SPECTROSCOPY AND COMPUTATIONAL

STUDY ON ANTHOCYANIN EXTRACTED FROM

MANGOSTEEN PEEL EXTRACT

AWANGKU AZIZAN BIN AWANGKU IFNI

INDUSTRIAL PHYSICS PROGRAMME

FACULTY SCIENCE AND NATURAL
RESOURCES
UNIVERSITI MALAYSIA SABAH

2023

i
SPECTROSCOPY AND COMPUTATIONAL STUDY ON
ANTHOCYANIN EXTRACTED FROM MANGOSTEEN
PEEL EXTRACT

AWANGKU AZIZAN BIN AWANGKU IFNI

DISSERTATION SUBMITTED IN PARTIAL

FULFILMENT OF THE DEGREE OF SCIENCE
WITH HONOUR

PHYSICS INDUSTRY PROGRAMME

FACULTY SCIENCE AND NATURAL RESOURCES
UNIVERSITI MALAYSIA SABAH

2022

ii
 DECLARATION

I officially state that everything in this thesis, with the exception of completely cited
quotations and summaries, is entirely my own original work.

27th February 2023

Awangku Azizan Bin Awangku Ifni
BS19160571

iii
 CONFIRMATION

NAME : AWANGKU AZIZAN BIN AWANGKU IFNI

MATRIC NUMBER : BS19160571

FYP TITLE : SPECTROSCOPY AND COMPUTATIONAL STUDY ON

ANTHOCYANIN EXTRACTED FROM MANGOSTEEN
PEEL EXTRACT

DEGREE : BACHELOR OF SCIENCE

FIELD OF STUDY : PHYSICS INDUSTRY

VIVA 2 DATE : 27TH FEBRUARY 2023

CERTIFIED BY;

SUPERVISOR Signature

(DR. ALVIE LO SIN VOI)

iv
 ACKNOWLEDGEMENT

First and foremost, I would like to thank my competence supervisor, Dr. Alvie Lo Sin
Voi, for his constant support and dedication throughout the process. I am fully aware
that without his aid, motivation, inspiration, and perceptive opinion, I would not be
able to complete this report writing satisfactorily. His dedication, genuine interest, and
wonderful personality for motivating his students were largely and alone responsible
for my career success. Not to mention his constant feedback in our meetings, rigorous
analysis, scientific counsel, and approach, all of which aided me greatly in finishing
the FYP 1 report writing.

I just want to thank my parents, Mr. Awangku Ifni Bin Awangku Bagong and
Mrs. Aini Binti Lastam,,Mr Awangku Ifni Bin Awangku Bagong and Mrs Aini Binti
Lastam, for all of their spiritual guidance, prayers, and inspiration, as well as their
unending love. I am also extremely grateful for the emotional and financial assistance
that they provided for me.

I also want to express my sincere gratitude to the professors, examiners, and

subject coordinator for giving me the necessary knowledge to finish my FYP 1 report.
Last but not least, I would also like to express my sincere gratitude to all of my helpful
friends, especially Alif Nur Mukhlisin Bin Isagani and Mohd Shafi Saiful Bin Mansor, for
their unending support—direct or indirect—during the drafting of my research paper.

Awangku Azizan Bin Awangku Ifni

22th June 2022

v
 ABSTRACT

The dye-sensitized solar cell (DSSC) is a third generation of solar cell that has been
studied by many researchers in order to improve efficiency, stability, and compatibility
with our environment. One example of progress is the use of a natural product or
organic material to substitute an artificial sensitizer like ruthenium sensitizer, which is
expensive, difficult to produce, and toxic. Due to its essential solution in energy
conversion at the lowest cost, dye sensitised solar cells have become a major study
topic in the last two decades. Aside from that, the dye sensitised solar cell's ease of
fabrication, versatility, and wide availability of materials have made it a potential
technology for future low-cost solar cell improvement. natural products such as
mangosteen is easily obtained as both are mainly grown in Southeast Asia such as
Malaysia and certain tropical areas around the globe. Mangosteen pericarps gave a
promising performance in natural dye research however unable to compete with
artificial due to low anchor groups such as carboxyl and hydroxyl. This paper highlights
and discusses the spectroscopy and computational study of anthocyanin using Fourier
Transform Infrared Spectroscopy (FTIR) and Ultraviolet–Visible Spectroscopy with the
aid of GaussView software that utilizes fundamental laws of quantum mechanics to
predict energies, molecular structures, spectroscopic data.

vi
 ABSTRAK

Sel suria peka pewarna (DSSC) ialah sel solar generasi ketiga yang telah dikaji oleh
ramai penyelidik untuk meningkatkan kecekapan, kestabilan dan keserasian dengan
persekitaran kita. Satu contoh kemajuan ialah penggunaan produk semula jadi atau
bahan organik untuk menggantikan pemeka buatan seperti pemeka ruthenium, yang
mahal, sukar untuk dihasilkan dan toksik. Disebabkan penyelesaian pentingnya dalam
penukaran tenaga pada kos terendah, sel suria pemekaan pewarna telah menjadi
topik kajian utama dalam dua dekad yang lalu. Selain daripada itu, pewarna yang
memudahkan fabrikasi sel suria, serba boleh dan ketersediaan bahan yang luas telah
menjadikannya teknologi yang berpotensi untuk penambahbaikan sel suria kos rendah
pada masa hadapan. produk semulajadi seperti manggis mudah diperoleh kerana
kedua-duanya ditanam terutamanya di Asia Tenggara seperti Malaysia dan kawasan
tropika tertentu di seluruh dunia. Perikarpa manggis memberikan prestasi yang
memberangsangkan dalam penyelidikan pewarna semula jadi namun tidak dapat
bersaing dengan tiruan kerana kumpulan penambat yang rendah seperti karboksil dan
hidroksil. Kertas kerja ini mengetengahkan dan membincangkan spektroskopi dan
kajian pengiraan antosianin menggunakan Spektroskopi inframerah fourier
transformasi (FTIR) dan Spektroskopi ultra lembayung-nampak (UV-Vis) dengan
bantuan perisian GaussView yang menggunakan prinsip asas mekanik kuantum untuk
meramalkan tenaga, struktur molekul, data spektroskopi.

vii
Table of Content
DECLARATION ...................................................................................................................................................iii
CONFIRMATION ...............................................................................................................................................iv
ABSTRACT ...........................................................................................................................................................vi
ABSTRAK ............................................................................................................................................................ vii
LIST OF FIGURES ..............................................................................................................................................x
LIST OF TABLES ................................................................................................................................................ xi
LIST OF ABBREVIATIONS ............................................................................................................................ xii
LIST OF SYMBOLS .......................................................................................................................................... xiii
CHAPTER 1.......................................................................................................................................................... 1
1.1 Background Study ................................................................................................................................ 1
1.2 Problem Statement .............................................................................................................................. 2
1.3 Objectives................................................................................................................................................ 3
1.4 Scope of Study ....................................................................................................................................... 4
CHAPTER 2.......................................................................................................................................................... 5
2.1 DSSC (Dye Sensitize Solar Cell) ...................................................................................................... 5
2.2 Natural Dyes Photosensitizers for DSSC ................................................................................ 6
2.3 Mangosteen Pericarp as Photosensitizers ................................................................................. 16
2.4 Anthocyanin .......................................................................................................................................... 18
2.5 Fourier Transform Infrared Spectroscopy (FTIR) ................................................................... 19
2.6 Ultraviolet–Visible Spectroscopy (UV-Vis) ................................................................................ 20
2.7 Density Functional Theory (DFT) .................................................................................................. 21
CHAPTER 3........................................................................................................................................................ 22
3.0 Introduction ......................................................................................................................................... 22
3.1 Materials ................................................................................................................................................ 22
3.1 Project Flow chart .............................................................................................................................. 23
3.2 Extraction of Mangosteen Peels .................................................................................................... 24
...................................................................................................................................................................... 24
3.4 Fourier Transform Infrared Spectroscopy (FTIR) Analysis ................................................. 25
3.5 Ultraviolet–Visible Spectroscopy (UV-Vis) Analysis .............................................................. 26
3.6 Density Functional Theory (DFT) with GaussView ................................................................. 27
CHAPTER 4........................................................................................................................................................ 28
4.0 Introduction ............................................................................................................................................. 28
4.1 FTIR Spectra of Mangosteen Pericarps with Methanol ........................................................ 28
4.2 UV-Vis Spectra of Mangosteen Pericarps with Methanol ..................................................... 29
4.3 Density Functional Theory (DFT) computation ........................................................................ 30
4.4 Theorical and Experimental Comparison ....................................................................................... 31
CHAPTER 5........................................................................................................................................................ 33
5.1 Conclusion ............................................................................................................................................. 33
5.2 Recommendation ................................................................................................................................ 33

viii
REFERENCES .................................................................................................................................................... 34
APPENDICES .................................................................................................................................................... 44

ix
 LIST OF FIGURES

Figure 2. 1 DSSC's efficiency progress (η) over the previous 5 years using various types of natural
sensitizers (Shalini et al., 2015) ......................................................................................................................... 6
Figure 2. 2 Chemical Arrangement of Rutin (Hug et al, 2014) .................................................................... 17
Figure 2. 3 Structure of three natural anthocyanidins .................................................................................. 18

Figure 3. 1 Project Flow Chart .......................................................................................................................... 23

Figure 3. 2 Extraction of Mangosteen Peels Dye ........................................................................................... 24
Figure 3. 3 Fresh Mangosteen .......................................................................................................................... 27
Figure 3. 4 Dried pericarp ................................................................................................................................ 27
Figure 3. 5 Crushed Mangosteen Peels soaked with Methanol ................................................................... 27
Figure 3. 6 The chemical structure of anthocyanin modelled in GaussView ............................................. 27

Figure 4. 1 The FTIR spectra of the mangosteen peels extracted with methanol ................................... 28
Figure 4. 2 UV-Vis Spectra of Mangosteen Pericarps extract with Methanol............................................. 29
Figure 4. 3 IR Spectrum DFT ............................................................................................................................ 30
Figure 4. 4 UV Spectrum TD DFT .................................................................................................................... 30

Appendix 1. 1 Fresh mangosteens................................................................................................................... 44

Appendix 1. 2 Dried Pericarp ............................................................................................................................ 44
Appendix 1. 4 UV-VIS (Agilent Cary 60) ......................................................................................................... 44
Appendix 1. 5 Computation with GaussView Software ................................................................................. 44
Appendix 1. 3 Mangosteen with Methanol ..................................................................................................... 44

x
 LIST OF TABLES

Table 2. 1 The most typical forms of plant pigments present in the colours of flowers and fruits ......... 7
Table 2. 2 Natural dye photoelectrochemical characteristics (Ludin et al.,2014) ....................................... 9
Table 2. 3 The Photovoltaic Performance of Mangosteen Pericarp Constituents (H.Zhou et al.,2014) 16

Table 4. 1 FTIR Result Comparison ................................................................................................................. 31

xi
 LIST OF ABBREVIATIONS

AZO Aluminium-Doped Zinc Oxide

CDCA Chenodeoxycholic acid

CdTe Cadmium Telluride

CE Counter Electrode

CIGS Copper Indium Gallium Selenide

DFT Density Functional Theory

TD DFT Time Dependent Density Functional Theory

DSSC Dye Sensitized Solar Cell

FF Fill Factor

FTIR Fourier Transform Infra Red

FTO Fluorine Doped Tin Oxide

FYP Final Year Project

HOMO Highest Occupy Molecular Orbital

LUMO Lowest Occupy Molecular Orbital

NIR Near-Infrared

NDSSC Natural Dye Sensitized Solar Cell

PV Photovoltaic

UV-Vis Ultraviolet-Visible

TCO Transparent Conducting Oxide

xii
 LIST OF SYMBOLS

𝐼− Iodide Ion

𝐼 3− Triiodide Ion

𝐽𝑠𝑐 Short Circuit Photocurrent

𝑆 Sensitizer

𝑆∗ Excited Sensitizer

𝑆+ Oxide Sensitizer

𝑆− Reduces Sensitizer

𝑉𝑜𝑐 Open Curicuit Photovoltage

𝑇𝑖𝑂2 Titanium Dioxide

𝑍𝑛𝑂 Zinc Oxide

𝑒− Electron

𝜆𝑚𝑎𝑥 Maximum Wavelength

𝜂 Efficiency

𝑃𝑖𝑛 Incident Light Power Density

xiii
 CHAPTER 1

INTRODUCTION

1.1 Background Study

Solar energy refers to the enormous amount of energy that the sun
constantly emits in the form of heat and radiation. Infinite and cost-free, solar energy
is available at all times (Chu et al., 2011; Choubey et al.,2012). When compared to
other traditional power sources, solar energy has a significant advantage because
sunlight can be directly converted into solar energy using tiny photovoltaic (PV) solar
cells. Additionally, extensive research has been done to comprehend and mimic the
photosynthetic process, which uses sunlight to break down carbon dioxide into
carbohydrates and break down water into its component parts (Kalyanasundaram,
2010). Following extensive research, it was hypothesised in 1912 that fossil fuels may
be replaced with solar electricity produced by the Sun (Ciamician, 1912).

A solar cell is a photovoltaic device that uses the photovoltaic effect to convert
light energy into electricity. The development of the solar cell has occurred over many
generations. The first generation of solar cells are made of silicon that is either
monocrystalline or polycrystalline. The second generation solar cell uses Cadmium
Telluride (CdTe) and Copper Indium Gallium Selenide (CIGS). The third generation of
solar cell research includes organic solar cells, perovskite solar cells, and dye-
sensitized solar cells (DSSC) (Kibria et al., 2014).

A dye-sensitized solar cell (DSSC) is a solar cell that absorbs light using a dye
or sensitizer to replicate the photosynthesis process in plants. Researchers are
increasingly interested in DSSC that uses natural dye since it has minimal fabrication
and manufacturing costs and is also environmentally benign. Natural dyes can be
obtained by extractions from fruits, plants, flowers, leaves, and vegetables.

1
1.2 Problem Statement

Due to their efficiency and low material costs, dye sensitised solar cells are
an appealing replacement for current technologies in "low-density" applications like
rooftop solar collectors. However, the technology still needs to advance significantly
before it can be used on a wide scale. These new generation solar cells might be
suitable for large-scale applications with even a minor increase in conversion efficiency
because the cost of adding more DSSCs would be justified by the cell's efficiency.
Natural products such as mangosteen peels can be the best candidate for DSSC
however the study anthocyanin compounds in mangosteen extract for the purpose of
fabricating this DSSC are not so detailed. In addition, anthocyanin compounds or
molecules contribute to DSSC efficiency is also not explained. Realizing the
advantages of mangosteen which is easy to find and has a high potential to become
a deep sensitizer NDSSC, therefore this study will focus on anthocyanin compounds
that possibly present in mangosteen peels extract. The presence of anthocyanin in
the mangosteen peel extract will be identified by using FT-IR and UV-Vis
spectroscopy. In addition, computing using DFT will be done to identify the types of
anthocyanin mangosteen peel extract by comparison of spectroscopic properties. The
method of study using spectroscopy and computational provide a better
understanding of anthocyanin compounds present in mangosteen peels extract and
the importance of further studies on DSSCs.

2
1.3 Objectives

The major goal of this research is to study the anthocyanin compound in

extracted mangosteen mixture using spectroscopy and computational aid of
GaussView software.

The following sub-objectives of the research are necessary to accomplish the

main goal:

a) To identify anthocyanin compound in the mangosteen peel extract.

b) To compare the IR and UV-Vis spectrum obtained from spectroscopy with

the IR and UV-Vis spectrum calculated from computational.

3
1.4 Scope of Study

The scope of study includes the use of research material from previous
researchers on DSSCs, N-DSSCs, anthocyanins and mangosteen as a natural dye for
DSSC. This study also utilizes methods and scientific techniques such as the use of
FT-IR spectroscopy, UV-VIS spectroscopy and computational study utilizing the
GaussView 5.0.8 and GaussSum 2.2.4 software. In addition, the selection of
mangosteen as a natural dye in this study is because relatively its high efficiency
compared to other natural dyes. Furthermore, Due to the richness of natural resources
of plants, leaves, and others in Malaysia because of its tropical weather and rainforest,
the mangosteen peel is ideal because of its complex chemical structure, xanthone of
hydroxyl, which allows for covalent interaction between titanium dioxide (TiO2) and
mangosteen peels.

4
 CHAPTER 2

LITERATURE REVIEW

2.1 DSSC (Dye Sensitize Solar Cell)

Photovoltaic (PV) device generate energy by separating charges at the

interface of two materials with varying conductivities. In the semiconductor industry,
the devices are typically a solid silicon-made devices. The third generation of solar
cells based on nanocrystalline and conducting polymer films then challenges the
inorganic traditional photovoltaic device by replacing the system with gel, liquid,
electrolyte, liquid, in the solar cell, which has a lower fabrication cost. The dye
sensitised solar cells are basically utilized the principle of photoelectrochemical cell,
with light absorbing photosensitizer and a wide band gap semiconductor with
nanocrystalline structure. Durning day time, the device possesses a 12% power
conversion efficiency and an outstanding stability (Grätzel et al., 1991).

Organic PV devices and dye-sensitized solar cells are just two examples of PV
devices. Organic materials containing donating and accepting electrons are used to
construct a junction(opposite) in a common type of PV device that makes the excited
electrons separated into two carriers. After the electrode receives the carriers, which
generates the exciton, using the organic with the same properties. The light gathering
and carrier conveying properties of this photovoltaic device are tough to realise. As a
result, dye sensitised solar cells (DSSC) creating charge at the dye and transferring it
to the electrolyte, the two specifications can be separated. Modifying the chemical
arrangement of the dye, as well as adjusting semiconductor and the properties of the
electrolytes, can be utilized to increase the attributes of the spectrum. (Nazeeruddin
et al., 2011).

5
2.2 Natural Dyes Photosensitizers for DSSC

Figure 2. 1 DSSC's efficiency progress (η) over the previous 5 years using
various types of natural sensitizers (Shalini et al., 2015)

Due to their low cost of production, ease of extraction, and environmental

friendliness, organic dye has been widely utilized in DSSCs (Dai et al., 2002). Punica
granatum peel had the highest efficiency in 2012, at 1.86 %, according to Figure 2.4
(Hernández-Martnez., 2012). Natural dyes can be easily obtained and used in dye
sensitized solar cells. They can be found in a variety of colours and contain a variety
of pigments in fruits, flowers, leaves, and microorganisms (Ho Chang & Lo, 2010).
Natural dyes are perfect for use as sensitizers in dye sensitized solar cells because
they have a high absorption coefficient (Luo et al., 2009).

- 1.7 % red turnip (Calogero et al.,2010)

- 1.5 % pomegranate juice (Bazargan et al, 2009)
- 1.5 % rhus fruit (Al-Bat'hi et al,2013)
- 1.49 % rhoeo spathacea (Lai, W. H et al.,2008)
- 1.3 % shiso leaf (Kumara et al., 2006)
- 1.1 7% fructus lycii (Zhou, H et al.,2011)
- 0.8 % chlorophyll a derivative (Wang, X. F. et al, 2005)
- 0.73 % shahtoot fruit (Mozaffari, S. A et al.,2016)
- 0.7 % rosella flower (Wongcharee, K. et al,2007)

6
Plant pigments have an electrical structure that interacts with sunlight, changing the
wavelengths that are transmitted or reflected by plant tissue. Plant pigmentation
results from this process, and each pigment is characterised by the wavelength of
maximum absorbance (𝜆𝑚𝑎𝑥 ) and the colour observed by humans (Obón & Rivera,
2006). When compared to synthetic new organic dyes, pigments for natural colours
are relatively easy to extract from natural materials. Chlorophyll, carotenoid, flavonoid,
and anthocyanin are the different types of plant pigments (Shalini et al., 2015). The
most common types of pigments found in flower and fruit colours in plants are listed
in Table 2.2 below.

Table 2. 1 The most typical forms of plant pigments present in the colours
of flowers and fruits (Obón & Rivera, 2006).
Colour Type of Group of Examples
Pigment Pigment
Black Delphinidin Caratenoid and Viola
colour Flavonoid Mix (pansy) and few flowers that are
black
Cream Flavonols or Flavonoid Most cream flowers
colour flavonones
Green Cholorophyll All flowers and fruit that are green
colour Delphinidin Flavonoid most flowers and fruit that are
blue
Cyanidin Flavonoid Ipomoea
(morning glory) flowers
Orange Carotenoid marigold
colour Pelargonidin Flavonoid Pelargoniumflowers
alone
Aurone and Flavonoid snapdragon flowers
Anthocyanin
mix
Chalcone Flavonoid Dianthus(carnation) flowers
and
anthocyanin
mix
Betacyanin Betalain Portulaca
(purslane) flowers

7
Colour Type of Group of Examples
Pigment Pigment
Pink Carotenoid tomato
to red fruit
colour Pelargonidin Flavonoid apple
/cyanidin
Caretonoid Caratenoid Tulipa flowers
and and
Anthocyanin Flavonoid
Betacyanin Betalain Bougainvillea
flowers
Purple Carotenoid pepper
colour Cyanidin/ Flavonoid Petunia,
Delphinidin eggplant)
Cyanidin/r Caratenoid Cymbidium
Delphinidin and orchids
Flavonoid
Mix
Yellow Carotenoid Most flowers and fruit that are
colour yellow
Aurone Flavonoid Antirrhinum
majus flowers
Chalcone Flavonoid Dianthusflowers
Betaxanthin Betalain Portulaca
flowers

8
 The category of natural photosensitizers known as anthocyanins has
received the most research, and have a range from 548nm to 510nm, depends on the type
of natural products utilized. (Narayan, 2012). Several research on the photoelectrochemical
characteristics of dyes based on seeds, flowers, leaves, fruits, and others have been
researched are mentioned in Table 2.2.

Table 2. 2 Natural dye photoelectrochemical characteristics (Ludin et al.,2014)

Type of Plant Semicon 𝜆𝑚𝑎𝑥 (𝑛𝑚) 𝐼𝑠𝑐 (𝑚𝐴/ 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference
ducting (Maximum 𝑐𝑚2 ) (Open (Fill (Effici Cite
wavelength) ency)
Oxide (Short Circuit Factor
Circuit Photovolt )
Photocur age)
rent)
Flower
Begonia 𝑇𝑖𝑂2 540 0.63 0.53 72.2 0.24 (H. Zhou,
Rhododendro 540 1.61 0.58 60.9 0.57 Wu, Gao,
n &
Marigold 487 0.51 0.54 83.1 0.23 Ma, 2011)

Perilla 665 1.36 0.52 69.6 0.5

China 665 0.84 0.51 62.6 0.27
loropetal
Yellow rose 487 0.74 0.6 57.1 0.26
Flowery 435 0.6 0.55 62.7 0.21
knotweed
Petunia 665 0.85 0.61 60.5 0.32
Violet 546 1.02 0.49 64.5 0.33
Chinese rose 516 0.9 0.48 61.9 0.27
Rose - 0.97 0.59 65.9 0.38
Lily - 0.51 0.49 66.7 0.17
Hibiscus
Adenium 300,400 0.10 0.10 0.40 0.006 (Hang,201
Obesum 5)

9
 Type of Semiconduc 𝜆𝑚𝑎𝑥 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference
Plant ting Oxide (𝑛𝑚) (𝑚𝐴/𝑐𝑚2 ) Cite
Flower
Hibiscus 𝑇𝑖𝑂2 520 1.63 0.4 0.57 0.37 Wongchare
sabdariffa L. e,Meeyoo,
Clitoriaterna 580 0.37 0.37 0.33 0.05 &Chavadej,
tea 2007)
Erythrinavar 451, 0.78 0.48 0.55 - (Hao,Wu,
ie gata 492 Huang,&

Rosa 560 0.64 0.49 0.52 - Lin, 2006)

xanthine

Hibiscus 545 5.45 0.39 0.54 1.14 (Fernando

surattensis &Senadeera
Neriumolen 539 2.46 0.4 0.59 0.59 , 2008)
der
Hibiscus 534 4.04 0.4 0.63 1.02
rosasinesis
Sesbaniagra 544 4.4 0.41 0.57 1.02
n
diflora
Ixoramacrot 537 1.31 0.4 0.57 0.3
h
yrsa
Red 482 2.34 0.26 0.74 0.45 Hernandez
Bougainville ,535 a
a ,
glabra 2011)
Violet 547 1.86 0.23 0.71 0.31
Bougainville
a
glabra
Red 480 2.29 0.28 0.76 0.48
Bougainville
a
spectabilis

10
Violet 535 1.88 0.25 0.73 0.35
Bougainville
a
spectabilis

Type of Semicond 𝜆𝑚𝑎𝑥 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference

Plant ucting (𝑛𝑚) (𝑚𝐴/𝑐𝑚2 ) Cite
Oxide
Fruits
Tangerine 𝑇𝑖𝑂2 446 0.74 0.59 63.1 0.28 (H. Zhou,
peel et al., 2011)
Fructuslycii 447 0.53 0.68 46.6 0.17
,425
Mangosteen 389 2.69 0.68 63.3 1.17
pericarp
Raspberries 540 0.26 0.42 64.8 1.5 Alhamed,
Grapes 560 0.09 0.34 61.1 0.38 Issa, &
Citrus Doubal,
2012)
sinensis 515 3.84 0.34 0.5 - (Calogero &
(Red Di Marco,
Sicilian) 2008)
Solanummel 522 3.4 0.35 0.4 -
ongena
(Eggplant)
Cherries 500 0.46 0.3 38.3 0.18 (Jasim et al.,
2011)
Pepper 455 0.23 0.41 0.63 - Hao et al.,
2006)
Kopsiaflavid 550 1.2 0.52 0.63 (Nishantha,
a Yapa, &
Perera, 2012)

11
Dye Semicon 𝜆𝑚𝑎𝑥 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference Cite
ducting (𝑛𝑚) (𝑚𝐴/𝑐𝑚2 )
Oxide
Fruits
Berberiesbu 𝑇𝑖𝑂2 533 6.2 0.47 0.3 - (Polo & Iha,
xi 6 2011)
folia Lam
(Calafate)
Myrtuscaulif 520 7.2 0.59 0.5 -
lora Mart 4
(Jaboticaba)
Dragon fruit 520 0.2 0.22 0.3 0.22 (Ali & Nayan,
2010)
Wild Sicilian 465 8.2 0.38 0.3 1.19 (Calogero et
Prickly Pear 8 al, 2010)

Chasteberry 548 1.06 0.39 0.4 (Garcia, Polo,

8 & Iha, 2003)
Mulberry 543 0.86 0.42 0.4
3
Cabbage 545 0.37 0.44 0.6
-palm fruit 1

Ivy gourd 458,48 0.24 0.64 0.4 0.09 Shanmugam,

fruits 0 9 Manoharan,
Anandan, &
Murugan,
2013)

12
 Type of Semicond 𝜆𝑚𝑎𝑥 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference
Plant ucting (𝑛𝑚) (𝑚𝐴/𝑐𝑚2 ) Cite
Oxide
Leaves
Herbaartemi 𝑇𝑖𝑂2 669 1.03 0.48 68.2 0.34 (H. Zhou et
si al., 2011)
aescopariae
Chinese - 1.19 0.6 65.4 0.47
holly
Bitter Leaf 400 0.07 0.34 0.81 0.69 (Boyo,
Shitta,
Oluwa, &
Adeola,
2012)
spinach 437 0.47 0.55 0.51 0.13 (H Chang et
al., 2010)

Ipomoea 410 0.91 0.54 0.56 0.28

Festucaovin 420,660 1.18 0.54 0.69 0.46 (Hernández

a -
Martínez et
al., 2012)
Red 537 0.5 0.37 0.54 0.13 (Dumbrava
cabbage et
al., 2008)

Allium cepa 532 0.51 0.44 0.48 0.14

(Red onion)

13
Type of Plant Semico 𝜆𝑚𝑎𝑥 (𝑛𝑚) 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference Cite
nductin (𝑚𝐴/𝑐𝑚2 )
g Oxide
Leaves
Punicagranat 𝑇𝑖𝑂2 412,665 2.05 0.56 0.52 0.59 (Ho Chang &
um Lo, 2010)
(Pomegranat
e)
Shiso 440,600 3.56 0.55 0.51 1.01 (Kumara et
al., 2006)
Botuje 400 0.69 0.05 0.87 0.12 (Hussain,
2013)
Lawsoniainer 518 1.87 0.61 0.58 0.66 (Aduloju,
mis (Henna) Shitta, &
Simiyu,
2011)
Ficusreusa 670 7.85 0.52 0.29 1.18 (Lai, Su,
Rhoeospatha 670 10.9 0.5 0.27 1.49 Teoh, & Hon,
c 2008)
ea
Garciniasubel 670 6.48 0.32 0.33 0.69
liptica
666 0.96 0.57 40 0.22 (Taya et al.,
Parsley 666 0.53 0.44 34 0.07 2013)
(Petroselinum
crispum)

Arugula 666 0.78 0.59 42 0.2

14
 Type of Semiconduc 𝜆𝑚𝑎𝑥 (𝑛𝑚) 𝐼𝑠𝑐 (𝑚𝐴/𝑐𝑚2 ) 𝑉𝑜𝑐 (𝑉) FF 𝜂(%) Reference
Plant ting Oxide Cite
Seeds
Coffee 𝑇𝑖𝑂2 - 0.85 0.55 68.7 0.33 (H. Zhou,
Wu, Gao, &
Ma, 2011)
Black 560 1.14 0.55 0.52 - (Hao et al.,
Rice) 2006)
achiote 𝑇𝑖𝑂2 474 1.1 0.57 0.59 0.37 (Gómez-
𝑍𝑛𝑂 0.08 0.32 0.37 0.01 Ortíz
et al., 2010)
Other
Algae 𝑇𝑖𝑂2 660 0.1300 0.410 21.00 0.01 (Taya et al.,
(Green) 0 2013)
seaweed 670 0.430 0.440 0.620 (Lai et al.,
2008)

15
2.3 Mangosteen Pericarp as Photosensitizers

Mangosteen or Garcinia mangostana, is belongs to Guttiferae family. In tropical

countries, purple mangosteen (Garcinia mangostana) is a common tropical fruit and
it can be found across the Malay Archipelago, particularly in Malaysia. Due to its
outstanding biological properties, mangosteen is basically famous as the queen of
fruits across the globe (Aizat WM et al., 2019). Xanthones, phenolic acids,
anthocyanins, flavonoids, tannins, and carotenoids all contribute to the biological
activity of purple mangosteen (Orozco et al.,2013, Palakawong et al.,2018).

The rutin pigment (Figure 2.5), which had an efficiency of 1.12 percent
despite the fact that it does not does not have the same beneficial effects as oα-
Mangostin or β-mangostin structure from mangosteen peels, is the main effective
pigment responsible for the untreated mangosteen peels' high efficiency, which is
shown in Table 2.5. (H. Zhou et al., 2011). To extract the most suitable chemical
components from the mangosteen peels for a variety of uses, including antioxidant
chemicals, a variety of extraction techniques and conditions were examined (Jung et
al.,2006), (Zarena et al., 2009); (H.-C. Zhou et al., 2011).

Table 2. 3 The Photovoltaic Performance of Mangosteen Pericarp

Constituents (H.Zhou et al.,2014)

Type of Structural Photoactive 𝐼𝑠𝑐 𝑉𝑜𝑐 (𝑚𝑉) 𝜂(%) FF

Plant class area (𝑐𝑚2 ) (𝑚𝐴
/𝑐𝑚2 )
Mangosteen - 0.2 2.69 686 1.17 0.63
peels
Mangosteen α- 0.2 2.55 621 0.92 0.58
peels Mangostin/
β-
mangostin
Mangosteen Rutin 0.2 2.92 611 1.12 0.63
peels

16
Figure 2. 2 Chemical Arrangement of Rutin (Hug et al, 2014)

17
2.4 Anthocyanin

Some plant tissues contain blue, purple, and scarlet pigments called
anthocyanins. Depending on the pH of the solution, anthocyanins are present in
various chemical structure. When the pH is extremely acidic, anthocyanin is primarily
found in the cavity flavylium structure, which gives the plant its purple and crimson
red colour. Naturally, anthocyanins are always attached to the glycoside group in
anthocyanidin substances. In addition to the glycoside group, the anthocyanidin
molecule serves as the primary determinant of anthocyanin type.

Figure 2. 3 Structure of three natural anthocyanidins

Cyanidin, petunidin, and malvidin are a few examples of anthocyanidins that

commonly found in nature. Due to its ability to neutralise free radicals, anthocyanin
functions as an antioxidant. This ability skill involves disabling the free radicals that
are caused by conjugated anthocyanin structure. Anthocyanin is a substance that can
be used as an active ingredient in a dye-sensitized solar cell due to its linked structure.
The use of anthocyanin from plant products in dye-sensitized solar cells has been the
subject of numerous studies in recent decades. Through computational modelling and
calculations, the actual potential of anthocyanin as the active component in a dye-
sensitized solar cell can be determined.

18
2.5 Fourier Transform Infrared Spectroscopy (FTIR)

A technique for examining the chemical characteristics of a substance,

whether organic or inorganic, is known as Fourier Transform Infrared Spectroscopy
(FTIR). It is possible to identify the radiation that is absorbed by a sample and the
radiation that manages to pass through by passing a range of infrared radiation
through it. This allows for the molecular identification of various substances.

Any absorption spectroscopy has the objective of determining how well a

material absorbs light at various wavelengths. With this method, the sample is
illuminated by a beam of light that contains a variety of frequencies in place of a
monochromatic beam, and the amount of that beam that is absorbed by the sample
is then measured. A second data point is then obtained by modifying the beam to
include a different parameter combination of frequencies. Several times, this
procedure is repeated. After that, a computer uses all of these data to calculate the
absorption at each wavelength by going backwards. FTIR is rarely used to detect
contaminants, additions, and oxidation in a material, in addition to evaluating chemical
components. Moreover, it can identify uncured or decomposing monomers in a
substance. It is an easy-to-use method for determining the chemical compositions of
materials. Except from homo-nuclear diatomic molecules due to their inactive infrared
state, all materials are appropriate for FTIR investigation.

19
2.6 Ultraviolet–Visible Spectroscopy (UV-Vis)

In the ultraviolet-visible spectral region, absorption spectroscopy or

reflectance spectroscopy are referred to as ultraviolet-visible spectroscopy (UV-Vis) or
ultraviolet-visible spectrophotometry (UV-Vis). This indicates that it makes use of light
in the visible and nearby (near-UV and near-infrared (NIR) spectrums. The visual
absorption or reflectance in a chemical directly impacts how that chemical is perceived
to be coloured. Electronic transitions occur in molecules in this area of the
electromagnetic spectrum. Since absorption monitors transitions from the ground
state to the excited state, it is a supplementary approach to fluorescence
spectroscopy, which deals with transitions from the excited state to the ground state.

In analytical chemistry, UV-Vis spectroscopy is frequently employed for the

quantitative determination of various analytes. Although solids and gases as well as
liquids can be examined by spectroscopy. Each substance absorbs to a different
extent. Moreover, organic substances absorb light in the UV or visible ranges of the
electromagnetic spectrum, especially those with a high degree of conjugation.
According to the Beer-Lambert rule, the absorbance of a solution is inversely
correlated with both the route length and the concentration of the absorbent in the
solution. UV-Vis spectroscopy can be used to ascertain the concentration of the
absorber in a solution for a fixed route length.

20
2.7 Density Functional Theory (DFT)

An excellent insight into molecular/cluster systems from several angles is given

by effective computer programming of the theoretical model. Both the fundamental
knowledge of atomic/molecular systems and its application in diverse domains of
interest have been significantly influenced by these computer-aided simulation
approaches. Protons and electrons are abundant in all materials, and each one of them
generates a Coulomb's potential around it. The motions and interactions of each and
every particle in the system must be considered while studying condensed matter
physics. The DFT views electron density as a fundamental variable for defining the
interaction of electrons, which gives rise to the features of the ground state. When an
effective potential is used in the Kohn-Sham DFT, the interacting electrons in a static
external potential are switched in favour of the non-interacting electron. The effective
potential includes the external potential and the Coulombic interactions amongst the
electrons.

21
 CHAPTER 3

METHODOLOGY

3.0 Introduction

This chapter discusses the methods used to achieve research objective. Among
the methods carried out are maceration method for the mangosteen extraction,
mangosteen extract characterization using FT-IR and UV-Vis spectroscopy to identify
the existence of anthocyanin and finally identify the types anthocyanin present in
mangosteen extract through DFT computation with the comparison of theoretical and
experimental IR and UV spectra.

3.1 Materials

The materials used for the experiment includes:

• Mangosteen
• Methanol 99%
• Beaker
• Filter funnel
• Mortar
• Pestel
• Kitchen Knife
• Glass stirring Rod
• Plastic Cup
• Metal Spoon

In this study, the materials involved in the sample preparation process and extraction
is mangosteen and methanol. Methanol was used because solvents such as methanol
can maintain the anti-oxidant properties of anthocyanins at a level which is high .The
mangosteen fruit were obtained from the Pasar Besar Kota Kinabalu. While methanol
and the materials involved were obtained from Materials Science Laboratory and
Materials and Computing Laboratory, University Sabah Malaysia (UMS).

22
3.1 Project Flow chart

Start

Research

Literature Review

Sample Extraction

GaussView Modelling & Calculation

Spectroscopy Analysis

Final Report

End

Figure 3. 1 Project Flow Chart

23
3.2 Extraction of Mangosteen Peels

10g of Mangosteen peels were washed and

dried

The mangosteen peels crushed with mortar

and pestle,and immersed in 50 mL of
Methanol

The mixture is then left at 24°C for 30 minutes

After 30 minutes,the solid then filtered

Using UV-Vis and FTIR,the solution is then

characterized

Figure 3. 2 Extraction of Mangosteen Peels Dye

Figure 3. 3 Fresh Mangosteen Figure 3. 4 Dried pericarp

Figure 3. 5 Crushed Pericarp soaked

with methanol

24
 Methanol was used to extract all the dye. 10g of fresh mangosteen peels
were washed and dried using sunlight first to make sure there is no residue left. The
peels are then pounded into powder with a mortar and pestle, soaked in methanol for
half an hour at room with temperature of 24°C. The solids were then filtered out.
Then, the characteristic of the mixture was also been investigated using UV-VIS and
(FTIR) Spectroscopy.

3.4 Fourier Transform Infrared Spectroscopy (FTIR) Analysis

Characterization of the mangosteen peels extract was done using a Fourier

Transform Infrared Spectrometer (FTIR), BRUKER ALPHA-P. The frequencies of
vibrations between the bonds of the atoms building up the materials are represented
by the infrared spectra of the specimens that were collected. Results from infrared
spectroscopy show the qualitative analysis of the mangosteen peel extract at various
wavenumbers. This relates to the various types of molecules, bonding, and elements
found in the extract. The spectra's absorption peak indicates the existence of a specific
compound in a sample. Since there were no sample preparation steps prior to testing,
attenuated total reflectance (ATR) was used as the examination technique and from
500 to 3500 cm-1 at incidence angle of 45°. It calculates the changes that take place
in the infrared beam's total internal reflection when it comes into touch with the
sample. The molecule's transmission and absorption spectra were observed.

25
3.5 Ultraviolet–Visible Spectroscopy (UV-Vis) Analysis

The absorption and reflectance spectroscopy of the extract within the ultraviolet-
visible spectral region has been identified using UV-VIS. The electrons in the sample
are stimulated to a higher energy band when it absorbs energy from ultraviolet or
visible light; the easier the electrons are excited, the longer the wavelength of the
electromagnetic spectrum that is absorbed. The wavelength of the light source is
separated by the diffraction grating, allowing for the measurement of light intensity
as a function of wavelength. By detecting the beam, the detector both the light
source's and the beam's intensity after they have passed through it. When the distinct
wavelengths, or differences in intensity, are known, it is possible to calculate the
sample's absorbance. The investigations in the UV-Visible range were carried out using
the UV-VIS (Agilent Cary 60) with the wavelength ranging from 200 nm to 800 nm at
scan rate of 24000 nm/min.

26
3.6 Density Functional Theory (DFT) with GaussView

Figure 3. 6 The chemical structure of anthocyanin modelled in

GaussView

Molecular structure modelling and frequency vibration calculations for anthocyanin

using GaussView 5.0.8 and GaussSum 2.2.4 software were used to do each and every
calculation. To examine the structural optimization and the electronic of the ground
state of the dyes in the gas phase, the Becke's three parameter functional and the
Lee-Yang-Parr functional (B3LYP) 21. and 6-31G (d) basis set were used in the density
functional theory (DFT). Also, in that work, the electronic absorption spectra and
vertical excitation energy were simulated using the TD-DFT-B3LYP approach. When
trying to accurately replicate or forecast the experimental spectra, the solvent effect
must be taken into account in theoretical calculations.

27
 CHAPTER 4

RESULTS AND DISCUSSION

4.0 Introduction

As discussed in previous chapter, the spectroscopy used to obtain the experimental

result are FTIR and UV-Vis. After characterization of the sample using both
spectroscopies have been made, the computation analysis using GaussView software
as the theorical approach to obtain the theorical result. In this section, both
experimental and theorical result will be discussed.

4.1 FTIR Spectra of Mangosteen Pericarps with Methanol

Figure 4. 1 The FTIR spectra of the mangosteen peels extracted with methanol

The characteristics of mangosteen peels extract was studied by using FTIR BRUKER on
wave number 3500 to 500 𝑐𝑚−1 in order to detect the functional groups. The FTIR of the
methanolic extract shown eight main absorption peaks at 3327.13, 2946.00, 2835.10,
1654.12, 1452.39, 1109.87, 1017.48 and 590.62 𝑐𝑚−1. Alkyl groups could be detected by
the peaks for C-H sp3 stretching (2946 and 2835.10 𝑐𝑚−1.), −𝐶𝐻2 - bending (1452.39
cm-1), and −𝐶𝐻3- bending (1109.87 𝑐𝑚−1 ), while the presence of the carboxylic acid
functional group could be detected by peaks for O-H stretching (3327.13 𝑐𝑚−1), C=O
stretching (1654.12 𝑐𝑚−1), and C-O ester (1017.48 𝑐𝑚−1)

28
Due to the organic base of the natural dye, the extracted dye also contains aldehydes at
wavelengths of 1117.48 𝑐𝑚−1 and 590.62 𝑐𝑚−1. The structure of anthocyanin, which
consists of a benzene ring, a double bond, a carbonyl group, a C-H bond, and an OH
group, is established by all of these functional groups and this result suggests that
anthocyanin is present in the dye that was extracted.

4.2 UV-Vis Spectra of Mangosteen Pericarps with Methanol

Figure 4. 2 UV-Vis Spectra of Mangosteen Pericarps extract with Methanol

With the use of UV-Vis, the optical properties of extract were examined and UV-vis
spectra of mangosteen peels extract are presented in Figure 4.2 using methanol as
the media. The strength of the absorption was investigated at a specific wavelength
range between 200 and 800 nm using an Agilent Carry 60 UV-Vis. The UV-Vis spectra
of the methanol extract showed strong absorption peaks at 665, 410, and 440 nm.
The chemical compound of alpha-mangostin, beta-mangostin, gartanin, and garcinone
E) were detected in the UV-Vis of the methanol extracts, peaks at 370 and 295 nm,
whereas anthocyanin pigments were detected at absorption peak 265 nm (including
cyanidin-3-sophoroside and cyanidin-3-glucoside).

29
4.3 Density Functional Theory (DFT) computation

Figure 4. 3 IR Spectrum DFT

At the range of 4000 𝑐𝑚−1. to 3500 𝑐𝑚−1,the spectral band shows a fairly strong
bandwidth. Whereas, as shown in Figure 4.3 IR DFT spectrum, there is a difference
between the results of the theoretical spectrum and experiment spectrum. The
presence of a spectral band with a wavelength ranging from 2500 𝑐𝑚−1 to 3000
𝑐𝑚−1,indicating the presence of a C-H stretching. The presence of C=O stretching
can also be seen in the range of 2000𝑐𝑚−1 to 1500𝑐𝑚−1. The presence of C-O ester
can be also be proven by the present of spectral band ranging from 1250𝑐𝑚−1 to
1000𝑐𝑚−1.

Figure 4. 4 UV Spectrum TD DFT

30
For the UV spectrum TD DFT of anthocyanin, showed the absorption peaks ranging
from 400 and 600 nm, corresponding to the presence of the mangostin compounds
(including α-mangostin, β-mangostin, ɣ-mangostin, gartanin and garcinone E, while
the absorption peak at 500nm corresponding to the presence of anthocyanin
pigments (including cyanidin-3-sophoroside and cyanidin-3-glucoside). Therefore,
the type of anthocyanin in mangosteen extract is quite difficult to analyze because
the types of anthocyanins give almost the same UV spectrum. However, there is
only small difference from the calculated spectrum and the experimental spectrum.

4.4 Theorical and Experimental Comparison

Table 4. 1 FTIR Result Comparison

FTIR Experimental FTIR Theorical (DFT)

All functional group for anthocyanin Showing dissimilarity with experimental

were detected; result as not all functional group for
anthocyanin were detected in the theorical.

Carboxylic acid Carboxylic acid

3327.13 (OH) (OH) not detected
1654.12 (C=O) (1500-2000) (C=O)
1017.48 (C-O ester) (1250-1000) (C-O ester)
(Alkyl group)
(2835.10-2946.00) (Alkyl group)
1452.39 (2500.00-3000.00)
1109.87
Aldehyde Aldehyde
590.62 Not detected

31
 UV-Vis Experimental UV-Vis Theorical (TD-DFT)

Mangostin compounds and anthocyanin Showing identical result with experimental as

pigments were detected all the Mangostin compounds and
anthocyanin pigments were also detected.

665 and 410 nm (α-mangostin, β- 600 and 400 nm (α-mangostin, β-mangostin,

mangostin, ɣ-mangostin, gartanin and ɣ-mangostin, gartanin and garcinone E)
garcinone E)
500nm (cyanidin-3-sophoroside and
440nm (cyanidin-3-sophoroside and cyanidin-3-glucoside)
cyanidin-3-glucoside)

Overall, the vibrational difference between IR and FT-IR spectra which very noticeable
in the range of 3500 to 4000 cm-1 is due to the interaction of hydrogen bonds that
cause factors such as frequency shifts and enhancement of the IR intensity for the
band of vibrational modes of the bound functional groups directly with hydrogen
bonds. Therefore, all of the anthocyanin compound in mangosteen extract is quite
difficult to analyze because obtained results from both experimental and theorical give
almost the same UV spectrum but present a significant difference of the calculated IR
spectrum and the experimental IR spectrum

32
 CHAPTER 5

5.1 Conclusion

The preliminary results that were obtained from the characterization of mangosteen
pericarps dye using FTIR and UV-Vi’s spectroscopy indicates there is the presence of
anthocyanin in mangosteen peel extract. The result obtained from DFT computation
also showing similarities with the FTIR and UV-Vis values from the experimental and
the presence of chemical compounds of mangosteen based on literature can be
proven. However, because of the anthocyanin derivatives are nearly identical and the
methoxy derivative is the only variation, the DFT method for classifying anthocyanins
is not appropriate. Despite this, the mangosteen has a significant potential for usage
as a sensitizer in the creation of DSSC due to its special capacity to absorb UV and
visible light, which is brought on by the presence of anthocyanin pigments. The
existence of anthocyanin pigments in mangosteen, which aid in the excitation and
transfer of electrons are responsible for the fruit's comparatively high efficiency.

5.2 Recommendation

This study suggests that the variation of solvent use for the isolation of anthocyanins
should be widen before conducting a study to determine the types of anthocyanins in
natural dye extracts and this is because of isolation of the natural pigments from
purple mangosteen peels carried out through a maceration technique employing other
solvents such as distilled water, ethanol, acetone and etc. can help to determine the
best solvent for the extraction of mangosteen dye for the fabrication of DSSC. In
addition, other techniques like High Performance Liquid Chromatography (HPLC) and
Nuclear Magnetic Resonance (NMR) can be used to help in determining the types of
anthocyanins exists in natural dye.

33
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 APPENDICES

Appendix 1. 1 Fresh mangosteens Appendix 1. 2 Dried Pericarp

Appendix 1. 5 Mangosteen Appendix 1. 3 UV-VIS (Agilent

with Methanol Cary 60)

Appendix 1. 4 Computation with GaussView

Software

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