The designed bifunctional nanoparticles can act similar functions like core-shell structure nanoparticles, providing simultanously photoluminescence as labeling agent in biomedical appli[r]
Trang 1Original article
microemulsion method
a Faculty of Physics, Hanoi University of Science, Vietnam National University, Hanoi, 334 Nguyen Trai, Hanoi, Viet Nam
b University of Transport and Communications, 2 Cau Giay, Hanoi, Viet Nam
c Nano and Energy Center, Hanoi University of Science, Vietnam National University, Hanoi, 334 Nguyen Trai, Hanoi, Viet Nam
a r t i c l e i n f o
Article history:
Received 31 May 2016
Accepted 10 June 2016
Available online 17 June 2016
Keywords:
ZnS:Mn
Fe 3 O 4
Bifunctional nanoparticles
Magnetic materials
Inverse microemulsion
a b s t r a c t
ZnS:MneFe3O4 bifunctional nanoparticles were synthesized by inverse microemulsion method for biomedicine applications The bifunctional nanoparticles were combined from prepared ZnS:Mn and
Fe3O4nanoparticles in a SiO2cover matrix Results show that bifunctional nanoparticles, apart from exhibiting magnetism, have photoluminescence properties, which support the applications targeting biomedicinefluorescent diagnostics as well as magnetic cell sorting or drug delivery
© 2016 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)
1 Introduction
Multifunctional nanoparticles are of a great interest in recent
development due to the growing needs in biomedical applications
They have potential to integrate various functionalities such as
providing contrast for labeling agent, image-guided therapies,
targeted drug delivery, thermal therapies or simultaneously serve
as magnetic separator[1e4] At the beginning, core-shell
struc-tures were considered to improve appropriate physical as well as
chemical properties and combine them in one nanoparticle
Advanced polymer coating such as polyethylene glycol was usually
used as functionalizing agent to make the nanoparticles have good
bio-compatibility[5e9] Some semiconductor coatings have been
developed as photoluminescent shell to increase the luminescence
[10e12]as well as making a cover against the toxic element release
from core material, such as Se, Cd[11] In some other applications,
metal and silica shells were coated for protecting the core
mate-rials[13,14] However, the synthesis method of core-shell structure
referred tight conditions and expertise laboratory craftsmanship
In this paper, a simple method of inversed microemulsion was
used to prepare new bifunctional nanoparticles ZnS:MneFe3O4 from individual Mn-doped ZnS (ZnS:Mn) semiconductor nano-particles and Fe3O4magnetic nanoparticles in SiO2coating matrix ZnS:Mn semiconductor nanoparticles can be employed for label-ing of clinical tumor tissues[15] The magnetic nanoparticles with superparamagnetic properties can be used as targeted delivery of drug and/or gene, magnetic separation as well as magnetic ther-apies [16e19] The designed bifunctional nanoparticles can act similar functions like core-shell structure nanoparticles, providing simultanously photoluminescence as labeling agent in biomedical application, biocompatible and can be also purified by magnetic separator or can be used for drug delivery due to their magnetism, event under the coating of SiO2matrix
2 Experimental 2.1 Synthesis of ZnS:Mn nanoparticles ZnS:Mn nanoparticles were synthesized by ultrasound-assisted co-precipitation method using sodium sulphide (Na2S) as S2ion source ZnCl20.5 M were mixed with surfactance sodium dodecyl sulfate (SDS), CH3(CH2)11SO4Na) 0.25 M and Mn(CH3COO)20.5 M
to get precursor solution The molar ratio of Mn/Zn was 1/10 This solution was ultrasonicated with the pulse mode on:off being 2s:2s The ultrasonic power and the frequency was 225 W and
* Corresponding author Faculty of Physics, Hanoi University of Science, Vietnam
National University, Hanoi, 334 Nguyen Trai, Hanoi, Viet Nam.
E-mail address: namnh@hus.edu.vn (N.H Nam).
Peer review under responsibility of Vietnam National University, Hanoi.
Contents lists available atScienceDirect Journal of Science: Advanced Materials and Devices
j o u r n a l h o m e p a g e : w w w e l s e v i e r c o m / l o c a t e / j s a m d
http://dx.doi.org/10.1016/j.jsamd.2016.06.006
2468-2179/© 2016 The Authors Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi This is an open access article under the CC BY license
Journal of Science: Advanced Materials and Devices 1 (2016) 200e203
Trang 220 kHz, respectively During the ultrasonicating, Na2S solution was
slowly added into the precursor solution After 2 h, the ZnS:Mn
nanoparticles were collected by washing 5 times with distilled
water before being dispersed in isopropanol
2.2 Synthesis of Fe3O4nanoparticles
Fe3O4 nanoparticles were synthesized by co-precipitation
method[20,21]using Fe2þ/Fe3þwith 1:2 M ratios from the two
chloride salts of FeCl2and FeCl3, which were diluted to 0.01 M/
0.02 M concentration The mixed solution was vigorously stirred
and kept at 60C before NH4OH 30% was being added to have the
black color precipitation Thefinal solution was purified by
mag-netic separation with ethanol and distilled water several times to
decontaminate the auxiliary chemicals Fe3O4nanoparticles, then,
were dispersed in isopropanol
2.3 Synthesis of ZnS:MneFe3O4bifunctional nanoparticles
The bifunctional nanoparticles were combined from above two
kinds of nanoparticles by inverse microemulsion method The
in-verse microemulsion was created by mixing hydrophobic phase of
toluene and hydrophilic phase that was made from the mixture of
ZnS:Mn solution and Fe3O4 solution in isopropanol right after
synthesis and the solution of NH4OH with distilled water Under
sonic bath, tethraethylorthosilicate (TEOS) was added to react with
both types of particles
The morphology of the ZnS:Mn, Fe3O4and the ZnS:MneFe3O4
nanoparticles was investigated by transmission electron
micro-scope (TEM, JEOL- JEM1010) The structure of nanoparticles was
studied using X-ray diffractormeter (XRD, Bruker D5005) The
average crystallite size, d, is calculated from the line broadening
using Scherrer's formula: d¼ 0.9l/(Bcosq), where B is the half
chemical composition of the nanoparticles was studied by using an
energy dispersion spectroscopy (EDS) included in JEOL 5410LV
scanning electron microscope and the chemical bonding was
investigated by using Fourier Transformation Infra-Red (FTIR 6300,
Shimadzu) absorption Magnetic properties of samples were
studied by using DMS 880 Vibrating Sample Magnetometer (VSM)
Optical properties of sample were investigated by using the
Flourolog FL 3-22 photoluminescence (PL) spectroscopy (Jobine
Yvone Spex, USA)
3 Results and discussion
Fig 1shows the TEM images of the ZnS:Mn, Fe3O4, and the
ZnS:MneFe3O4nanoparticles The TEM image of ZnS:Mn does not
show very clear shape of nanoparticles, that may be due to the
amorphous cover of synthesized nanoparticles The TEM image of
the Fe3O4nanoparticles shows well-dispersed nanoparticles with
size of about 15 nm The TEM image of the ZnS:MneFe3O4
nano-particles shows the colloids with the mean size of around 45 nm
and does not show small colloids of around 15 nm and 5 nm, which
are typical sizes of Fe3O4and ZnS:Mn nanoparticles, respectively
The ZnS:MneFe3O4 nanoparticles contain ZnS:Mn and Fe3O4
nanoparticles inside This microstructure of the ZnS:MneFe3O4
nanoparticles is supported by the results of measurements
dis-cussed below
The XRD patterns of the Fe3O4, ZnS:Mn and ZnS:MneFe3O4
co-precipitation synthesized Fe3O4nanoparticles is characteristic of
the FeO structure with diffraction peaks at 30.1, 36.0, 43.9,
53.6, 57.5va 63.1which can be assigned with (200), (311), (400),
(422), (511) va (440) reflections, respectively Fe3O4nanoparticles have an inverse spinel structure with oxygen forming face-centered cubic (fcc) structure with F3dm space group From
8.36 ± 0.04 Å Using Scherrer's formula, the particle size was estimated to be around 10 nm The pattern of the synthesized ZnS:Mn nanoparticles shows diffraction peaks at 29.1, 48.1, 57.5
Fig 1 TEM images of (a) ZnS:Mn, (b) Fe 3 O 4 and (c) ZnS:MneFe 3 O 4 nanoparticles C.T Dung et al / Journal of Science: Advanced Materials and Devices 1 (2016) 200e203 201
Trang 3They can be ascribed as (111), (200), (220) reflections, respectively.
The obtained lattice parameter of 5.32± 0.02 Å for fcc structure
and the particle size was estimated to be around 4.7 nm, in
agreement with particles size observed by TEM image The XRD
typical amorphous structure of SiO2coated matrix with the sign of
the (311), (400), (422), (511) reflections of Fe3O4structure and the
weaker (200), (220) reflections of ZnS:Mn structure The SiO2
cover could absorb X-ray, leading to the disappearance of some
XRD peaks of ZnS:Mn and Fe3O4nanoparticles
The FTIR absorption spectra of the Fe3O4, ZnS:Mn and the
ZnS:MneFe3O4nanoparticles are shown inFig 3 All the spectra
show the broad peaks at 3400 cm1of OeH stretching vibration
assigned to CeO vibration of CO2[22,23]related to the air
back-ground of the measurement These peaks are due to the presence
of CO2and H2O in all the samples The spectrum of ZnS:MneFe3O4
shows typical absorption peaks of ZnS:Mn such as peaks at 1106,
617 and 465 cm1of ZneS bonding or peak at 1174 cm1 which
appears when Mn2þis doped into ZnS crystal[24] The two peaks
ZnS:MneFe3O4samples, are due to the microstructure formation
of ZnS:Mn nanoparticles[24] The spectrum of ZnS:MneFe3O4also shows typical absorption peaks of Fe3O4 nanoparticles such as peak at 560 cm1of FeeO vibration[25] Furthermore, this spec-trum has peaks of SiO2such as peaks at 797 cm1and 960 cm1
[26,27] These results and the XRD results support that the ZnS:MneFe3O4 nanoparticles were successfully combined from ZnS:Mn and Fe3O4nanoparticles in SiO2matrix
Fig 4 shows the PL spectrum of ZnS:Mn and that of ZnS:MneFe3O4nanoparticles excited at 335 nm The spectrum of ZnS:Mn nanoparticles have the peak at 438 nm which is originated from defects caused by missing of some Zn ion in ZnS crystal structure, and the peak at 595 nm which is originated from the
4T1/6A1 transition in 3d5electronic layer of Mn2þion[28e30] The spectrum of ZnS:MneFe3O4nanoparticles also has two pho-toluminescence peaks, one at 595 nm and the other at 425 nm, similar to that of ZnS:Mn However the intensity of the peak at
595 nm of ZnS:MneFe3O4 nanoparticles is lower than that of ZnS:Mn nanoparticles This can be explained by the presence of
Fe3O4and SiO2in ZnS:MneFe3O4nanoparticles, which reduces the
influence of Mn2 þ ion on PL result These results indicate that
ZnS:MneFe3O4nanoparticles contain ZnS:Mn nanoparticles and have similar PL properties with ZnS:Mn nanoparticles in visible region, which can be used for labeling application in biomedicine
Fig 5shows magnetization curves measured on the ZnS:Mn,
Fe3O4and ZnS:MneFe3O4nanoparticles It can be seen that the magnetization of ZnS:Mn nanoparticles is very low, of 1 emu/g, compared to those of Fe3O4 and ZnS:MneFe3O4 nanoparticles, which reaches around 59.4 emu/g and 31.7 emu/g at 13.5 kOe, respectively The fact that the ZnS:MneFe3O4nanoparticles have lower magnetization can be explained by the presence of ZnS:Mn nanoparticles inside the sample as well as the presence
similar to Fe3O4 nanoparticles, indicating that the synthesized ZnS:MneFe3O4nanoparticles contain Fe3O4nanoparticles inside
Fig 2 X-ray patterns of ZnS:Mn, Fe 3 O 4 and ZnS:MneFe 3 O 4 nanoparticles.
and ZnS:MneFe
Fig 4 Photoluminescence spectra of ZnS:MneFe 3 O 4 and ZnS:Mn nanoparticles C.T Dung et al / Journal of Science: Advanced Materials and Devices 1 (2016) 200e203
202
Trang 4These results also support the successful combining of Fe3O4and
ZnS:Mn nanoparticles in SiO2matrix The magnetic properties of
nanoparticles investigated also show that ZnS:MneFe3O4
nano-particles can be used for magnetic delivery, therapies or DNA
separating applications in biomedicine
4 Conclusions
ZnS:MneFe3O4 bifunctional nanoparticles were successfully
synthesized from ZnS:Mn and Fe3O4nanoparticles in
bifunctional nanoparticles have photoluminescence similar to
ZnS:Mn photoluminescence nanoparticles and magnetic propeties
similar to Fe3O4 magnetic nanoparticles, which support their
use in both labeling and separating applications in biomedicine
Furthermore, with the biocompartible SiO2 cover matrix, these
nanoparticles can be easily surface-modified in many
biomedicine-application purposes
Acknowledgment
This paper is dedicated to the memory of Peter Brommer He
was a good friend of the Vietnamese physicists during the years of
cooperation between the Hanoi and Amsterdam Universities With
his deep knowledge of 'Magnetism of Metals' he was always ready
to assist his colleagues We are grateful for his involvement in the
cooperation over a period as long as thirty years
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C.T Dung et al / Journal of Science: Advanced Materials and Devices 1 (2016) 200e203 203