Fabrication of Optical Fibre

Microheaters

MF F377

Fabrication of Optical Fibre

Microheaters

Submitted By :
Mrudula
ID:2016ABPS0842

Submitted To:
Dr. Venkatesh KP
Asst. Professor,
Department of Mechanical Engineering.
Fabrication of Optical Fibre Microheaters Mrudula

Contents
1 Abstract 2

2 Introduction 2

3 Fabrication of Bi-metallic core-shell Nanoparticles 4

3.1 Fabrication of Au@Ag, Ag@Au Nanoparticles . . . . . . . . . . . . . 4
3.2 CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3 Coating of Gold Nano Particles on MWCNTs . . . . . . . . . . . . . 6
3.3.1 Method 1- Sputtering . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.2 Method 2- Chemical Attachment . . . . . . . . . . . . . . . . 6
3.3.3 For the thiol functionalisation of MWCNTs . . . . . . . . . . 7
3.3.4 For the Gold Nanoparticle coating onto the thiol function-
alised MWCNTs . . . . . . . . . . . . . . . . . . . . . . . . . 7

4 Fabrication of the Optical Fibre Microheater 9

5 Evaluation of Photothermal effects 9

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Fabrication of Optical Fibre Microheaters Mrudula

1 Abstract
Photothermal therapy has been shown to be a promising method for treating cancer
cells. Many studies have been done on the effectiveness of geerating heat via the
use of Carbon Nanotubes (CNTs). It has also been reported about the use of
metallic nanoparticles (Gold, Silver) deposited onto the surface of CNTs for increase
in efficiency of hyperthermia. This work uses bimetallic nanoparticles of varying
compositions and tests their efficiency in the visible region of 630 nm. This work
also tests the bimetallic nanoparticles in conjunction with the CNTs to test the
difference in heat produced.

2 Introduction
Photothermal therapy has been a promising means to treat malignant tissues. Ex-
perimental evidence suggests that thermal therapy, by increasing temperature above
normal body temperature has different biological consequences, such as damage to
subcellular structures, blood coagulation. Inducing apoptic signalling pathways or
tissue charring. Cornel Iancu and Lucian Mocan. “Advances in cancer therapy
through the use of carbon nanotube-mediated targeted hyperthermia”. In: Inter-
national journal of nanomedicine 6 (2011), p. 1675; Yoshikiyo Hatakeyama, Kei
Onishi, and Keiko Nishikawa. “Effects of sputtering conditions on formation of
gold nanoparticles in sputter deposition technique”. In: RSC Advances 1.9 (2011),
pp. 1815–1821; JW Nicholson, RS Windeler, and DJ DiGiovanni. “Optically driven
deposition of single-walled carbon-nanotube saturable absorbers on optical fiber end-
faces”. In: Optics express 15.15 (2007), pp. 9176–9183; Kanwal Ahmed and Syed
Faisal Zaidi. “Treating cancer with heat: hyperthermia as promising strategy to
enhance apoptosis”. In: J Pak Med Assoc 63.4 (2013), pp. 504–508
In recent years, a promising technique in photothermal therapy is the use of light to
heat biological tissues using highly focused ultrasound probesWilliam N McMullen,
Luigi Solbiati, and Eric VanSonnenberg. Tumor Ablation: Principles and Practice.
Springer, 2005- the use of optical light provides advantages over other methods due
to the possibility of space control and precise in-situ administration with the use of
optical fibres. Furthermore, some wavelengths of light allow for greater penetration
depths reaching deep tissues, providing attractive capabilities for non-invasive or
minimally invasive therapy. Thomas J Vogl et al. “Laser-induced thermotherapy
of malignant liver tumors: general principals, equipment (s), procedure (s)–side
effects, complications and results”. In: European Journal of Ultrasound 13.2 (2001),
pp. 117–127
Several studies have explored the effects of photothermal therapy, both in animals

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Fabrication of Optical Fibre Microheaters Mrudula

and humans. In most studies shown, the main limitation is the availability of de-
sired wavelengths (i.e. Near Infra-Red region light) to generate the desired pho-
tothermal effects in tumours and also avoiding damage to surrounding healthy tis-
sue. This problem has earlier been tackled with the use of high powered lasers
(several Watts of optical power) along with prolonged therapy time (¿10 minutes).
Large doses of energy causes breakdown of tissue as well as cell death due to cav-
itation effects.Mehrdad Nikfarjam, Caterina Malcontenti-Wilson, and Christopher
Christophi. “Focal hyperthermia produces progressive tumor necrosis independent
of the initial thermal effects”. In: Journal of gastrointestinal surgery 9.3 (2005),
pp. 410–417
To counter this problem, Nanotechnology provides an elegant solution with the
fabrication of nanoparticles. These nanoparticles have proven to be highly efficient
converters of light to heat and this attractive feature allows for the possibility of
their development into nanoheaters.
Along with nanoparticles, another extremely efficient mode of light-to-heat conver-
sion are Carbon Nanotubes (CNTs). CNTs are long, hollow structures with their
walls formed by one-atom thick sheets of graphene. These sheets are rolled at spe-
cific chiral angles to give rise to different physical and chemical properties. These
Nanotubes are characterised as Single Walled Carbon Nanotubes (SWCNTs) and
Multi-Walled Carbon Nanotubes (MWCNTs).
In our study, we have employed the use of metallic, multi-walled carbon nanotubes
due to the higher efficiency of light to heat as compared to SWCNTs in the biological
tissue window of 650-950 nm. The light used in this work is however in the range of
630-635 nm (red light). This biological tissue window is crucial for the application of
light due to optical transparency of tissues in this region. MWCNTs have shown to
show vibrational resonance over a range of frequencies overlapping with the biological
widow whereas SWCNTs have shown only peak resonances. Furthermore, due to
their economic viability, MWCNTs (Sigma Aldrich , 724769) have been used.
Gold, silver and other metallic nanoparticles have been used in several works Ari-
valagan Pugazhendhi et al. “Inorganic nanoparticles: a potential cancer therapy
for human welfare”. In: International journal of pharmaceutics 539.1-2 (2018),
pp. 104–111Catarina Oliveira Silva et al. “Current Trends in Cancer Nanothera-
nostics: Metallic, Polymeric, and Lipid-Based Systems”. In: Pharmaceutics 11.1
(2019), p. 22Terry B Huff et al. “Hyperthermic effects of gold nanorods on tumor
cells”. In: (2007) due to their photothermal properties in the visible and NIR re-
gion. In this work, Au@Ag and Ag@Au core-shell nanoparticles were fabricated in
different composition and tested alone as well as with MWCNTs for their heating
efficiencies.

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Fabrication of Optical Fibre Microheaters Mrudula

3 Fabrication of Bi-metallic core-shell Nanoparti-

cles
3.1 Fabrication of Au@Ag, Ag@Au Nanoparticles
The core-shell nanoparticles were fabricated in different compositions using HAuCl4
and AgNO3 with beta-cyclodextrin according to the following reaction mechanism.

Figure 1: Showing reaction mechanism of fabrication of core-shell nanoparticles

using beta-cyclodextrin

Beta-Cyclodextrin is part of a family of oligosaccharides. In the given reaction mech-

anism, it acts as a stabilisng agent (see Fig 2.) by surrounding the mono-metallic
Au/Ag Nanoparticles. Subsequent reaction of the monometallic nanoparticle with
the shell metal salt gives a core-shell bimetallic nanoparticle. Varying the concen-
tration ratios of the shell and the core salts will fabricate a bi-metallic nanoparticle
of varying core-shell dimensions.

3.2 CNTs
Carbon Nanotubes are allotropes of carbon with a cylindrical nanostructures and
consist of one or more seamless, cylindrical graphitic sheets of sp2 carbon atoms
bonded together in an edgeless, hexagonal network. The absence of sp3 bond-
ing, and the presence of large surface area to volume ratio, especially in the ring
structure of graphene, results in high tensile strengths. Furthermore, the combi-
nation of their electrical, thermal and spectroscopic properties has evoked great
interest in the biological field- particularly properties such as their ability to pene-
trate biological tissue with minimal toxicity, and the high light-to-heat conversion
ratio especially in the biological window of the Near Infra-Red region of 700-950

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Fabrication of Optical Fibre Microheaters Mrudula

Figure 2: Figure illustrating stabilising mechanism of beta-cyclodextrin on

monometallic nanoparticle

nm leads them to be highly useful in the field of Photothermal Therapy (PTT).

andersson1988photodynamic
CNTs are broadly categorised into Single walled (SWCNTs) and Multi walled carbon
nanotubes (MWCNTs) depending upon the number of sheets or rolls of graphene in
the tube. Tubes with only one graphene sheet (one atom thick) are known as single
walled carbon nanotubes whereas tubes with multiple sheets (with subsequent sheets
of higher outer diameter) are known as multi-walled carbon nanotubes (MWCNTs).
Although NIR absorption and energy transduction effect remains high across a wide
frequency range, studies have shown that MWCNTs are 60% more efficient at light-
to-heat conversion than SWCNTs in the biological window. Due to this, and the
economic viability of MWCNTs, it has been proposed that MWCNTs in the diameter
range of 5-10 nm and length <= 30µm be used.
The reason for the proposed dimensions lies in the dependence of nanoparticle coat-
ing on nanotube on the defect density of the tube. The defect density of CNTs has
been theoretically, as well as experimentally been found to depend on the outer di-
ameter as well as the total length of the tube. For nanotubes with length <= 30 µm,

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Fabrication of Optical Fibre Microheaters Mrudula

it has been found that nanoparticle aggregation takes place on defect sites on the
CNTs and consequently, aggregation increases with increase in defect density. In the
same study, it has been found that grain size is inversely proportional to aggregation
density of nanoparticles.

3.3 Coating of Gold Nano Particles on MWCNTs

3.3.1 Method 1- Sputtering
Sputter deposition of metals in a medium with extremely low vapor pressure is a
simple and convenient method for the generation of metal nanoparticles without
chemical reactions. Careful selection of capture medium, medium pressure, sputter-
to-substrate distance, in-situ heating temperature as well as applied voltage, the
size of the synthesised NPs can be controlled.Hatakeyama, Onishi, and Nishikawa,
“Effects of sputtering conditions on formation of gold nanoparticles in sputter de-
position technique”, op. cit.
The sputtering is to be done in an inert gas environment at an approximate chamber
pressure of 0.1 mbar and a current of 40 mAReinher Pimentel-Domı́nguez et al.
“Photothermal lesions in soft tissue induced by optical fiber microheaters”. In:
Biomedical optics express 7.4 (2016), pp. 1138–1148. The sputter coater used in the
referred study is a D.C. sputter coater with a gold cathode and the carbon nanotube
coated optic fibre as the cathode, however, in our study we will coat the Carbon
Nanotube first with the Au-NPs and then use ultra-sonication for the subsequent
coating of Optic Fibre with the Au-NP coated MWCNTs.
The desired dimension of the gold layer is to be 10 nm with the grain size to be
between 5-13 nm.

3.3.2 Method 2- Chemical Attachment

Although sputtering offers an attractive method of obtaining a uniform layer of
metal nanoparticle on the substrate, the grain size desired may not be accurately
controlled in this method. As a result, the chemical attachment of Au-NPs onto the
CNTs is preferable. This may further be obtained via two methods.
Method a) Use of 3-(aminopropyl) triethoxysilane (APTES)
In Fig 2., the MWCNT-OH + APTES reaction is to be carried out in anhydrous
toluene with in situ heating of 120◦ C for 24 hours under argon protection. The
resultant MWCNT-Au NPs obtained are to be washed with distilled water and
ethanol and subsequently centrifuged and dried in vacuum for 10 hours at 60◦ C.
The reaction conditions control the size of the resultant Au-NPs obtained and in a

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Fabrication of Optical Fibre Microheaters Mrudula

Figure 3: Reaction mechanism of attachment of Au-NPs on MWCNTs using APTES

referred study have been shown to be having an average diameter of 12 nm under

SEM, FTIR analyses.
Method b)For the thiol functionalisation of MWCNTs
MWCNTs are to be functionalised using aliphatic bifunctional thiols (1,4-butanedithiol,
1,6-hexanedithiol, 1,8-octanedithiol, and 2-aminoethanethiol) through a direct sol-
vent procedure. MWCNTs functionalised with amino thiols have shown a greater
grain size ( 7 nm) due to a coalescence phenomenon.Rodolfo Zanella et al. “Deposi-
tion of gold nanoparticles onto thiol-functionalized multiwalled carbon nanotubes”.
In: The Journal of Physical Chemistry B 109.34 (2005), pp. 16290–16295

3.3.3 For the thiol functionalisation of MWCNTs

The thiol functionalisation of the MWCNTs is to be carried out as a solvent free
gas-phase procedure. MWNTs (100 mg) and dithiol or aminothiol (ca. 20 mg) are to
be placed together into the reactor, and the reaction is to be performed at 130−150
◦
C for 2 h. During this procedure, thiol vapours react with MWNTs; excess of the
reagent condensed a few centimetres above the heated zone.

3.3.4 For the Gold Nanoparticle coating onto the thiol functionalised
MWCNTs
Gold nanoparticles are to be prepared via the reaction of HAuCl4 (Aldrich) and citric
acid (Baker) as reducing agent. In a typical experiment, 0.05 g of functionalised
MWNTs are to be dispersed in 2-propanol (30 mL) and ultrasonicated for 3−5 min.
Then 0.016 g of HAuCl4 and 0.017 g of citric acid, both dissolved separately in
10 mL of 2-propanol, are to be simultaneously added dropwise to the dispersion of
MWNTs. The final volume is to be 50 mL. Ultrasonication is to be maintained

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Fabrication of Optical Fibre Microheaters Mrudula

Figure 4: Schematic procedure of Au-NP formation using thiol functionalised MWC-

NTs

during HAuCl4and citric acid addition for about 3 min, then the dispersion is to
be vigorously stirred at room temperature for 2 h. After the procedure, the solid
phase is to be separated by centrifugation (5000 rpm for 10 min), washed in 20 mL
of 2-propanol under stirring for 10 min, and then centrifuged again. The resulting
MWNTs are to be dried under vacuum at room temperature for 2 h. The dry
samples are stored away from light in a vacuum desiccator. ibid.

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Fabrication of Optical Fibre Microheaters Mrudula

4 Fabrication of the Optical Fibre Microheater

The fabricated Au-NP coated MWCNT is to be coated on to the optical fibre tip.
The fibre to be used is a standard single-mode optical fibre (SMF 28-e, 8 micron
core) and is to be cleaned and cleaved to obtain a flat end face.

Figure 5: Reaction mechanism of attachment of NPs on MWCNTs using APTES

As shown in Fig 4., the deposition technique apparatus consists of a light source,
and a solution of dispersed nanotubes in ethanol. The deposition technique was
originally performed using single walled carbon nanotubes, but has been successfully
demonstrated using MWCNTs as well. The solution of ethanol and NP-coated
MWCNTs is to be prepared using 0.5 mg of nanotubes with 12 cc of ethanol and
ultrasonicating for 15-30 minutes. The optical fibre is to be prepared by removing
the coating and cleaving and placing the fibre into the solutionPimentel-Domı́nguez
et al., “Photothermal lesions in soft tissue induced by optical fiber microheaters”,
op. cit. Optical radiation from a laser diode of 975-980 nm is to be propagated via
the fibre. The output power and the irradiation time of the laser diode is to be 137
mW and 240 s respectively to ensure an adequate layer.

5 Evaluation of Photothermal effects

The optical bre microheater (OFMH) once fabricated is to be used to provoke light-
induced localised lesions at the surface of malignant liver tissue extracted from lab-
oratory mice to demonstrate proof of this technique.

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Fabrication of Optical Fibre Microheaters Mrudula

The laboratory mice to be used are to be male, and of a CD-1 strain. Malignant
liver tissue from the CD-1 strain mice is to be removed for testing. The OFMH is
to be placed directly onto the liver tissue and optical light to be passed through the
OFMH to induce thermal lesions onto the liver tissue.
A zirconia ferrule is to be used to x the OFMH to a linear translational stage intended
to draw the microheater towards the liver surface. The opposite ends of the OFMH
are to be connected to a bre-coupled laser diode and light of varying wavelengths is
to be propagated for di erent amounts of irradiaion time to test their e ect on size
of lesions produced in the liver.ibid.
Once lesions are produced, they are to be characterised using Scanning Electron
Microscopy (SEM).ibid.

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Fabrication of Optical Fibre Microheaters Mrudula

References
Ahmed, Kanwal and Syed Faisal Zaidi. “Treating cancer with heat: hyperthermia
as promising strategy to enhance apoptosis”. In: J Pak Med Assoc 63.4 (2013),
pp. 504–508.
Hatakeyama, Yoshikiyo, Kei Onishi, and Keiko Nishikawa. “Effects of sputtering
conditions on formation of gold nanoparticles in sputter deposition technique”.
In: RSC Advances 1.9 (2011), pp. 1815–1821.
Huff, Terry B et al. “Hyperthermic effects of gold nanorods on tumor cells”. In:
(2007).
Iancu, Cornel and Lucian Mocan. “Advances in cancer therapy through the use of
carbon nanotube-mediated targeted hyperthermia”. In: International journal of
nanomedicine 6 (2011), p. 1675.
McMullen, William N, Luigi Solbiati, and Eric VanSonnenberg. Tumor Ablation:
Principles and Practice. Springer, 2005.
Nicholson, JW, RS Windeler, and DJ DiGiovanni. “Optically driven deposition of
single-walled carbon-nanotube saturable absorbers on optical fiber end-faces”. In:
Optics express 15.15 (2007), pp. 9176–9183.
Nikfarjam, Mehrdad, Caterina Malcontenti-Wilson, and Christopher Christophi.
“Focal hyperthermia produces progressive tumor necrosis independent of the ini-
tial thermal effects”. In: Journal of gastrointestinal surgery 9.3 (2005), pp. 410–
417.
Pimentel-Domı́nguez, Reinher et al. “Photothermal lesions in soft tissue induced by
optical fiber microheaters”. In: Biomedical optics express 7.4 (2016), pp. 1138–
1148.
Pugazhendhi, Arivalagan et al. “Inorganic nanoparticles: a potential cancer therapy
for human welfare”. In: International journal of pharmaceutics 539.1-2 (2018),
pp. 104–111.
Silva, Catarina Oliveira et al. “Current Trends in Cancer Nanotheranostics: Metallic,
Polymeric, and Lipid-Based Systems”. In: Pharmaceutics 11.1 (2019), p. 22.
Vogl, Thomas J et al. “Laser-induced thermotherapy of malignant liver tumors:
general principals, equipment (s), procedure (s)–side effects, complications and
results”. In: European Journal of Ultrasound 13.2 (2001), pp. 117–127.
Zanella, Rodolfo et al. “Deposition of gold nanoparticles onto thiol-functionalized
multiwalled carbon nanotubes”. In: The Journal of Physical Chemistry B 109.34
(2005), pp. 16290–16295.

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