Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
DOI 10.1007/s10856-015-5466-7
Received: 10 October 2014 / Accepted: 25 January 2015 / Published online: 18 February 2015
Springer Science+Business Media New York 2015
1 Introduction
After decades of intense study, the superparamagnetic
nanoparticles have been explored for various biomedical
applications, including magnetic resonance imaging [1, 2],
drug targeting [3] magnetic separation [46] and hyperthermia [79]. In hyperthermia, an AC magnetic field is
S. Sabale (&) X. Zhu M. Xin H. Chen
Laboratory of Biosensing Technology, School of Life Sciences,
Shanghai University, Shanghai 200444,
Peoples Republic of China
e-mail: srsabale@gmail.com
S. Sabale V. Jadhav
P.G. Department of Chemistry, Jaysingpur College,
Jaysingpur 416101, MH, India
V. Khot
Center for Interdisciplinary Research, D. Y. Patil University,
Kolhapur 416006, MH, India
123
127 Page 2 of 9
2 Experimental
2.1 Polyol synthesis of superparamagnetic MFe2O4
(M = Zn, Ni, Mn, Co) nanoparticles
MFe2O4 (M = Zn, Ni, Mn, Co) superparamagnetic
nanoparticles were prepared by the simple polyol method.
The reagents, ferric chloride (FeCl3), manganese chloride
(MnCl24H2O), nickel chloride NiCl26H2O,zinc chloride
(ZnCl2), cobalt chloride (CoCl26H2O), diethylene glycol,
ethanol, ethyl acetate and sodium acetate were used are of
analytical grade and are used without further purification.
The mixture of 5.0 mmol ferric chloride and 2.5 mmol of
zinc chloride, nickel chloride, manganese chloride and
cobalt chloride were mixed in 60 mL diethylene glycol to
obtain ZnFe2O4, NiFe2O4, MnFe2O4 and CoFe2O4 respectively. The mixture was stirred to dissolve the salts.
About 3.6 g sodium acetate was added to clear solution and
123
stirred until it dissolves. The whole clear solution was refluxed at controlled temperature of 210 C for 3 h. The
obtained solution was cooled at room temperature and kept
to settle the particles under magnetic field. The supernatant
was drained off and the MNPs were repeatedly washed
with anhydrous ethanol/ethyl acetate mixture (1:2 v/v) to
remove excess diethylene glycol and then air dried at room
temperature to obtain black sample powders.
2.2 Characterization of obtained nanoparticles
The structural and phase identification were carried out
from X-ray diffraction patterns using Rigaku Miniflex 600
X-ray deffractometer equipped with a crystal monochromator employing copper radiation (CuKa) of wavelength
at 40 kV, 25 mA over the 2h range 10100.
1.5418 A
The spectral studies were carried out using FTIR, Alpha
ATR Bruker (Eco ATR 5004000 cm-1) for structural
elucidations. Transmission electron microscopy (JEOL3010 at an operating voltage of 300 kV) was used to observe the morphology and size of the prepared MNPs. The
magnetic properties like saturation magnetization, coercivity and remnance magnetization were recorded from M
H curves obtained using alternating gradient magnetometer
(AGM), Micromeg Tm 2900; Princeton measurement
corporation at room temperature.
2.3 Induction heating studies
Induction heating studies of superparamagnetic MFe2O4
nanoparticles were performed to find the ability of magnetic nanoparticles for cancer hyperthermia treatment. The
studies were carried out in plastic microcentrifuge tube
(1.5 mL) using the instrument (Easy Heat 8310, Ambrell,
UK) with 6 cm diameter coil (4 turns). To maintain the
ambient temperature of the coil, water circulation in coil
was provided. Sample (1020 mg) suspended in 1 mL of
distilled water was placed at the centre of the coil and the
frequency 276 kHz was applied. Samples were treated for
20 min with desired magnetic field (H) from 251.4 to
419.0 Oe. Temperature rise was measured using an alcohol
thermometer with accuracy 0.1 C.
2.4 Cell viability
For this study the TBDE Assay method was adopted to determine the toxicity of nanoparticles. Adenocarcinoma lung
cancer cell line A549 was used and the detailed toxicity
studies were done in School of Life Sciences, Shanghai
University, Shanghai. The cells were grown in RPMI-1640
medium supplemented with 10 % fetal bovine serum
(KeyGen Biotech Co. Nanjing, China) and incubated for
24 h in a 5 % CO2 incubator at 37 C. After 24 h, the old
Page 3 of 9 127
440
442
333
422
331
NiFe2O4
MnFe2O4
CoFe2O4
ZnFe2O4
Intensity (A.U.)
400
220
311
25
30
35
40
45
50
55
60
65
70
75
2 (Degree)
with two hydroxyl groups, DEG can hold free metal ions
tightly in the solution. With the addition of NaAc into the
solution, CH3COO- is attracted to the vicinity of the metal
ions, assisting in the DEG-mediated conversion of metal
salts into spinel phase sample under reaction temperature
of 200 C. [26]
Phase and structure of as synthesized MNPs were elucidated by X-ray diffraction pattern (Fig. 1). XRD patterns of
ZnFe2O4, NiFe2O4, MnFe2O4 and CoFe2O4 were well matched with standard JCPDS file number 82-1049, 10-0325,
38-0430 and 22-1086 of respective ferrites. The formation of
spinel phase cubic ferrite with space group fd3 m is clearly
confirmed from the XRD. Absence peaks (210) and (300)
confirms the phase purity of prepared ferrites.
The crystallite size of these as synthesized MNPs was
estimated from the full width at half-maximum (FWHM)
of strongest diffraction peak (311) using the Scherrers
formula [27],
D
0:9k
;
b cos h
Table 1 Crystallite size calculated from XRD (DXRD), TEM diameter (DTEM), lattice constant (a), X-ray density (DX), surface area (S), volume
(a3), coercivity (Hc), saturation magnetization (Ms) and remnant magnetization (Mr) of obtained MNPs
Sample
DXRD (nm)
DTEM (nm)
)
a (A
Dx (g/cm3)
S (m2/g)
a3 (cm3)
ZnFe2O4
8.35
10.0
8.5471
5.294
135.73
604.85 9 10-24
NiFe2O4
8.10
7.0
8.3754
5.299
139.78
587.52 9 10-24
MnFe2O4
7.13
7.0
8.4079
5.088
165.39
594.38 9 10-24
CoFe2O4
4.0
4.0
8.4557
5.154
291.04
604.57 9 10-24
Hc (Oe)
Ms (emu/g)
Mr (emu/g)
67.3
41.06
0.6249
20.04
17.49
0.0213
44.52
51.99
0.5225
48.01
0.7239
123.8
123
127 Page 4 of 9
30
ZnFe 2O 4
NiFe 2O 4
MnFe 2O 4
CoFe 2O 4
Moment (emu/g)
1076
1399
2917
1565
40
3733
Transmittance (A.U.)
50
20
10
0
-10
ZnFe2O4
NiFe2O4
MnFe2O4
CoFe2O4
-20
532
-30
-40
-50
4000
3500
3000
2500
2000
1500
1000
500
-1
-60
-10000 -7500
-5000
-2500
2500
5000
7500
10000
Fig. 3 TEM images of a ZnFe2O4; b NiFe2O4; c MnFe2O4; d CoFe2O4 MNPs, the inset shows SAED pattern corresponds to XRD patterns
123
Page 5 of 9 127
60
A 48
ZnFe2O4
NiFe2O4
MnFe2O4
CoFe2O4
55
44
Temperature ( C)
Temperature ( C )
50
45
170.28 sec
40
251.4 Oe
335.2 Oe
419.0 Oe
46
35
42
237 sec
40
38
36
34
32
30
30
28
0
25
0
200
400
600
800
1000
B 52
48
1000
1200
44
42
886 sec
160 sec
40
38
36
34
32
30
44
191.9 sec
Temperature ( C)
48
800
46
251.4 Oe
335.2 Oe
419.0 Oe
600
251.4 Oe
335.2 Oe
419.0 Oe
50
Temperature ( C)
52
400
Time (seconds)
Time (seconds)
200
1200
28
893.0 sec
356.2 sec
26
40
0
36
200
400
600
800
1000
1200
Time (seconds)
32
28
24
200
400
600
800
1000
1200
800
1000
1200
Time (seconds)
B 60
251.4 Oe
335.2 Oe
419.0 Oe
56
48
Temperature ( C)
52
44
172.9 sec
40
422.7 sec
36
32
28
24
0
200
400
600
Time (seconds)
123
127 Page 6 of 9
ZnFe2O4
NiFe2O4
MnFe2O4
CoFe2O4
Concentration
(mg mL-1)
SAR (W/g)
(251.4 Oe)
(335.2 Oe)
(419.0 Oe)
10
14.1
42.26
28.19
20
3.56
8.9
12.5
10
20
1.8
10
20
1.8
10
14.1
21.14
35.24
20
7.12
14.24
28.5
123
Page 7 of 9 127
Fig. 10 IFM images of cell lines a control; b, c In medium containing 0.6 mg ZnFe2O4 and CoFe2O4 MNPs after 48 h incubation period
123
127 Page 8 of 9
than 10 nm were obtained by this method. This study reveals that, doping of transition metals in the ferrite will
affect its magnetic properties which directly alter its
threshold hyperthermia temperature. Hence by controlling
the temperature, time and doping metal it will be possible
to control and tune the size and magnetic properties of
ferrite desired for hyperthermia applications. From this
study it is also concluded that, only ZnFe2O4 and CoFe2O4
MNPs are able to produce threshold hyperthermia temperature. The cell viability of these MNPs is also appreciable for in vivo application studies.
Acknowledgments One of author (Dr. Sandip Sabale) is thankful to
Prof. Dr. Genxi Li for his valuable discussion during this research
work. Authors are also thankful to Dr. N. Basavaiah, IIGM, Mumbai,
India for magnetic measurements. Authors extend their vote of thanks
to D.S.T.-New Delhi for sanctioning funds under DST-FIST program
to Jaysingpur College, Jaysingpur.
4 Conclusion
Refluxing in polyol method was used to synthesize
ZnFe2O4, NiFe2O4, MnFe2O4, and CoFe2O4 MNPs. These
prepared nanoparticles are further characterized for its
application in cancer hyperthermia application. Quasi
spherical superparamagnetic nanoparticles with size less
123
References
1. Jung CW, Jacobs P. Physical and chemical properties of superparamagnetic iron oxide MR contrast agents: ferumoxides,
ferumoxtran, ferumoxsil. Magn Reson Imaging. 1995;13(5):66174.
2. Gupta AK, Gupta M. Synthesis and surface engineering of iron
oxide nanoparticles for biomedical applications. Biomaterials.
2005;26(18):39954021.
3. Alexiou C, Jurgons R, Schmid RJ, Bergemann C, Henke J, Erhard
W, Huenges E, Parak F. Magnetic drug targeting-biodistribution
of the magnetic carrier and the chemotherapeutic agent mitoxantrone after loco regional cancer treatment. J Drug Target.
2003;11:13949.
4. Melville D, Paul F, Roath S. Direct magnetic separation of redcells from whole blood. Nature. 1975;255(5511):706.
5. Bahaj AS, James PAB, Moesschler FD. A comparative study of
the magnetic separation characteristics of magnetotactic and
sulphate reducing bacteria. J Appl Phys. 1998;83:64446.
6. Hergt R, Hiergeist R, Zeisberger M, Glockl G, Weitschies W,
Ramirez LP, Hilger I, Kaiser WA. Enhancement of AC-losses of
magnetic nanoparticles for heating applications. J Magn Magn
Mater. 2004;280:35868.
7. Hergt R, Hiergeist R, Hilger I, Kaiser WA, Lapatnikov Y, Margel
S, Richter U. Maghemite nanoparticles with very high AC-losses
for application in RF-magnetic hyperthermia. J Magn Magn
Mater. 2004;270:34557.
8. Chan DCF, Kirpotin DB, Jr, Bunn PA. Magnetic nanoparticles as
contrast agents for MR imaging. In: Hafeli U, editor. Scientific
and clinical applications of magnetic carriers. New York: Plenum
Press; 1997.
9. Hiergeist R, Andra W, Buske N, Hergt R, Hilger I, Richter U,
Kaiser W. Application of magnetite ferrofluids for hyperthermia.
J Magn Magn Mater. 1999;201:4202.
10. Khot VM, Salunkhe AB, Thorat ND, Phadtare MR, Pawar SH.
Induction heating studies of combustion synthesized MgFe2O4
nanopartilces for hyperthermia applications. J Magn Magn Mater.
2013;332:4851.
11. Park J, An K, Hwang Y, Park JG, Noh HJ, Kim JY, Park JH,
Hwang NM, Hyeon T. Ultra-large-scale synthesis of monodisperse nanocrystals. Nat Mater. 2004;3:8915.
12. Lee Y, Lee J, Bae CJ, Park JG, Noh HJ, Park JH, Hyeon T.
Large-scale synthesis of uniform and crystalline magnetite
13.
14.
15.
16.
17.
18.
19.
20.
21.
Page 9 of 9 127
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
123