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MATEC Web of Conferences 156, 01020 (2018) https://doi.org/10.1051/matecconf/201815601020 RSCE 2017

Chemical Modifications for Intensity Variation and Spectrum Extension of Brazilein Extract from Sappanwood (Caesalpinia sappan L.)

Edia Rahayuningsih1,*, Wiratni Budhijanto1, Hana Fitria Prasasti2, and Meyta Tias Wahyuningrum2

1Bioresource Engineering Group, Chemical Engineering Department, Universitas Gadjah Mada, Jl. Grafika 2 Yogyakarta, 2Undergraduate Study Program, Chemical Engineering Department, Universitas Gadjah Mada, Jl. Grafika 2 Yogyakarta, Indonesia

Abstract. Aqueous extract of sappanwood (Caesalpinia sappan L.) was treated using -base and additions in order to expand the intensity and spectra of the colors. The colorant molecule of sappanwood was brazilein, which gained its color characteristics through its double bonds. The results of this study confirmed three basic mechanisms which formed the fundamental for systematic optimization of natural applications. Acid addition induced protonation of the hydroxyl groups in the brazilein structure so that the electrons were distributed in the molecule more evenly. Therefore, the color intensity was reduced. Basic treatment created deprotonation of the hydroxyl groups and hence localized the electron on several spots. This made the color of the extract shifted to deeper tones. The addition of mordant created more significant change in color spectrum through the mechanism of to form coordinated complexes. Transitional from group 1 and 2 did not chelate strongly so that the spectrum shift was not very obvious. However, transitional metals from group 3 had strong chelating character and consequently they could strongly bind the dye molecules to increase its intensity and shift the spectrum towards deeper colors.

1 Introduction odern era with wider uses as food colorant p indicator and dyesensitied solar cell The plant of sappanwood or “kayu secang” in Bahasa ndonesia Caesalpinia sappan L is considered a coon plant in tropical region including ndonesia t is known as edicinal plant with arious enefits The clai of its pharacological effect ranges fro anti inflaatory up to cancer cell inhiitor The heartwood of this sappanwood ig is known as the source of railin ig a and railein ig the (a) (b) Brazilein oidated for of railin which are oth the actie copounds in the wood to hae the pharaceutical Fig. 2. tructure of railin and railein as the actie enefits copounds in sappanwood etract

Brailein color spectra coer the range of yellow red depending upon the p of the solution and the ordanting agents used in the process ordant is the cheicals added in the dyeing process to ind the chroophores into the tetile fiers Besides fiation function ordants which are the of transition etals also play iportant role in changing Fig. 1. haed heartwood of sappanwood the depth of the color and creating various shades of the same origin [5]. According to the classic Reichs-Aussch Brailin is colorless ut railein ears natural für Lieferbedingungen (RAL) system for color color widely used in tetile dyeing practices as water standardization, the possible colors obtainable from solule This natural color had een detected sappanwood extract are presented in Fig. 3. Both the in ancient farics to proe its attractieness as tetile spectrum and the intensity of the colors could be created lthough it has een known and used for such a from the same original extract of sappanwood by long tie its popularity still een increases into the changing pH and addition of of the mordant salts [5], [6].

* Corresponding author: [email protected]

© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0 (http://creativecommons.org/licenses/by/4.0/). MATEC Web of Conferences 156, 01020 (2018) https://doi.org/10.1051/matecconf/201815601020 RSCE 2017

using high speed liuid lender traction was run at its optiu conditions which were preiously otained with auadest as solent using the concentration of solid in the solent of g with the iing speed of rp and inutes of etraction at constant o teperature of The second step was the iproeent of the etract in ter of its color spectru Fig. 3. lassic yste for color standard and intensity y cheical odification using addities Two routes were tested for the cheical odification any studies hae een pulished regarding the which were acidase reaction and cation reaction application of natural dyes for arious uses heical odification using acidase addition ther studies focused on the optiiation of the was conducted to check the color characteristics under etraction procedure such as the rigorous ethods to different p alues or acidic p of citric separate railin and railein till liited acid or oth at concentration was nuers of studies were focused on the color added into of original etract while for asic characteristics of the natural dyes This paper presented a p of sodiu hydroide or calciu hydroide study on the effort to epand the intensity and spectra of solution oth at concentration was added into the sappanwood etract The study aied to define the of original etract ther type of additie tested effect of p and ordant salts in a systeatic way so in this study was cation addition olutions of usetat that the prospectie users could decide which procedures g l and e were used as the proider to follow for their particular purposes of cations fter the process with each ethod the asorance of the odified etract was uantitatiely easured using is spectrophotoeter pectrophotoeter 2 Research methodologies was chosen oer chrooeter ecause it offered wider and ore fleile easureent range coerage of 2.1 Materials spectra The data were recorded as the asorance easured at the optiu waelength for each color The raw aterial of sappanwood Caesalpinia sappan L spectru ie the waelength which gae the iniu was otained fro Beringharo arket ogyakarta in transittance for a particular saple canning of the for of dried thin shaed wood itric acid and optiu waelength was conducted y easuring the acetic acid were used for acid odification while sodiu asorance of each saple at arious waelengths hydroide was chosen for the asic treatent ll cheicals were otained fro erck at technical grades purities of the cheicals were not disturing the accuracy of the color foration ecause the solutions 3 Results and discussions were uite diluted y water or other ariations of spectra four cheicals were also tested ie ucetate 3.1 Acid-base modifications u g e and l which were all analytical grade fro igaldrich 3.1.1 Addition of

2.2 Experimental set up ccording to the lassic yste the color of the original etract was categoried as traffic red Both acid The eperients were carried out in laoratory scale addition ie acetic acid and citric acid shifted the color atch stirred reactor euipped with antle heater and category into dahlia yellow The isual coparison of condenser ig the colors is presented in ig or ore oectie coparison ig presents the asorance data of the original and odified etracts The asorance data in ig reeals that all etracts ehiits the highest asorance at the sae waelength ie n indicated y ertical line on ig This fact translates into ore oectie interpretation than the isual oseration that acid

1. Thermometer 3. Batch reactor 5. Motor 7. Clamp 9. Stirrer addition does not change the spectru of the color 2. Mantle heater 4. Condenser 6. Holder 8. Electrical source although isually the colors look different The change caused y acid addition was actually on the intensity of the colors ig shows that the addition of acids Fig. 4. Experimental set up significantly lowered the color intensity of the original etract The eperients were run in two steps The first step was railein etraction fro the shaed sappanwood which was lended first with the solent

2 MATEC Web of Conferences 156, 01020 (2018) https://doi.org/10.1051/matecconf/201815601020 RSCE 2017

a b c a b c d

Fig. 7. isual coparison of original etract a with Fig. 5. isual coparison of original etract a with the citric acid added etract c and citric acid added etract and acetic acid added etract d of citric acid into of original etracts c

a b c d

Fig. 8. isual coparison of original etract a with acetic acid added etract c and d of acetic acid into of original etracts

3.1.2 Base addition Fig. 6. The change of color intensity by acid addition into original extract of sappanwood based on UV-Vis The addition of ases into the original etract of absorbance data sappanwood gae totally different results fro the acid additions Both ases tested in this eperient ie Both ig and ig show that different acids a dan a shifted the originally traffic red of citric acid and acetic acid did not cause different the original etract into ruy red ig presents a isual spectru or different intensity This confirs that the coparison etween the original etract and the ase change of intensity y acid addition was caused y the added etract which used a as the ase The protons so that different acyl group addition of a led to the sae color change arrangeent of the acids did not atter The effect of howeer it was not suggested as it turned out that proton concentration was then tested y the addition of a solution induced precipitation of the etract different aount of citric acids which gae the The asorance analysis was then only conducted on ariations of color intensity presented in ig for citric a added etract and the result is presented in ig acid addition and ig for acetic acid addition ith the etra protons aailale in the solution fro acid partial dissociation the hydroyl groups of the railein ecae protonated s a result of that the initially localied electrons in the conugated oritals of the doule onds in railein olecule ecae soehow delocalied ence slightly different shade of color

was osered a b light difference in proton concentration was created y the addition of different aount of acid solutions ie and in of Fig. 9. isual coparison of original etract a with original etract ig and ig show that color a added etract intensity was not ery sensitie to proton concentration as the echanis of color changes was only due to electron delocaliation

3 MATEC Web of Conferences 156, 01020 (2018) https://doi.org/10.1051/matecconf/201815601020 RSCE 2017

3.2 Effect of cations from mordant salts our transition etal cationic solutions of ordant salts were tested which were g u e and l s eing displayed in ig the addition of g solution or l solution into the original etract did not change the color spectru as it was still traffic red ther color claret iolet which gae optiu asorance at n of waelength was resulted when u solution was added with dilution ddition of e solution also with dilution gae red lilac color optially asoring light at n of waelength The arious spectra created y cation addition fro the solutions studied in this

research were presented in ig The change of color intensity and color Fig. 10. The new spectra found y the addition of ordant spectru y ase addition into original etract of salts were roader than those otained in acidase sappanwood ased on is asorance data euiliria eplained in the preious section Transitional

etals were known for their aility of chelating ie ig ehiits that the addition of a solution cople foration with organic copounds The d and f induced not only the change of color intensity ut also oritals of the transition etal were only partially filled shifted the waelength which gae the aiu so that it was easy to for onding with any asorance fro n for the original etract into nucleophiles although the onding could e weak or n t eans that the color resulted fro ase strong depending upon the period of the etal t can addition was of uite different spectru fro the e noticed in ig that ost intense colors were original etract uch change could only e caused y caused y e and u cations while l and g the change of the the electron distriution caused y the did not induce such strong colors siilar to the color addition of a which shifted the p into asic with the presence of a descried in the preious enent section These results were in good accordance to the The hydroyl ions fro the ase dissociation created theoretical reasons of the chelating strength of different deprotonation of the hydroyl groups in the railein groups of transitional etals roup cation g olecules onseuently there were spots with high and group cation l did not hae strong tendency to density electrons in soe parts of the olecules This for coplees with the railein so that they failed to ariations in electron localiation created different concentrate the electrons to create deeper colors n the shades of colors urther tests were conducted to other hand group cations e and u were known strengthen this speculation ie the addition of different for their aility to for coordinated coplees with concentrations of a solution ig n ig railein p to olecules of railein could e ond referring to the syste of color standardiation the around one cation and hence it induced ery deep color addition of of a resulted in signal red addition of a solution gae ruy red and of a addition ade pearl ruy red n contrast to the protonation of hydroyl groups in the preious section which did not change the color shade the deprotonation occurred in the railein olecules ore significantly affected the color spectru of the etract a b c d e

Fig. 12. isual coparison of original etract a and with addition of e l c u d and g e

(a) (b) (c) (d)

Fig. 11. isual coparison of original etract a with a added etract c and d of a solution into of original etracts

4 MATEC Web of Conferences 156, 01020 (2018) https://doi.org/10.1051/matecconf/201815601020 RSCE 2017

References iral aput rasad and had sian ac Trop ed 8 – ichhariya uar Tekasakul and B upta enew ustain nergy e 69, – ondo eias e elo ina elo T itorino and arola hys he 117 – anhita antos argas andeias T erreira and B ias ult erit 14 – oi lee hed ausar hed and ohail audi he oc 14 – Fig. 13. The change of color intensity and color asood andhawa Butt and spectru y cation addition into original etract of sghar ood rocess reser 40 – sappanwood ased on is asorance data T ahyuningru Penentuan Kondisi Operasi Optimum Ekstraksi Brazilin dari Kayu 4 Conclusions Secang No Title,” Yogyakarta, rasasti Peningkatan intensitas dan The phenoenological study on the efforts of perluasan spektrum warna dari ekstrak kayu intensifying the color and epanding the spectra of secang (Caesalpinia sappan L) ogyakarta sappanwood etract raised iportant understandings as the following oloons ryhle and S. Snyder, “Org a cid addition changed color intensity ut did not he affect the spectru The intensity ariations ight e doinantly influenced y the proton fro the

dissociated acids which induced protonation of the hydroyl groups in the railein structure The protonation created delocaliation of electrons so that they were not concentrated on the doule onds and hence the colors of the etract turned lighter The alkyl group of the organic acids tested in this study had no influence on oth color intensity and spectru Base addition not only changed the intensity of the color ut also epanded the spectra n this case the hydroyl fro the ase caused deprotonation of the hydroyl groups in the railein structure onseuently the electrons ecae localied around the deprotonated hydroyl groups and induced deeper colors c ifferent cations created different shades of colors The sources of cations were usually ordant salts which were salts fro transitional etal etals fro group and such as g and l ight e useful as ordant to fi the color onto the fier howeer they did not hae the chelating strength to for coplees with the railein They could not concentrate dye olecules to create deeper colors n the other hand etals fro group e and u could for strong coordinated coplees with the railein Therefore e and u were not only functioning as the ordant ut also could create deeper colors as well

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