Chemistry, Ado-Ekiti, off Iworoko Road, P.M.B. 5363, Ekiti State, Nigeria,
                        Tel. +2348038006023, E-mail: olajide.ayodele@eksu.edu.ng </institution>
                </aff>
            </contrib-group>
            <author-notes>
                <corresp id="cor1">
                    <label>&#x002A;</label>Corresponding author: Funmilayo Deborah Adewumi, College
                    of Science, Industrial Chemistry, Department of Chemical Sciences, Afe-Babalola
                    University. P.M.B 5454, Ado-Ekiti, Ekiti State, Nigeria, Tel. +2348038521105,
                        <email xmlns:xlink="http://www.w3.org/1999/xlink"
                        xlink:href="funmitj25@yahoo.com">funmitj25@yahoo.com </email>
                </corresp>
            </author-notes>
            <pub-date pub-type="epub">
                <day>28</day>
                <month>9</month>
                <year>2020</year>
            </pub-date>
            <pub-date pub-type="ppub">
                <month>9</month>
                <year>2020</year>
            </pub-date>
            <volume>14</volume>
            <issue>1</issue>
            <fpage>682 </fpage>
            <lpage>691 </lpage>
            <history>
                <date date-type="received">
                    <day>4 </day>
                    <month>11 </month>
                    <year>2019</year>
                </date>
                <date date-type="accepted">
                    <day>17 </day>
                    <month>2 </month>
                    <year>2020</year>
                </date>
            </history>
            <permissions>
                <copyright-statement>&#x00A9; Association HACCP Consulting. All rights
                    reserved.</copyright-statement>
                <copyright-year>2020</copyright-year>
            </permissions>
            <abstract>
                <p>Starches were isolated from cocoyam (<italic>Xanthosoma sagittifollium</italic>),
                    white yam (<italic>Dioscorea rotundata</italic>) and bitter yam
                        (<italic>Dioscorea dumentorum</italic>). Starch modification was carried out
                    using acetic anhydride and phthalic anhydride. The native and modified starches
                    were characterized using Fourier Transformed Infra-red Spectroscopy (FTIR) for
                    identification of the functional groups. Functional properties such as water
                    absorption capacities, oil absorption capacity, swelling power, solubility,
                    gelation temperature, least gelation capacity, amylose content and pH were
                    determined using standard procedures. Acetylation increased the water absorption
                    capacity, oil absorption capacity, swelling power, amylose content, and
                    solubility of the starches while phthalation decreased water absorption
                    capacity, oil absorption capacity, swelling power, and solubility of the
                    starches. Native cocoyam starch has the highest gelation temperature (85
                    &#xB0;C) while Acetylated bitter yam has the lowest gelation temperature (74
                    &#xB0;C). The pH of the native and modified starches was within the range of
                    4.14 − 6.55. Phthalation and acetylation increased the bulk density of the
                    starches. Native cocoyam, white yam, and bitter yam starches had the lowest
                    gelation concentration (6%). Modification of native starches will improve the
                    usage of starch in food and non-food applications. </p>
                <p>
                    <bold>Keywords:</bold> native starch; phthalation; gelation; amylose;
                    pregelatinized starch </p>
            </abstract>
        </article-meta>
    </front>
    <body>
        <sec sec-type="intro">
            <title>INTRODUCTION</title>
            <p>Starch is one of the most available natural polymers is a starting material or an
                intermediate for many chemical industries (<xref ref-type="bibr" rid="b39">Yadav and
                    Garg, 2013</xref>). Starch is a useful raw material for adhesive industries
                because of its availability and abundance (<xref ref-type="bibr" rid="b40">Yu et
                    al., 2009</xref>). Starch has been applied as a filler and bonding agent in the
                making of tablets, it is also used as an additive to improve the shelf life of soaps
                and detergents. Other uses of starch are in the rubber and foam industries (<xref
                    ref-type="bibr" rid="b34">Tonukari, 2004</xref>) and the food industry (<xref
                    ref-type="bibr" rid="b9">Dura and Rosell, 2016</xref>).</p>
            <p>In the food sector, starch is being used to give divers functionalities which include
                stabilizing, gelling, encapsulating, thickening, texturing, and shelf-life
                elongation. Despite the numerous advantageous properties in chemical industries,
                however, many starches in their crude form have limited applications in industrial
                processes as they have a high level of retrogradation which limits their application
                in food processing industries (<xref ref-type="bibr" rid="b31">Singh, Kaur and
                    Singh, 2004</xref>). However, it is necessary to modify crude starches to
                incorporate some specific properties which thereafter make them useful in the
                industrial sector (<xref ref-type="bibr" rid="b35">Torruco-Uco and Betancur-Ancona,
                    2007</xref>).</p>
            <p>Cocoyam (<italic>Colocasia esculenta</italic>) which is an ancient tuber of
                    <italic>Araceae</italic> family originated from South-East, Asia, and has been
                cultivated for over 2000 years (<xref ref-type="bibr" rid="b37">Wang, Truong and
                    Wang, 2003</xref>). It has both red and white varieties. White yam
                    (<italic>Dioscorea rotundata</italic>) is widely cultivated in Africa as an
                edible tuber with economic importance (<xref ref-type="bibr" rid="b26">Omonigho and
                    Ikenebomeh, 2000</xref>). Bitter yam (<italic>Dioscorea dumetorum</italic>)
                belongs to <italic>Dioscoreacae</italic> family. It is rich in phyto-nutrients such
                as proteins (<xref ref-type="bibr" rid="b19">Medoua et al., 2005</xref>); still, it
                remains one of the underutilized tropical tubers in the world (<xref ref-type="bibr"
                    rid="b27">Owuamanam et al., 2013</xref>).</p>
            <p>The present study focuses on the modification of four different starches using
                acetylation and phthalation processes, and also the determination of the functional
                properties of both native and the modified starches.</p>
            <sec>
                <title>Scientific hypothesis</title>
                <p>This research evaluated the significance of chemical modifications of native
                    starches and the subsequent effects by comparing the characterizations and
                    properties with their modified derivatives.</p>
            </sec>
        </sec>
        <sec sec-type="materials|methods">
            <title>MATERIAL AND METHODOLOGY</title>
            <sec>
                <title>Materials</title>
                <p>Cocoyam, white yam, and bitter yam (Figure <xref ref-type="fig" rid="F1"
                    >1</xref>) were bought from a local market in Ado-Ekiti, Ekiti State, Nigeria.
                    All the reagents used were of analytical grade.</p>
                <fig id="F1" position="float">
                    <label>Figure 1</label>
                    <caption>
                        <p>Pictorial representations of cocoyam (A), white yam (B) and bitter yam
                            (C).</p>
                    </caption>
                    <graphic xlink:href="PSJFS-14-1-682_F1.jpg"/>
                </fig>
                <p>Starch Isolation: The starches were isolated using the wet extraction method as
                    described by (<xref ref-type="bibr" rid="b30">Shujun et al., 2006</xref>). The
                    tubers were thoroughly washed with water, cut into small sizes, and homogenized
                    blended for about five minutes. The produced slurry was transferred into a
                    muslin cloth and released into a bucket with distilled water. The content was
                    continuously squeezed to eject the starch into the bucket of water, the starch
                    was allowed to settle overnight and the supernatant was decanted. The product
                    was rinsed continuously to remove soluble impurities until the supernatant was
                    clear, the final product was spread on a flat substrate and air-dried.</p>
            </sec>
            <sec>
                <title>Preparation of acetylated starches</title>
                <p>The method of (<xref ref-type="bibr" rid="b29">Sathe and Salunkhe, 1981</xref>)
                    was employed in the acetylation process. 100 g of starch was measured and
                    dispersed in 500 mL distilled water, the resulting mixture was magnetically
                    stirred for 20 min. The pH of the obtained slurry was adjusted to 8.0 using 1 M
                    NaOH. 10.2 g of acetic anhydride was added for a period of 1 h, and the reaction
                    was allowed to proceed for 5 min after the addition of acetic anhydride. The pH
                    of the slurry was then adjusted to 4.5 using 0.5 M HCl. The product was
                    filtered, washed several times with distilled water, and air-dried.</p>
            </sec>
            <sec>
                <title>Preparation of Pregelatinized Starch Phthalate</title>
                <p>Pre-gelatinized Starch Phthalate was prepared using the method of (<xref
                        ref-type="bibr" rid="b33">Surini, Ssputri and Anwar, 2014</xref>). Two basic
                    steps were involved: gelatinization and esterification. Gelatinization was
                    carried out by heating starch solution at 70 &#xB0;C, the gel was then
                    oven-dried, ground, and sieved. The esterification reaction was done by reacting
                    10% pregelatinized starch in distilled water with 16.7% solution phthalic
                    anhydride in 96% ethanol. 10 M NaOH was added continuously during the reaction
                    to keep the pH between 8 and 10. Anhydrous sodium sulphate was added to absorb
                    excess moisture. Stirring was carried out at 1000 rpm, the stirring was
                    continued for 30 more minutes and allowed to stay for 24 h. The mixture pH was
                    adjusted to 6.5 &#x2212; 7.0 using HCl solution. 50% Ethanol was added into the
                    neutralized solution to wash the un-reacted phthalate. The final precipitate was
                    dried, ground, and sieved to obtain pre-gelatinized starch phthalate (PCSP)
                    powder.</p>
            </sec>
            <sec>
                <title>Fourier Transform Infrared (FT-IR) Analysis</title>
                <p>The functional groups of native and modified cocoyam, bitter yam, and white yam
                    starches were obtained using Fourier Transform Infra-Red (Shimadzu Model FTIR –
                    8201PC).</p>
            </sec>
            <sec>
                <title>FUNCTIONAL PROPERTIES</title>
                <sec>
                    <title>Water absorption capacity (WAC)</title>
                    <p>Water absorption capacity was carried out using the method described by
                            (<xref ref-type="bibr" rid="b24">Omojola et al., 2010</xref>). One gram
                        of the sample was mixed with 10 mL distilled water for 5 min. The sample was
                        allowed to stay for 30 min, centrifuged at 3000 rpm for 30 min, the volume
                        of the supernatant was measured. Assuming the density of distilled water was
                        1 g.mL<sup>-1</sup>.</p>
                </sec>
                <sec>
                    <title>Swelling power and solubility</title>
                    <p>Swelling power and solubility were determined using the method described by
                            (<xref ref-type="bibr" rid="b6">Awokoya et al., 2011</xref>). One gram
                        of native starch was weighed and transferred into a clean and dried test
                        tube (W1). The native starch was dispersed in distilled water (20 mL). The
                        obtained slurry was heated at 60 &#xBA;C for 30 min in a calibrated water
                        bath. The mixture was centrifuged at 3000 rpm for 20 min, the supernatant
                        was decanted and the swollen granules were weighed (W2). 10 mL of the
                        supernatant was oven-dried at 120 &#xB0;C. The residue obtained on drying
                        the supernatant indicates the quantity of starch solubilized. The swelling
                        and solubility are calculated as follows:</p>
                    <p>
                        <disp-formula id="M1">
                            <mml:math display="block" xmlns:mml="http://www.w3.org/1998/Math/MathML"
                                id="Eq1">
                                <mml:semantics>
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                                    </mml:mtable>
                                </mml:semantics>
                            </mml:math>
                        </disp-formula>
                    </p>
                </sec>
                <sec>
                    <title>Gelatinization temperature (GT)</title>
                    <p>Gelatinization temperature was determined by the method described by (<xref
                            ref-type="bibr" rid="b5">Attama et al., 2003</xref>). About 1 g of
                        starch sample was transferred into a beaker and 10 mL of distilled water was
                        added. The dispersion was heated on a hot plate. The gelatinization
                        temperature was then taken with a thermometer suspended in the slurry.</p>
                </sec>
                <sec>
                    <title>Determination of least gelation concentration</title>
                    <p>The method of (<xref ref-type="bibr" rid="b29">Sathe and Solunkhe,
                            1981</xref>) was used with slight modification. Appropriate sample
                        suspensions of 2, 4, 6, 8, 10, 12, 14, 16 w.v<sup>-1</sup> were prepared in
                        5 mL distilled water. The test tubes containing the suspensions were heated
                        for 1 h in boiling water cooled under running tap water. The least gelation
                        concentration was determined as concentration when the sample from the
                        inverted test tube did not fall down or slip.</p>
                </sec>
                <sec>
                    <title>Determination of bulk density</title>
                    <p>Bulk density was determined using the procedure of (<xref ref-type="bibr"
                            rid="b11">Gbadamosi and Oladeji, 2013</xref>) with slight modification.
                        The sample (10 g) was put into a 100 mL graduated cylinder. The cylinder was
                        tapped forty times and the bulk density was calculated as weight per unit
                        volume (g.mL<sup>-1</sup>)</p>
                    <p>
                        <disp-formula id="M2">
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                                id="Eq2">
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                            </mml:math>
                        </disp-formula>
                    </p>
                </sec>
                <sec>
                    <title>pH Determination</title>
                    <p>The pH was determined using the procedure of (<xref ref-type="bibr" rid="b25"
                            >Omojola et al., 2012</xref>). 20 g of the sample was shaken in 100 mL
                        of distilled water for 5 min and the pH was determined using a pH meter.</p>
                </sec>
                <sec>
                    <title>Amylose content</title>
                    <p>The amylose content of the samples was determined by the colorimetric
                        measurement of the blue amylose-iodine complex (<xref ref-type="bibr"
                            rid="b20">Mir, Srikaeo and Garc&#xED;a, 2013</xref>). In summary, 100 mg
                        of sample was weighed into a 100 mL volumetric flask, mixed with 1 mL
                        ethanol and 9 mL of 2 M NaOH. The samples were diluted and the iodine
                        solution was added. After 10 min incubation at room temperature, the
                        absorbance at 620 nm was analyzed using UVspectrophotometer (Beckman DU640
                        UV/Vis Spectrophotometer) and the amylose content was calculated based on
                        the standard curve. The samples were analyzed in triplicate.</p>
                </sec>
            </sec>
            <sec>
                <title>Statistical analysis</title>
                <p>All the analyses were done in triplicate and the data were statistically
                    subjected to Analysis of Variance (ANOVA) using SPSS (IBM Statistics 21).
                    Results are means of replicates (determined on a dry weight basis) &#xB1;
                    standard deviation, significantly different at
                    <italic>p</italic>&#x003C;0.05.</p>
            </sec>
        </sec>
        <sec sec-type="results|discussion">
            <title>RESULTS AND DISCUSSION</title>
            <p>FTIR spectroscopy was used to verify the changes in the chemical structures of starch
                molecules resulting from acetylation and phthalation. The FTIR spectra of native,
                acetylated and phthalated cocoyam starches are presented in Figure <xref
                    ref-type="fig" rid="F2">2</xref>, Figure <xref ref-type="fig" rid="F3">3</xref>,
                and Figure <xref ref-type="fig" rid="F4">4</xref>. In the spectrum of native starch,
                the peak at 3421.72 cm<sup>-1</sup> and 2929.87 cm<sup>-1</sup> correspond to O-H
                and C-H stretching, while the peaks at 1654.92 cm<sup>-1</sup> and 1458.18
                    cm<sup>-1</sup> correspond to O-H and C-H bending. Acetylated starches show new
                strong absorption bands at 1732.08 cm<sup>-1</sup>; this indicates C=O stretching of
                acetyl group. <xref ref-type="bibr" rid="b18">Mano, Koniarova and Reis (2003)</xref>
                submitted a similar report. Phthalated starch showed new absorption bands at 1849.73
                    cm<sup>-1</sup>, this new absorption indicates that phthalated starches were
                formed during the esterification process.</p>
            <fig id="F2" position="float">
                <label>Figure 2</label>
                <caption>
                    <p>FTIR spectrum of native Cocoyam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F2.jpg"/>
            </fig>
            <fig id="F3" position="float">
                <label>Figure 3</label>
                <caption>
                    <p>FTIR spectrum of acetylated Cocoyam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F3.jpg"/>
            </fig>
            <fig id="F4" position="float">
                <label>Figure 4</label>
                <caption>
                    <p>FTIR spectrum of phthalated Cocoyam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F4.jpg"/>
            </fig>
            <p>The FTIR spectra of native, acetylated and phthalated white yam starches are
                presented in Figure <xref ref-type="fig" rid="F5">5</xref>, Figure <xref
                    ref-type="fig" rid="F6">6</xref>, and Figure <xref ref-type="fig" rid="F7"
                    >7</xref>. For the native starch, the peak at 3423.65 cm<sup>-1</sup> and
                2929.87 cm<sup>-1</sup> correspond to O-H and C-H stretching, while the peaks at
                1653.00 cm<sup>-1</sup> and 1458.18 cm<sup>-1</sup> correspond to O-H and C-H
                bending. Acetylated and the phthalated white yam starch did not show a new
                absorption band.</p>
            <fig id="F5" position="float">
                <label>Figure 5</label>
                <caption>
                    <p>FTIR spectrum of native White yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F5.jpg"/>
            </fig>
            <fig id="F6" position="float">
                <label>Figure 6</label>
                <caption>
                    <p>FTIR spectrum of acetylated White yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F6.jpg"/>
            </fig>
            <fig id="F7" position="float">
                <label>Figure 7</label>
                <caption>
                    <p>FTIR spectrum of phthalated white yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F7.jpg"/>
            </fig>
            <p>The FTIR spectra of native, acetylated and phthalated bitter yam starches are
                presented in Figure <xref ref-type="fig" rid="F8">8</xref>, Figure <xref
                    ref-type="fig" rid="F9">9</xref> and Figure <xref ref-type="fig" rid="F10"
                    >10</xref>. For native starch, the peaks at 3394.72 cm<sup>-1</sup> and 2929.87
                    cm<sup>-1</sup> correspond to O-H and C-H stretching, while the peaks at 1654.92
                – 1637.56 cm<sup>-1</sup> and 1438.18 cm<sup>-1</sup> corresponds to O-H and C-H
                bending. Acetylated starches show new strong absorption bands at 1909.53
                    cm<sup>-1</sup>; this indicates C=O stretching of acetyl group. Phthalated
                starch showed new absorption bands at 1703.14 cm<sup>-1</sup> due to the carbonyl
                group of esters.</p>
            <fig id="F8" position="float">
                <label>Figure 8</label>
                <caption>
                    <p>FTIR of sample native bitter yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F8.jpg"/>
            </fig>
            <fig id="F9" position="float">
                <label>Figure 9</label>
                <caption>
                    <p>FTIR of acetylated bitter yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F9.jpg"/>
            </fig>
            <fig id="F10" position="float">
                <label>Figure 10</label>
                <caption>
                    <p>FTIR of sample phthalated bitter yam starch.</p>
                </caption>
                <graphic xlink:href="PSJFS-14-1-682_F10.jpg"/>
            </fig>
            <p>The results of the functional properties of native and modified starches are
                presented in Table <xref ref-type="table" rid="T1">1</xref>. Native cocoyam starch
                has a water absorption capacity (WAC) of 8.70 &#xB1;0.02 g.g<sup>-1</sup>, the value
                was increased after acetylation (9.37 &#xB1;0.15), and reduced after phthalation
                (6.50 &#xB1;0.30). The WAC values for native white yam and bitter yam starches were
                8.17 &#xB1;0.15 and 8.94 &#xB1;0.05 g.g<sup>-1</sup>, respectively, however, the
                values were increased (8.87 &#xB1;0.15, 8.50 &#xB1;0.01 g.g<sup>-1</sup>) after
                acetylation and decreased (5.33 &#xB1;0.50 and 4.56 &#xB1;0.21 g.g<sup>-1</sup>)
                after phthalation. Acetylated white yam starch showed the highest water absorption
                capacity while the phthalated bitter yam showed the least WAC. Acetylation increased
                the WAC of all the starches compared to their corresponding native starches, whereas
                phthalation decreased the WAC. A similar increase in the WAC upon acetylation was
                obtained in acetylated starches of sweet potato (<xref ref-type="bibr" rid="b17">Lee
                    and Yoo, 2009</xref>) and corn (<xref ref-type="bibr" rid="b8">Diop et al.,
                    2011</xref>). The increase in the WAC in acetylated starches could be associated
                with the introduction of acetyl groups that impeded intermolecular chain
                associations, causing structural disorganization that facilitated water access in
                the amorphous region (<xref ref-type="bibr" rid="b38">Xu, Dzenis and Hanna,
                    2005</xref>).</p>
            <table-wrap id="T1" position="float">
                <label>Table 1</label>
                <caption>
                    <p>Functional properties of native and modified starches.</p>
                </caption>
                <table frame="hsides" rules="none" width="100%">
                    <thead>
                        <tr>
                            <th align="left" valign="top">Sample</th>
                            <th align="left" valign="top">WAC (g.g<sup>-1</sup>)</th>
                            <th align="left" valign="top">OAC (g.g<sup>-1</sup>)</th>
                            <th align="left" valign="top">SWP (g.g<sup>-1</sup>)</th>
                            <th align="left" valign="top">Solubility (g.g<sup>-1</sup>)</th>
                            <th align="left" valign="top">Gelation temp. (&#x00B0;C)</th>
                            <th align="left" valign="top">Amylose content (%)</th>
                            <th align="left" valign="top">pH</th>
                            <th align="left" valign="top">Bulk density (g.mL<sup>-1</sup>)</th>
                            <th align="left" valign="top">Amylopectin %</th>
                        </tr>
                        <tr>
                            <th colspan="10">
                                <hr/>
                            </th>
                        </tr>
                    </thead>
                    <tbody>
                        <tr>
                            <td>
                                <bold>Native cocoyam sample</bold>
                            </td>
                            <td>8.70 &#x00B1;0.22<sup>h</sup></td>
                            <td>2.57 &#x00B1;0.21<sup>c</sup></td>
                            <td>2.84 &#x00B1;0.05<sup>g</sup></td>
                            <td>1.56 &#x00B1;0.06<sup>d</sup></td>
                            <td>85</td>
                            <td>20.90 &#x00B1;0.06<sup>d</sup></td>
                            <td>6.50</td>
                            <td>0.61 &#x00B1;0.08<sup>a</sup></td>
                            <td>79.10 &#x00B1;0.25<sup>b</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetylated yam sample</bold>
                            </td>
                            <td>9.37 &#x00B1;0.15<sup>k</sup></td>
                            <td>3.33 &#x00B1;0.42<sup>f</sup></td>
                            <td>4.39 &#x00B1;0.20<sup>k</sup></td>
                            <td>2.25 &#x00B1;0.25<sup>g</sup></td>
                            <td>78</td>
                            <td>18.73 &#x00B1;0.64<sup>b</sup></td>
                            <td>3.91</td>
                            <td>0.45 &#x00B1;0.05<sup>e</sup></td>
                            <td>81.27 &#x00B1;0.24<sup>d</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalated cocoyam sample</bold>
                            </td>
                            <td>6.50 &#x00B1;0.30<sup>c</sup></td>
                            <td>1.63 &#x00B1;0.25<sup>a</sup></td>
                            <td>1.84 &#x00B1;0.05<sup>c</sup></td>
                            <td>0.54 &#x00B1;0.04<sup>a</sup></td>
                            <td>80</td>
                            <td>30.31 &#x00B1;0.17<sup>k</sup></td>
                            <td>5.72</td>
                            <td>0.32 &#x00B1;0.06<sup>d</sup></td>
                            <td>69.69 &#x00B1;0.05<sup>e</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Native white yam</bold>
                            </td>
                            <td>8.17 &#x00B1;0.15<sup>e</sup></td>
                            <td>3.47 &#x00B1;0.06<sup>h</sup></td>
                            <td>2.15 &#x00B1;0.05<sup>d</sup></td>
                            <td>2.58 &#x00B1;0.06<sup>h</sup></td>
                            <td>82</td>
                            <td>21.53 &#x00B1;0.30<sup>e</sup></td>
                            <td>6.20</td>
                            <td>0.65 &#x00B1;0.22<sup>h</sup></td>
                            <td>78.47 &#x00B1;0.12<sup>c</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetlated white yam </bold>
                            </td>
                            <td>8.87 &#x00B1;0.15<sup>b</sup></td>
                            <td>4.53 &#x00B1;0.06<sup>l</sup></td>
                            <td>3.87 &#x00B1;0.08<sup>j</sup></td>
                            <td>3.00 &#x00B1;0.08<sup>i</sup></td>
                            <td>78</td>
                            <td>18.63 &#x00B1;0.17<sup>b</sup></td>
                            <td>4.52</td>
                            <td>0.69 &#x00B1;0.03<sup>i</sup></td>
                            <td>81.37 &#x00B1;0.21<sup>f</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalaled white yam </bold>
                            </td>
                            <td>5.33 &#x00B1;0.50<sup>a</sup></td>
                            <td>3.37 &#x00B1;0.21<sup>g</sup></td>
                            <td>1.64 &#x00B1;0.04<sup>b</sup></td>
                            <td>1.50 &#x00B1;0.16<sup>c</sup></td>
                            <td>80</td>
                            <td>28.67 &#x00B1;0.38<sup>j</sup></td>
                            <td>5.67</td>
                            <td>0.53 &#x00B1;0.08<sup>f</sup></td>
                            <td>71.33 &#x00B1;0.32<sup>g</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Native bitter yam</bold>
                            </td>
                            <td>8.94 &#x00B1;0.05<sup>j</sup></td>
                            <td>3.62 &#x00B1;0.20<sup>i</sup></td>
                            <td>3.70 &#x00B1;0.25<sup>i</sup></td>
                            <td>2.18 &#x00B1;1.26<sup>f</sup></td>
                            <td>82</td>
                            <td>22.73 &#x00B1;0.31<sup>f</sup></td>
                            <td>6.75</td>
                            <td>0.51 &#x00B1;0.04<sup>c</sup></td>
                            <td>77.27 &#x00B1;0.51<sup>b</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetylated bitter yam</bold>
                            </td>
                            <td>8.50 &#x00B1;0.27<sup>g</sup></td>
                            <td>4.03 &#x00B1;0.06<sup>k</sup></td>
                            <td>4.63 &#x00B1;0.15<sup>l</sup></td>
                            <td>3.24 &#x00B1;0.17j</td>
                            <td>74</td>
                            <td>21.37 &#x00B1;0.15<sup>g</sup></td>
                            <td>4.61</td>
                            <td>0.43 &#x00B1;0.03<sup>b</sup></td>
                            <td>78.63 &#x00B1;0.22<sup>d</sup></td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalated bitter yam</bold>
                            </td>
                            <td>7.56 &#x00B1;0.21<sup>d</sup></td>
                            <td>2.23 &#x00B1;0.15<sup>b</sup></td>
                            <td>2.61 &#x00B1;0.15<sup>e</sup></td>
                            <td>1.56 &#x00B1;1.24<sup>d</sup></td>
                            <td>80</td>
                            <td>27.53 &#x00B1;0.38<sup>i</sup></td>
                            <td>5.22</td>
                            <td>0.34 &#x00B1;0.07<sup>k</sup></td>
                            <td>72.47 &#x00B1;0.05<sup>h</sup></td>
                        </tr>
                    </tbody>
                </table>
                <table-wrap-foot>
                    <fn id="T1FN1">
                        <p>Note: Values are means of three replicates (determined on dry weight
                            basis) &#x00B1; standard deviation, significantly different at
                                <italic>p</italic> &#x003C;0.05. WAC &#x2013; water absorption
                            capacity; OAC &#x2013; oil absorption capacity; SWP &#x2013; swelling
                            power.</p>
                    </fn>
                </table-wrap-foot>
            </table-wrap>
            <p>A decrease in WAC in phthalated starches could be that phthalation reinforces the
                structure of starch granules and limit water absorption which restricts the mobility
                of starch chain in the amorphous region (<xref ref-type="bibr" rid="b12">Gunaratne
                    and Corke, 2007</xref>). An increase in water absorption capacity of acetylated
                starches gave it the advantage of being used as a thickener in liquid and
                semi-liquids foods, it could be used in the development of confectionery products
                such as hard candies, the acetylated starches could also be used to produce
                absorbent materials such as disposable diapers and female napkins. The decreased
                water absorption capacity of phthalated starches suggests that they could be used in
                biodegradable films because of their reduction in hydrophilic property.</p>
            <p>In the case of oil absorption capacity (OAC), Native cocoyam starch has an OAC of
                2.57 &#xB1;0.21 which increased after acetylation (3.33 &#xB1;0.42 g.g-<sup>1</sup>)
                and reduced after phthalation 1.63 &#xB1;0.25 g.g<sup>-1</sup>. The OAC of the
                native white yam and bitter yam were 3.47 &#xB1;0.06 and 3.62 &#xB1;0.20
                    g.g<sup>-1</sup>, respectively. However, the OAC values increased after
                acetylation and decreased after phthalation. Acetylated white yam starch showed the
                highest oil absorption capacity and phthalated cocoyam showed the least OAC.
                Acetylation increased the OAC of all the starches compared to their corresponding
                native starches, whereas phthalation decreased the OAC. This result suggested that
                acetylation enhanced the hydrophobic tendencies of the starches. A similar result
                was reported by <xref ref-type="bibr" rid="b36">Uzomah and Ibe, (2011)</xref>. WHO
                indicated that Acetylated starches had the strongest affinity for oil absorption.
                The obtained results showed that acetylation could be used to improve the oil
                absorption capacity of native starches.</p>
            <p>Swelling power and solubility centre on the interaction between starch chains within
                the amorphous and crystalline regions, and the results are presented in Table <xref
                    ref-type="table" rid="T1">1</xref>. The swelling power of the native cocoyam,
                white yam, and native bitter yam starches increased after acetylation and decreased
                after phthalation. Acetylated bitter yam showed the highest swelling power while
                (4.63 &#xB1;0.15 g.g<sup>-1</sup>) while phthalated white yam starch (1.64
                &#xB1;0.04 g.g<sup>-1</sup>) has the least swelling property. Increase observed in
                the swelling power of acetylated starches may be due to the weakening and disrupting
                of intra- and inter molecular hydrogen bonds in the starch chains, which may
                increase the accessibility of the starch granules to water. (<xref ref-type="bibr"
                    rid="b17">Lee and Yoo, 2009;</xref>
                <xref ref-type="bibr" rid="b23">Olu-Owolabi et al., 2014</xref>). Similar reports on
                swelling power after modifications have been documented (<xref ref-type="bibr"
                    rid="b22">Olayinka, Adebowale and Olu-Owolabi, 2013</xref>). The reduction in
                swelling power after phthalation could be linked to the possible structural
                disintegration within the starch matrix as a result of the modification. <xref
                    ref-type="bibr" rid="b14">Lawal (2004);</xref>
                <xref ref-type="bibr" rid="b2">Adebowale and Lawal (2003)</xref> reported that the
                lower swelling power of phthalated starches denotes the stability of starch granule.
                Starch swelling power is very important in the formulation of tablets and capsules,
                it is conceived that disintegrant works through swelling action (<xref
                    ref-type="bibr" rid="b1">Adebayo and Itiola, 1998</xref>). Consequently, starch
                with high swelling power is expected to release active pharmaceutical ingredients at
                a faster rate. Also, high swelling power leads to high digestibility which suggests
                improved dietary attributes (<xref ref-type="bibr" rid="b21">Nuwamanya et al.,
                    2010</xref>). The reduction in the swelling power of phthalated starches is an
                important property for their applications in biodegradable films.</p>
            <p>Table <xref ref-type="table" rid="T1">1</xref> shows the water solubility of native
                and modified starches. Native cocoyam starch has a solubility of 1.56 &#xB1;0.06
                    g.g<sup>-1</sup> which then increased after acetylation to 2.25 &#xB1;0.25
                    g.g<sup>-1</sup>, and reduced after phthalation to 0.54 &#xB1;0.04
                    g.g<sup>-1</sup>. The water solubility values for native white yam and bitter
                yam starches were 2.58 &#xB1;00.06 and 2.18 &#xB1;1.26, respectively. There was an
                increase in the values after acetylation, a reduction in value was however observed
                after phthalation. The increase in water solubility of acetylated form could be due
                to the structural rearrangement which weakens the granules and improves amylose
                leaching (<xref ref-type="bibr" rid="b14">Lawal, 2004</xref>). Similar reports on
                water solubility on African yam bean and corn were submitted by (<xref
                    ref-type="bibr" rid="b4">Akintayo and Akintayo, 2009</xref>) and (<xref
                    ref-type="bibr" rid="b7">Ayucitra, 2007</xref>) starches. A decrease in water
                solubility after modification of Acha starch has been reported by <xref
                    ref-type="bibr" rid="b23">Olu-Owolabi et al. (2014)</xref>.</p>
            <p>The gelatinization temperatures of the native, acetylated and phthalated starches,
                are presented in Table <xref ref-type="table" rid="T2">2</xref>. Acetylated and
                phthalated starches (cocoyam, whiteyam, and bitter yam) have lower gelatinization
                temperature compared to their corresponding native starches. These observations are
                in agreement with previous studies (<xref ref-type="bibr" rid="b15">Lawal,
                    2011;</xref>
                <xref ref-type="bibr" rid="b16">Lee and Yoo, 2011</xref>). A decrease in
                gelatinization temperatures could be traced to the phthalation and acetylation
                processes in the starch polymer backbone, which permits improved flexibility (<xref
                    ref-type="bibr" rid="b32">Singh, Chawla and Singh, 2004</xref>). A decrease in
                gelatinization temperature is useful as a thickening agent in various industries,
                whereby the starch will form a gel at a lower temperature. Hoewever, thermal
                treatment reduced antinutritional agents (<xref ref-type="bibr" rid="b13"
                    >Laukov&#xE1; et al., 2020</xref>).</p>
            <table-wrap id="T2" position="float">
                <label>Table 2</label>
                <caption>
                    <p>Least gelation concentration of native and modified starches.</p>
                </caption>
                <table frame="hsides" rules="none" width="100%">
                    <thead>
                        <tr>
                            <th align="left">Sample</th>
                            <th align="left">2%</th>
                            <th align="left">4%</th>
                            <th align="left">6%</th>
                            <th align="left">8%</th>
                            <th align="left">10%</th>
                            <th align="left">12%</th>
                            <th align="left">14%</th>
                            <th align="left">16%</th>
                        </tr>
                        <tr>
                            <th colspan="9">
                                <hr/>
                            </th>
                        </tr>
                    </thead>
                    <tbody>
                        <tr>
                            <td>
                                <bold>Native cocoyam sample</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetylated yam sample</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalated cocoyam sample</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Native white yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetlated white yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalaled white yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Native bitter yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Acetylated bitter yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                        <tr>
                            <td>
                                <bold>Phthalated bitter yam</bold>
                            </td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>-Viscous</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                            <td>+ Gel</td>
                        </tr>
                    </tbody>
                </table>
                <table-wrap-foot>
                    <fn id="T2FN1">
                        <p>Note: Determination were carried out in triplicates. (-) No gelation and
                            (+) gelation.</p>
                    </fn>
                </table-wrap-foot>
            </table-wrap>
            <p>The pH values for acetylated and phthalated starches were found to be slightly lower
                than their corresponding native starches, but still fall within the pH range of 3
                &#x2212; 9 obtained for most starches used in pharmaceutical, domestic, and food
                industries. The reduction in pH of native starches after acetylation and phthalation
                can be attributed to the modification processes thereby increasing the acidity of
                starch molecules. The amylose content of native cocoyam starch (20.90% &#xB1;0.06)
                was reduced (18.73% &#xB1;0.64) after acetylation, and increased after phthalation
                (30.31% &#xB1;0.17), amylose content of the native white yam(21.53% &#xB1;0.30) and
                bitter yam (22.73% &#xB1;0.31) decreased (18.63% &#xB1;0.17; 31.37% &#xB1;0.15)
                after acetylation, and increased (28.67% &#xB1;0.38; 27.53% &#xB1;0.38) after
                phthalation. Phthalated cocoyam starch showed the highest amylose content while
                acetylated white yam starch showed the least amylose content. The decrease in
                amylose content of acetylated starch was in agreement with the report of <xref
                    ref-type="bibr" rid="b14">Lawal (2004)</xref>, on the reduction of amylose
                content of new cocoyam starch after acetylation. <xref ref-type="bibr" rid="b28"
                    >Reddy, Haripriya and Suriya (2014)</xref> also submitted a similar report on
                acetylated banana starch. Increased amylose contents of phthalated starches were in
                consonance with the report submitted by <xref ref-type="bibr" rid="b32">Singh,
                    Chawla and Singh (2004)</xref> on modified potato and corn starches. Amylose
                content undergoes changes upon modification, also, structural differences between
                amylose and amylopectin can be considered as one of the most important factors of
                starch properties. Low amylose level makes starch a good source of food for diabetic
                and other health conscious beings (<xref ref-type="bibr" rid="b3">Agbo and Odo,
                    2010</xref>). However, high amylose content often leads to retrogradation.</p>
            <p>Table <xref ref-type="table" rid="T1">1</xref> shows the bulk density of native and
                modified starches. Native cocoyam starch has a bulk density of 0.61 &#xB1;0.08
                    g.g<sup>-1</sup>, which decreased after both acetylation and phthalation to 0.45
                &#xB1;0.05 and 0.32 &#xB1;0.06 g.g<sup>-1</sup>. The bulk density values of the
                native white yam and bitter yam starches (0.65 &#xB1;0.22 and 0.51 &#xB1;0.04
                    g.g<sup>-1</sup>) decreased after both acetylation (3.00 &#xB1;0.08 and 3.24
                &#xB1; 0.17 g.g<sup>-1</sup>,) and phthalation (1.50 &#xB1;0.16 and 1.56 &#xB1;1.24
                    g.g<sup>-1</sup>). Native white yam starch has the highest bulk density of 0.65
                &#xB1;0.22 g.g<sup>-1</sup>, while phthalated cocoyam starch (0.32 &#xB1;0.06) has
                the least bulk density. Acetylation and phthalation reduced the bulk density of the
                starches. The higher bulk density of a material, the more the quantity which can be
                packaged in a confined space (<xref ref-type="bibr" rid="b10">Fagbemi, 1999</xref>).
                Materials with high bulk density are regarded as heavy.</p>
            <p>The results of the least gelation of native and modified starches are presented in
                Table <xref ref-type="table" rid="T2">2</xref>. The lowest gelation concentration
                for native cocoyam, white yam, and bitter yam starches was 6%. However, none of the
                starches showed positive results at the concentrations of 2 and 4%. At 8%
                concentration, all the native and modified starches formed a gel, all other higher
                concentrations showed positive results. It was observed that an increase in
                concentration leads to gel formation. A similar increase in the least gelation
                concentration upon acetylation was obtained in acetylated starches of African
                yambean starch (<xref ref-type="bibr" rid="b4">Akintayo and Akintayo, 2009</xref>)
                and sweet potato starch (<xref ref-type="bibr" rid="b8">Diop et al., 2011</xref>).
                Thus, the results suggested that the native starches are better gelating food
                additives than acetylated and phthalated starches.</p>
        </sec>
        <sec sec-type="conclusion">
            <title>CONCLUSION</title>
            <p>It can be concluded that phthalation of native starches reduced water absorption
                capacity, swelling capacity, solubility, oil absorption capacity, swelling power,
                amylose content of the starches which are better properties of biodegradable
                polymers while acetylation increased water absorption capacity, oil absorption
                capacity, swelling power and solubility of the starches which make the starches to
                be useful in confectioneries. This study, apart from establishing the
                characterization differences between native and modified starches has also provided
                information that the modified starches have more and improved applications in food
                industries.</p>
        </sec>
    </body>
    <back>
        <ack>
            <title>Acknowledgments:</title>
            <p>The authors hereby acknowledge the founding father and the President of Afe-Babalola
                University, Aare-Afe Babalola for the timely encouragement that facilitated this
                manuscript.</p>
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