Name: synthesis of plant phenol-derived polymeric dyes for direct or mordant-based hair dyeing
Uploaded: 2016-12-01T12:00:00
Description: Watch this Scientific Journal Video about Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing at JoVE.com

This work was supported by the New Professor Research Foundation Program, funded by Gyeongsang National University (Grant Number 2015-04-020).

1. Preparation of Plant Phenol-derived Polymeric Dyes
<ol>
	<li>Dissolve catechol (0.1 g) and (+)-catechin hydrate (0.1 g) in 32 ml of 100 mM sodium acetate buffer (pH 5.0) and 8 ml of absolute ethanol.</li>
	<li>Add 10 mg of T. versicolor laccase to the catechol- and catechin-containing buffer. Mix vigorously and pour the solution into a square Petri dish. Incubate the dish at room temperature in a shaking incubator (25 rpm) for 24 hr. Dramatic color change of the solution from transparent to dark black can b...

<ol>
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Interestingly, our method reduced the time it took to dye keratin hair with oxidant-induced polymerizations of natural phenolics. It also induced diverse colors in the hair through simple manipulations of the polymeric dyes, such as changing the pH and applying mordant.
In situ incubation of keratin hair with laccase-catalyzed oxidation of plant phenols requires overly long incubation times to attain effective dyeing7. Such slow dyeing kinetics may be due to the poor bindin...

Laccases are oxidases that are active towards phenolic and polyphenolic compounds. They have been identified in various living organisms, including plants, fungi, insects, and bacteria. Their enzymatic actions contribute to several morphogenetic phenomena1. The enzymes catalyze single-electron oxidation of the substrates, resulting in the formation of radicals that are further coupled to small organics and to solid surfaces. Such coupling processes lead to syntheses of oligomers and polymers and to surface functionalizations2, 3. When laccase substrates are from natural sources, such as plant phenolics, the enzymatic reactions are of great interest with respect to green chemistry. Here, both reactants and catalysts are from natural sources. In addition, the resulting products are similar to the natural products, since the overall reactions mimic the in vivo syntheses of natural phenolic polymers-including plant lignin, poly(flavonoid), and humus-wherein small plant phenolic compounds are highly cross-linked by oxidase-induced radical coupling4.
Products derived from laccase-catalyzed coupling reactions of plant-derived phenols can be used to dye gray hair through in situ incubation and can be developed as alternatives to commercially available dyes1. Such alternatives are important, since commercial hair-dyeing agents are based on p-phenylenediamine (PPD), PPD-related diamine compounds, and hydrogen peroxide, which have been shown to be toxic, carcinogenic, and allergenic to humans5, 6. In the laccase-catalyzed coupling reactions, the laccases and plant phenols functionally replace hydrogen peroxide and p-phenylenediamine, respectively7. However, the dyeing speed of the laccase-based systems is much slower than that of the commercial one. In general, the PPD-based dyeing agents require less than one hour to achieve effective color change in keratin hair, while the laccase-based reactions require an overnight incubation7. The slow dyeing kinetics could be explained by two possible phenomena. First, the use of a low-pH buffer (e.g., pH 5) to maximize laccase activity has been observed to decrease the degree of swelling in the keratin matrices, thus inhibiting deep penetration of dyes into the matrices. Indeed, agents allowing the dyeing reactions to proceed in high-pH conditions have been shown to be integral to commercial hair-dyeing products8. Second, the number of possible chromophore molecules exhibiting strong adsorption to keratinous surfaces during the polymerization reaction has been shown to be proportional to the incubation time (i.e., the extent of polymerization). For example, the transformation of dopamine to polydopamine was shown to induce a strong adhesion to many surfaces that was concomitant with the formation of a black color9.
In the current work, pre-synthesized polymeric products obtained from T. versicolor laccase-catalyzed oxidation of catechin and catechol were used to treat keratin hair for dyeing. We hypothesized that the adsorption ability of the polymers would be much stronger than that of the monomeric plant phenols and that they would initially form low-molecular-weight oligomers. Results demonstrated that, when using the pre-synthesized polymers, the enzymatic oxidation power was no longer necessary. This indicates that the pH can be controlled and that metal ions can be used in hair-dyeing treatments, regardless of enzyme activity. This protocol provides a simple and fast method to dye keratin hair in various shades of color while using eco-friendly and renewable plant-derived phenolics (Figure 1).

<table border="0" cellpadding="0" cellspacing="0" width="802">
	<tbody>
		<tr height="32">
			<td height="32" style="height:32px;width:208px;">Sodium dodecyl Sulfate</td>
			<td style="width:205px;">Promega</td>
			<td style="width:208px;">H5114</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">Laccase from Trametes versicolor</td>
			<td style="width:205px;">Sigma</td>
			<td style="width:208px;">38429-1G</td>
			<td style="width:181px;">Enzyme activity is denoted as 0.53 U/mg</td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">(+)-catechin hydrate</td>
			<td style="width:205px;">Sigma</td>
			<td style="width:208px;">C1251-5G</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">1,2-dihydroxybenzene (catechol)</td>
			<td style="width:205px;">Sigma</td>
			<td style="width:208px;">135011-5G</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">Ammonia water&#160;</td>
			<td style="width:205px;">Duksan</td>
			<td style="width:208px;">701</td>
			<td style="width:181px;">Ammonia contents is denoted as 25 ~ 30%</td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">Acetic acid, glacial</td>
			<td style="width:205px;">Duksan</td>
			<td style="width:208px;">448</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="28">
			<td height="28" style="height:28px;width:208px;">Iron (II) sulfate heptahydrate</td>
			<td style="width:205px;">JUNSEI</td>
			<td style="width:208px;">83380-1250</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:208px;">Ultracell 5kDa</td>
			<td style="width:205px;">Amicon</td>
			<td style="width:208px;">PLCC06210</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:208px;">Stirred ultrafiltration cells</td>
			<td style="width:205px;">Millipore</td>
			<td style="width:208px;">Model 8200</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:208px;">Human gray hair</td>
			<td style="width:205px;">PheonixKorea</td>
			<td style="width:208px;">Not available</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:208px;">Colorimeter</td>
			<td style="width:205px;">SPEC</td>
			<td style="width:208px;">JCS-10</td>
			<td style="width:181px;"></td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:208px;">Square dish</td>
			<td style="width:205px;">SPL</td>
			<td style="width:208px;">10125</td>
			<td style="width:181px;">125 * 125 * 20 (mm)</td>
		</tr>
	</tbody>
</table>

synthesis of plant phenol-derived polymeric dyes for direct or mordant-based hair dyeing

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been previously demonstrated. However, the dyeing process takes a long time to complete compared to commercial hair-dyeing products. To overcome this bottleneck, pre-synthesized polymeric products of the oxidative reaction of Trametes versicolor laccase on catechin and catechol, either with or without mordant agents (e.g., FeSO4), were here employed to achieve permanent keratin hair dyeing in various colors and shades. The laccase action in acidic sodium acetate buffer led to a deep black coloration after coupling reactions between the plant phenols. The colored dye products were then desalted and concentrated with ultrafiltration. The dyes, with or without mordant agents, caused a significant increase in &#916;E values (i.e., color difference value) in gray human hair within 2.5 hours. In addition, different keratin colors and shades were induced depending upon the mordanting and pH changes. The dyed hair also exhibited a strong resistance to detergent treatments, indicating that our methods can give rise to permanent hair dyeing.&#160;Overall, our work has provided novel insight into developing eco-friendly hair-dyeing methods as alternatives to commercial toxic diamine-based dyes.

First, the dyeing ability of polymeric dyes was compared to that of plant-derived monomers (i.e., catechin and catechol). The polymeric dyes induced a significant change in the color of gray keratin hair (Figure 2A and Figure 3), while the innate gray color of the hair remained very stable with plant monomers (data not shown). The effects of mordanting agents on the dyeing abilities of polymeric products were then evaluated. As s...

Watch this Scientific Journal Video about Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing at JoVE.com

Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing

Here, we present a protocol to use pre-synthesized polymeric products derived from fungal laccase-catalyzed polymerization of plant phenols, either with or without mordant agents (e.g., FeSO4), to induce detergent-resistant keratin hair dyeing within 2.5 hours.

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been ...

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