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Silica-coated Cobalt Ferrite Nanoparticles for Magnetic Hyperthermia

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Silica-coated Cobalt Ferrite Nanoparticles for Magnetic Hyperthermia

Yousaf Iqbal · Hongsub Bae · Ashfaq Ahmad · Ilsu Rhee

Department of Physics, Kyungpook National University, Daegu 702-701, Korea

Sungwook Hong

Division of Science Education, Daegu University, Gyeongsan 712-714, Korea.

(Received 9 December 2014 : revised 27 January 2015 : accepted 29 January 2015)

We report the synthesis and the characterization of silica-coated cobalt ferrite nanoparticles with a core-shell structure for magnetic hyperthermia. The silica-coated cobalt ferrite nanoparticles were synthesized by using the reverse micelle method. X-Ray diffraction (XRD) confirmed the crystallinity of the cubic spinel structure. Transmission electron microscopy (TEM) results depicted a spherical core-shell structure with a uniform size distribution of nanoparticles having an average diameter of 17 nm. The binding of the silica on the surface of the cobalt ferrite nanoparticles was revealed by using measurements made with a Fourier-transform infrared spectrometer (FTIR). The saturation magnetization of our synthesized nanoparticles was 42.4 emu/g, as measured by using a vibrating sample magnetometer (VSM). Moreover, the specific absorption rate of the nanoparticles dispersed in water at a concentration of 30 mg/ml was investigated in an alternating magnetic field of 1.03 kA/m with a frequency of 260 kHz. The nanoparticles showed significant heat release, demonstrating their potential for magnetic hyperthermia.

PACS numbers: 81.05.Ni, 76.60.Es, 61.46.Df, 87.61.-c

Keywords: Cobalt ferrite, Silica coating, Magnetic hyperthermia, Specific absorption rate (SAR).

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´o  – Ð  ïh A ) a  ïµ 1 Ïà Ô ` … s à Ô  ” ¸{ 9  \  ¦ % i  p ! s q (reverse micelle)~ ½ ÓZ O `  ¦ s 6   x # Œ + þ A$ í % i 



. XRD (X-ray Diffraction)\  ¦ : Ÿ x K   ïµ 1 Ïà Ô ` … s à Ô { 9  _    & ñ ½ ¨› ¸\  ¦ › ' a ¹ 1 Ï % i  . s \  ¦ : Ÿ x K   ï µ

1 Ïà Ô ` … s à Ô { 9    H { 9 ~ ½ Ó Û ¼x 3 A q (cubic spinel)½ ¨› ¸\  ¦ f ” `  ¦ ^  ¦ à º e ” % 3  . TEM (Transmission Electron Microscope)`  ¦ : Ÿ x K   ” ¸{ 9    H f ”  â s  17 nm “   ½ ¨+ þ A_  { 9  e ” `  ¦ · ú ˜ à º e ” % 3  . z  ´o   _

  ” ¸{ 9   ³ ð€  \ _   ҂ à Ì © œI   H FTIR (Fourier Transform Infrared Spectrometer)`  ¦ : Ÿ x K  › ' a ¹ 1 Ï 

%

i  .  ” ¸{ 9  _   l & h  $ í | 9 “ É r VSM (Vibrating Sample Magnetometer)`  ¦ : Ÿ x K  œ í © œ $ í `  ¦ ˜ Ðe ” 

` 

¦ · ú ˜ à º e ” % 3 “ ¦, Ÿ í o  o• ¸  H 42.4 emu/ge ” s  › ' a ¹ 1 Ï÷ &% 3  .  ” ¸{ 9   à º6   xÓ  o`  ¦  l  © œ_  [ jl  1.03 147

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License

(http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any

medium, provided the original work is properly cited.

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kA/m (13 Oe) s “ ¦ ”  1 l x à º 260 kHz“   „   l  \  Z  ~`  ¦  â Ä º 600œ í Ê ê 42 C  t _  “ : r • ¸7 £ x \  ¦ ˜ Ð e ”

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PACS numbers: 81.05.Ni, 76.60.Es, 61.46.Df, 87.61.-c Keywords:  ïµ 1 Ïà Ô ` … s à Ô, z  ´o    ïh A,  $ í \ P “ : r ´ òõ , SAR

I. " e  ] Ø

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 H \  s \  @ /ô  Ç ƒ  ½ ¨  Ö ¸ µ 1 Ïy  ”  ' Ÿ  ×  æ s   [5–7].

E-mail: [email protected]



$ í  ” ¸{ 9   ü @ Ò l  © œ\  _ K  \ P s  µ 1 ÏÒ q t   H B j

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m 7 £ §“ É r Neel õ  Brown ’ < Hz  ´ (loss)\  _ K " fs  . Neel

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  [8,9].



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 ³ ð€  `  ¦ Ò q t^ ‰& h ½ + Ë$ í s  a % ~“ É r Ó ü t| 9 – Ð  ïh A # Œ  ô  Ç .



ïh A Ó ü t| 9 – Ѝ  H  oÛ ¼à Ôê ø Í (dextran), PEG (polyethylene glycol), v ž Ðí ß –, z  ´o  , F K, ò ø ͙ è 1 p x  € ª œô  Ç Ó ü t| 9 s  s 6   x

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Ð  ïh A % i  . TEMÜ ¼– Ð S X ‰ “  ô  Ç  ” ¸{ 9    H ¨ î ç  H f ”  â s

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~

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+ þ

A$ í ÷ &  H l 2 £ § î ß –_  Ó ü t ~ ½ ÓÖ  ¦ (water-in-oil, reverse micelle)

½

¨› ¸  H  A _  õ & ñ `  ¦ : Ÿ x K  ë ß –[ þ t # Q& ’  . 3.5 g_  sodium dodecylbenzenesulfonate (NaDBS)\  ¦ 30 ml _  xylene (l  2

£ §, isomers plus ethylbenzene, 98.5%) \  0 l q # Œ" f È Ò" î K

| 9  M : t  œ í6 £ § \  ¦  6   x % i  . 0 A õ & ñ `  ¦  u €  

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 ¦ 500 rpm Ü ¼– Ð $ Ü ¼€  " f, Cobalt (II) chloride hexahy- drate (CoCl 2 -6H 2 O, 99%) ü < iron (III) nitrate nanohy- drate (Fe(NO 3 ) 3 -9H 2 O, 98%)  1:2– Ð [ O # Œ e ”   H à º6   xÓ  o 1.8 ml\  ¦ V , % 3  . 0 A ™ D ¥ ½ + Ë6   xÓ  o`  ¦ 16-18 r ç ß – 1 l x î ß – ƒ  5 Å q& h  Ü

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1.5 r ç ß – 1 l x î ß – …  ;…  ;y  ™ D ¥ ½ + ËÓ  o`  ¦ 40 C – Ð d ” + À I . s  õ & ñ

(3)

Fig. 1. (Color online) (a) TEM image of the silica-coated cobalt oxide nanoparticles (b) Particle size distributions for one hundred particles obtained from a TEM image.

1 l

x î ß – Ó ü t ~ ½ ÓÖ  ¦ (reverse micelle) î ß –\ " f  ïµ 1 Ïà Ô ` … s à Ô  

”

¸{ 9   + þ A$ í  ) a  . ! Ó P :, 0 A_  õ & ñ `  ¦ : Ÿ x K  + þ A$ í  ) a  ïµ 1 Ï à

Ô ` … s à Ô  ” ¸{ 9  \  ¦ z  ´o  – Ð  ïh A l  0 AK " f 0 A 6

  xÓ  o`  ¦ 40 C – Ð Ä »t  €  " f 4 ml_  TEOS (tetraethyle orthosilicate)\  ¦ È Ò{ 9  “ ¦, 500 rpmÜ ¼– Ð 6r ç ß – 1 l x î ß – $ # Q Å

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Ô  ” ¸{ 9    H  [ j— : r`  ¦ s 6   x # Œ l 2 £ § Ü ¼– РÒ'  { 9  & h  Ü

¼– Ð ì  r o  “ ¦, 13,000 rpm_  " é ¶ d ” ì  r o l \  ¦ : Ÿ x K  ¢ - a„  y  ì

 r o  % i  .



” ¸{ 9  _  — ¸€ ª œõ  ß ¼l \  ¦ › ' a ¹ 1 Ï l  0 AK  È Òõ „   ‰ & ³ p

 â (TEM, H-7600, Hitachi Ltd.)`  ¦  6   x % i  . Õ ªo 

“

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  l & h “   : £ ¤$ í _  › ' a ¹ 1 Ï`  ¦ 0 AK " f  H VSM (Lakeshore 7400)`  ¦  6   x % i  .  ” ¸{ 9  _   o† < Æ& h  $ í ì  rì  r$ 3 `  ¦ 0 A K

" f  H Ä »• ¸  ½ + Ëe  ¦  Ý ¼  ì  rF g l  (ICP, Thermo Jarrell Ash IRISAP)\  ¦ s 6   x % i  . Õ ªo “ ¦  $ í \ P “ : r ´ òõ _  › ' a

¹

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‚

  “ : r • ¸>  (PyroUSB CF, Calex Electronics Limited)\  ¦



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III. + s ÇÊ ÝÑ ÷ À X Ø8 ý

Figure 1(a) \  TEM Õ ªa Ë >s  Å Ò# Q4 R e ”  . Õ ªa Ë >\ " f ˜ Ð 1

p

w s   ” ¸{ 9  [ þ t“ É r ½ ¨+ þ As “ ¦ core-shell ½ ¨› ¸\  ¦ ˜ Ð# ŒÅ ғ ¦ e ”

 . Figure 1(b)\   H Fig. 1(a) \ " f 100> h_  { 9  \  ¦ ‚  

× þ

˜ # Œ f ”  â _  ì  r Ÿ í\  ¦ Õ ª 2 ;  כ `  ¦ ˜ Ð# ŒÅ ғ ¦ e ”  . ¨ î ç  H f ” 

 â

“ É r 17 nme ” `  ¦ › ' a ¹ 1 Ͻ + É Ã º e ”  .

Figure 2 \   H XRD z  ´+ « >u  Å Ò# Q4 R e ”  . Õ ªa Ë >\ " f

˜

Ѝ  H x ß ¼[ þ t“   (220), (311), (400), (422), (511), (440)“ É r

Fig. 2. (Color online) XRD patterns of the silica-coated cobalt ferrite nanoparticles. The indices of the crystal plane in the figure match with those of inverse cubic spinel structure.

Fig. 3. (Color online) FTIR spectra of the silica-coated cobalt ferrite nanoparticles.

%

i  Û ¼x 3 A q ½ ¨› ¸\ " f ˜ Ðs   H t à º(indices)ü < { 9 u ô  Ç . Õ ª o

“ ¦ (440)`  ¦ s 6   x # Œ ½ ¨ô  Ç     © œÃ º “a”  H 8.31 ˚ A – Ð" f

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¹

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– Ð  ïh A ) a  ïµ 1 Ïà Ô ` … s à Ô  ” ¸{ 9  _   â Ä º ∼3400, 1633, ∼1090, ∼800, ∼460 cm −1 \ " f f  ¨ à º{ \  ¦ ˜ Ð# Œï  r



 [15–17]. Õ ªo “ ¦ 1,105 cm −1   H ~ ½ Ó_  f  ¨ à º{   H Si-

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ing vibration) õ  Si-O-Fe_  ”  1 l x M :ë  H \  µ 1 ÏÒ q tô  Ç  כ s  

[18].  t } Œ •Ü ¼– Ð 610 cm −1 \  e ”   H  Œ •“ É r f  ¨ à º{   H Fe-O-

Si   ½ + Ë\  e ”   H Fe-O Û ¼à ÔY Ug A\  _ ô  Ç  כ s  . 0 Aü < ° ú  

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Fig. 4. (Color online) Hysteresis curve of the silica- coated cobalt ferrite nanoparticles at room temperature.

“

É r FTIR _    õ   H z  ´o    ïµ 1 Ïà Ô ` … s à Ô  ” ¸{ 9  

³

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s à Ô  ” ¸{ 9  _   l  s § 4 / B G‚  s  Å Ò# Q4 R e ”  . ˜ Ð 

§

4  (coercive force)s     t  · ú §6 £ §“ É r  ïµ 1 Ïà Ô ` … s à Ô



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¡l  M :ë  H s l • ¸  .

Ä

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´

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

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s à Ô ì  r ´ ú ˜r « Ñ\  ¦ y Œ •y Œ • 30, 22.5, 15 mg\  ¦ 0 l q“   [ j > h _

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€

ª œ“ É r ICP\  ¦ s 6   x # Œ y Œ •y Œ • ½ ¨ % i  . r « Ñ_  “ : r • ¸8 £ ¤& ñ

`

 ¦ 0 AK  & h ü @‚   G ' p" f\  ¦ r « Ñ 0 A 10 cm b  # Q”   0 Au \  à º f ”

Ü ¼– Ð Z  ~ € Œ ¤Ü ¼ 9, s   â Ä º r « Ñ_  0 Au \ " f “ : r • ¸ 8 £ ¤& ñ _

 spot f ”  ⠓ É r 0.5 cm s  . s   H r « Ñ\  ¦ { Œ ™“ É r : Ÿ x _  f ”  â õ  ° ú  “ ¦, s \     r « Ñ\  @ /ô  Ç ¨ î ç  H“ : r • ¸ 8 £ ¤& ñ  ) a  .

Figure 5 \  [ j r « Ñ 30, 22.5, 15 mg/ml_  y h A (heating) r

ç ß –\    É r à º6   xÓ  o_  “ : r • ¸    o\  ¦ ˜ Ð# ŒÅ ғ ¦ e ”  . [ j r 

«

Ñ — ¸¿ º 600 - 800œ í_  r ç ß –  â õ  Ê ê\   H [ jŸ í º ¡ ¤  H “ : r

•

¸“   42 C \  • ¸² ú ˜† < Ê`  ¦ ˜ Ð# ŒÅ ғ ¦ e ”   [20].  $ í  ” ¸{ 9 



\  _ K  µ 1 ÏÒ q t ) a \ P “ É r r « Ñ_  y Œ •  Òì  r _  “ : r • ¸\  ¦ Z  }“   .

s

 \ P \  _ K  r « Ñ_  „  ^ ‰& h “   “ : r • ¸   o ∆T  €  

∆Q = m W c W ∆T +m Si c Si ∆T +m Co c Co ∆T +m F e c F e ∆T (1)

Fig. 5. (Color online) Heating effect of the dispersions of the silica-coated cobalt ferrite nanoparticles.

ü

< ° ú  s  ³ ð‰ & ³ ) a  . # Œl " f c W , c Si , c Co , c F e   H Ó ü t, z  ´o 

,  ïµ 1 Ïà Ô, ^ o = 1 p x _  q \ P s “ ¦, m W , m Si , m Co , m F e   H r 

«

Ñ\  Ÿ í† < ʝ ) a Ó ü t (1 ml), z  ´o  ,  ïµ 1 Ïà Ô, ^ o = 1 p x _  | 9 | ¾ Ó

`

 ¦    · p . Õ ªo “ ¦  $ í  ” ¸{ 9  _  \ P “ : r ´ òõ \  ¦   

?

/  H SAR (specific absorption rate)“ É r  $ í  ” ¸{ 9   à º 6

  xÓ  o\  Ÿ í† < ʝ ) a  $ í  ” ¸{ 9  _  é ß –0 A | 9 | ¾ Ó { © œ \ P  µ 1 ÏÒ q tÒ  ¦ (dissipation heat) – Ð & ñ _ ÷ &Ù ¼– Ð, d ”  1`  ¦ s 6   x €  

SAR = ∆Q − ∆T m Co + m F e

= ∆T /∆t m Co + m F e

= [m W c W + m Si c Si + m Co c Co + m F e c F e ]

∼ = m W c W

m Co + m F e

 ∆T

∆t



(2) ü

< ° ú  s  & ñ _   ) a   [21,22]. 0 A d ” \ " f  t } Œ •_    H  d ” `  ¦

½

¨ô  Ç  כ “ É r Ó ü t _  q \ P “ É r c W = 4.2 J/g C – Ð" f c Si = 0.7 J/g C, c Co = 0.42 J/g C, c F e = 0.45 J/g C 1 p x õ  q “ §

€    H ° ú כs “ ¦, ¢ ¸ô  Ç, Ó ü t _  | 9 | ¾ Ó (1 g)“ É r à º6   xÓ  o\  ” > r F 

  H z  ´o  ,  ïµ 1 Ïà Ô, ^ o = 1 p x`  ¦ ½ + Ëô  Ç 8 ú x | 9 | ¾ Ó (30 mg)\  q  K

  Å Ò ß ¼l  M :ë  H s  .   " f  ïh A ) a  ” ¸{ 9  _  “ : r • ¸

\

 ¦ `  ¦ o   H X <  H ´ ú §“ É r \ P s  כ ¹½ ¨÷ &t  · ú §l  M :ë  H \  \ P “ : r ´ ò õ

\  _ K  µ 1 ÏÒ q t÷ &  H \ P _  @ / Òì  r“ É r Ó ü t _  “ : r • ¸\  ¦ `  ¦ o   H X

<  6   xÙ þ ¡ “ ¦ ½ + É Ã º e ”  . [ j r « Ñ\  @ /ô  Ç SAR“ É r y Œ •y Œ • 72, 51.10, 40.80 W/g Ü ¼– Ð > í ß –  ) a  . # Œl " f ∆T ∆t   H % ƒ6 £ § 60 œ í 1 l x î ß –_  “ : r • ¸   o\  ¦ s 6   x % i  . 0 A_    õ   H z  ´o 

– Ð  ïh A ) a  ïµ 1 Ïà Ô  ” ¸{ 9    $ í \ P “ : r ´ òõ \  ´ òõ 

&

h e ” `  ¦ ˜ Ð# ŒÅ ғ ¦ e ”   [21].

IV. + s Ç Â ] Ø

%

i  p ! s q ~ ½ ÓZ O Ü ¼– Ð z  ´o  – Ð  ïh A ) a  ïµ 1 Ïà Ô ` … s à Ô



” ¸{ 9  \  ¦ + þ A$ í % i  . TEMÜ ¼– Ð › ' a ¹ 1 Ïô  Ç  ” ¸{ 9  [ þ t

(5)

“ É

r ½ ¨+ þ As % 3 “ ¦, ¨ î ç  H f ”  â s  17 nm% i  . XRD– Ð › ' a ¹ 1 Ï ô

 Ç   & ñ $ í “ É r  ” ¸{ 9   % i  { 9 ~ ½ ÓÛ ¼x 3 A q ½ ¨› ¸e ” `  ¦ ˜ Ð# Œ Å

Ò% 3  . FTIR\ " f z  ´o  ü <  ” ¸{ 9  ü <_    ½ + Ë\  › ' aº  

 )

a f  ¨ à º{  › ' a ¹ 1 Ï÷ &% 3 “ ¦, s \  ¦ : Ÿ x K  z  ´o    ïµ 1 Ïà Ô ` …



s à Ô  ” ¸{ 9  \  ¸ ú ˜  ҂ à Ì÷ &# Q e ” 6 £ §`  ¦ ^  ¦ à º e ” % 3  .  

”

¸{ 9  _   l s § 4 / B G‚  \ " f  l s § 4 s  › ' a ¹ 1 Ï÷ &t  · ú §€ Œ ¤

“

¦, s   H  ” ¸{ 9   œ í © œ $ í `  ¦   Í Ç r`  ¦ ˜ Ð# ŒÅ Ò% 3  .

Õ

ªo “ ¦  ” ¸{ 9   à º6   xÓ  o_  \ P “ : r ´ òõ _  › ' a ¹ 1 Ï\ " f SARs 

\ P

“ : r ´ òõ \  6 £ x6   x ½ + É Ã º e ” `  ¦ & ñ • ¸_  ° ú כ`  ¦ ˜ Ð# ŒÅ Ò% 3  .   



: r& h Ü ¼– Ð z  ´o  – Ð  ïh A ) a  ïµ 1 Ïà Ô ` … s à Ô  ” ¸{ 9    H



$ í \ P “ : r ´ òõ \  6 £ x6   x ½ + É Ã º e ”   H Ó ü t o & h  : £ ¤$ í `  ¦ — ¸¿ º ˜ Ð

#

ŒÅ Ò% 3  .

P

c p 8 ý ò k >

s

 ƒ  ½ ¨  H ô  Dz D G õ † < ÆF é ß – (õ ] j    ñ: 2010-0021315)ƒ  

½

¨q  x 9 “ §¹ ¢ ¤ Â Ò õ † < Æl Õ ü t”  < É ª l F K  \ O q \  _ K  à º' Ÿ ÷ &

% 3

_ þ v m  .

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수치

Fig. 1. (Color online) (a) TEM image of the silica-coated cobalt oxide nanoparticles (b) Particle size distributions for one hundred particles obtained from a TEM image.
Fig. 4. (Color online) Hysteresis curve of the silica- silica-coated cobalt ferrite nanoparticles at room temperature.

참조

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