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spectroscopy of CTAB modulated interactions of

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Cite this: RSC Adv., 2017, 7, 3628

magnetic nanoparticles with biomolecules†
Delina Joseph,a Raul D. Rodriguez,b Akash Verma,b Elaheh Pousaneh,c
Dietrich R. T. Zahn,b Heinrich Langc and Sudeshna Chandra*a

In this study, we use cyclic voltammetry (CV) to depict the association of magnetic iron oxide nanoparticles
(MNPs) with two different coating materials namely, bovine serum albumin (BSA) and dextran. The role of
a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB) in stabilizing the MNPs and
augmenting the association with BSA and dextran is also investigated. CV of the MNPs/CTAB systems
shows a diffusion-controlled mechanism on interaction with BSA and dextran. In the presence of CTAB,
the reduction potential of MNPs shifted to a higher value indicating hindrance in the electron transfer
process. Raman spectroscopy is used to study the structural change of MNPs during the associations.
Surface-enhanced Raman spectroscopy (SERS) provides an insight into the mode of interaction by
enhancing the otherwise weak signals arising due to Raman active carbon skeletal modes in organic
Received 3rd November 2016
Accepted 22nd December 2016
coating materials. BSA tends to associate with the MNPs by diffusing through the CTAB molecule by
hydrophobic interactions, while dextran is attached with the hydrophilic head groups of CTAB. Zeta
DOI: 10.1039/c6ra26235j
potential and saturation magnetization of the nanoparticles show good colloidal stability and retention of
[Link]/advances magnetic properties, respectively after coating.

polysaccharide moieties remain a preferred choice of coating

Introduction material due to their inherent biocompatibility.
Magnetic iron oxide (Fe3O4) nanoparticles (MNPs) are next Surfactants are widely used during the synthesis of nano-
generation high performance materials in the eld of biomed- particles since they act as a capping agents preventing nano-
ical applications like diagnostics, hyperthermia and as thera- particle aggregation.10,11 Besides stabilizing, surfactants can
peutic vehicles.1,2 The unique magnetic properties of MNPs also play a major role in enhancing the binding interaction of
allow them to be guided by external magnetic elds and hence the MNPs with biomolecules. In an attempt to understand the
they are utilized as MRI contrast agents for targeted drug or role played by cationic and anionic surfactant, hexadecyl-
gene delivery, and for cell tracking.3,4 To address the key issues trimethylammonium bromide (CTAB) and sodium dodecyl
of MNPs like size, dispersibility, macrophage invasion and sulfate (SDS) respectively at the interface of MNP core, bare and
cytotoxicity, normally MNPs are stabilized using various coating surfactant modied MNPs were investigated with BSA and
materials. By the virtue of nanoscale dimension coupled with dextran molecules.12,13
a cytocompatible surface coating, MNPs can pass through blood Cyclic voltammetry (CV) serves as a fast, simple, sensitive
vessels and penetrate into cell barriers to interact with cell and cost effective technique to study the response of various
organelles and provide organo-specic therapeutics.5,6 Some of materials with different analytes.14–16 CV is also helpful in
the coating materials used for this purpose include protein, elucidating the reaction mechanism of a system. Yadav et al.
polysaccharides, surfactants and polymers.7–9 Simple biological recently explored the use of CV to understand the role of
compounds produced by living organisms, such as protein or graphene/titanium oxide modied electrode in charge transport
and diffusion mechanism.17 Similarly, Oliveira et al. studied the
interaction of quinones with amino acids and thiols using CV.18
a
Department of Chemistry, Sunandan Divatia School of Science, NMIMS University, The study of electrochemical behavior like redox reaction of
Vile Parle (West), Mumbai-400056, India. E-mail: [Link]@[Link] metals at the electrode surface is also well investigated.19 On
b
Technische Universität Chemnitz, Faculty of Natural Sciences, Institute of Physics, similar lines, the electrochemistry of magnetite in bulk had
Semiconductor Physics, 09107 Chemnitz, Germany
c
been established,20–22 however, very few works have investigated
Technische Universität Chemnitz, Faculty of Natural Sciences, Institute of Chemistry,
it in its nanoscale form.23,24
Inorganic Chemistry, 09107 Chemnitz, Germany
† Electronic supplementary information (ESI) available. See DOI:
Raman spectroscopy is a very sensitive and reliable technique
10.1039/c6ra26235j to monitor the structural and chemical changes in a molecule.

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With the advent of SERS, the limitation in Raman spectroscopic (Horiba JY). The laser wavelengths used for the study were
technique to recognize weak signals from noise signals were also 785 nm for conventional Raman and the 532 nm laser line for
solved. Some of the recent works25–28 reported in the analysis of SERS since the plasmonic nanoparticles used were resonant in
biomolecules using SERS highlights the importance of such that range. Laser power of 2 mW was incident on the samples
studies with respect to advances in research. Molecular associ- with a 80 long working distance objective in the backscattering
ation of the iron oxide nanoparticles with protein and poly- geometry. The scattered signal was analyzed using a diffraction
saccharide in presence of CTAB was probed using this technique. grating of 1200 lines per mm. The acquisition time was 10 s for
Knowledge of these interfacial association and their structure are an average of 10 spectra per sample. The nanoparticles samples
imperative in the design of a biocompatible MNPs.3,29 were prepared by incubating the MNPs/CTAB solution with BSA
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In this study, cyclic voltammetry was used to unearth the and dextran for 2 h. The magnetic sample mixture was decanted
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electrochemical behavior of MNPs/CTAB and their interaction using bar magnet and further rinsed with DI water 3–4 times
with biomolecules. Detailed investigation of the nanoparticles along with subsequent magnetic separation before being
surfaces by confocal Raman spectroscopy and SERS gave an vacuum dried. Thus surfactant mediated nanoparticles with BSA
insight into the conformational changes that occurred during and dextran coatings were obtained and named as MNPs/CTAB–
the molecular association and the mode of interaction. BSA and MNPs/CTAB–dextran respectively. For recording SERS
spectra, Ag nanoparticles cages were used on a silicon substrate.
Typical sample preparation method for SERS consisted of drying
Experimental
5 ml Ag nanoparticles over silicon substrate and then 3 ml of
Reagents sample solution was added on it and then dried.
Fatty acid free bovine serum albumin (BSA) $ 98%, dextran
from Leuconostoc spp. (Mr 15 000–25 000) $ 98%, CTAB $ 99%
were purchased from Sigma-Aldrich, Germany. All other
Results and discussion
chemicals were of analytical grade and used as received. MNPs Electrochemical performance of MNPs and MNPs/CTAB
were synthesized by chemical co-precipitation and were char- towards bovine serum albumin (BSA)
acterized using various techniques (see ESI S1†). Deionized (DI) The electrochemistry of MNPs proceeds via the redox reactions
water was used as the solvent medium for all experiments. of Fe3+/Fe2+. However the redox process is affected due to the
interaction of nanoparticles with the associating molecules.
Electrochemical studies Cyclic voltammetry helps to monitor the electron transfer effi-
Cyclic voltammetry was used to study the electrochemical ciently and determine the energetic forces driving the interac-
behaviour of the MNPs/CTAB system. The CV measurements tion over a wide potential range.
were performed on a CH Instrument Model 660D electro- Fig. 1 shows the cyclic voltammograms of MNPs in a poten-
chemical workstation (CH Instruments Inc., US) using a 3-elec- tial window of 1 to +1 V, at a scan rate of 50 mV s 1. The
trode single-cell system. Phosphate buffer solution (0.1 M) and negative potential at 0.62 V signies the reduction peak of
KCl solution (0.1 M) was used as electrolyte and supporting MNPs. Cyclic voltammetry studies in previous reports proved
electrolyte respectively. Pt-Wire and Ag/AgCl electrodes were various pathways of magnetite reduction as under different
employed as counter and reference electrodes respectively. All experimental conditions.24,30 Basically, Fe3+ of MNPs are
the solutions were degassed and purged with nitrogen gas prior reduced to Fe2+ according to the following equation:
to electrochemical measurements to eliminate the presence of
Fe3O4 + 8H+ + 2e / 3Fe2+ + 4H2O (1)
dissolved oxygen and the studies were carried out at room
temperature. Glassy carbon electrode (GCE) of 2 mm diameter
was used as the working electrode. GCEs were polished with 1,
0.3, and 0.05 mm slurries of alumina powder and thoroughly
rinsed with DI water. The electrodes were alternatively sonicated
in water and methanol for 10 min and this process was repeated
4–5 times. MNPs and MNPs/CTAB sample solutions were
prepared comprising of (0.1 mg ml 1) MNPs and MNPs in
2.2 mM CTAB (above post micellar surfactant concentration),
respectively. 20 ml of the nanoparticles were deposited on the
GCE surface and were air-dried overnight to obtain a thin lm
coating of the nanoparticles on the electrode. The modied
electrodes were then subjected to cyclic voltammetry for evalu-
ating their electrochemical interaction towards BSA and dextran.

Raman spectroscopic studies

Fig. 1 Cyclic voltammograms of modified electrodes with and
Raman spectra for the MNPs/CTAB–dextran and MNPs/CTAB– without 0.1 mg ml 1 BSA and 0.2 mg ml 1 dextran respectively at
BSA systems were obtained on Xplora Raman spectrometer a scan rate of 50 mV s 1.

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In MNPs–BSA system as seen in Fig. 1, an enhancement of

redox peak currents was noticed. BSA normally possesses
intrinsic electroactivity due to presence of tyrosine and trypto-
phan residues.31,32 By associating with the MNPs, the residual
amino acids are oxidized and an anodic peak is observed as
shown in Fig. 1. However the potential separation (DEp) for the
MNPs–BSA increases to 250 mV from an initial DEp of 16.6 mV
of MNPs, indicating a slow electron transfer kinetics15,33 and
a quasi-reversible association of nanoparticles with BSA.
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In the MNPs/CTAB system, a prominent reduction peak was

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observed at 0.48 V and hence a higher reduction potential

compared to MNPs. This shi can be attributed to the insu-
lating effect provided by the CTAB layer, which decreases the
electron transfer process of the MNPs redox species. For MNPs/
CTAB–BSA the reduction potential was observed at 0.53 V. The
shi of the reduction potential to lower side signied an easy
reduction process and an intercalative binding of the MNPs/
CTAB with BSA. However, since the ratio of the anodic to
cathodic peak current deviated from unity, it can be presumed
that the association is irreversible. In this system, wherein
a surfactant modied electrode was used, the peak potential
separations were recorded as 232 mV and 281 mV for MNPs/
CTAB and MNPs/CTAB–BSA, respectively. Peak separation is
a function of the rate constant for electron transfer and hence
Fig. 2 Peak current versus Oscan rate plot for (A) MNPs–BSA and
a higher value denotes slow electron kinetics involved in the
MNPs/CTAB–BSA system and (B) MNPs–dextran and MNPs/CTAB–
redox activity of the system. dextran system.

Electrochemical performance of MNPs and MNPs/CTAB

towards dextran Diffusion coefficients were calculated using Randle–Sevcik
Fig. 1 also depicts the cyclic voltammogram of the modied equation33 and are given in Table 1. A steady decrease in
electrodes towards dextran in a potential window of 1 to +1 V diffusion coefficient in both MNPs/CTAB–BSA and MNPs/
at a scan rate of 50 mV s 1. Since dextran is a non-electroactive CTAB–dextran were observed due to the presence of a CTAB.
material, it is not expected to contribute in the electron transfer
process. This is experimentally veried by the slight reduction Raman spectroscopic studies
in the peak current. The CV scan of MNPs/CTAB–dextran
Normally for metal oxides, intense Raman bands are observed up
showed the reduction peak of CTAB as observed in the BSA
to the 700 cm 1 region. This region serves as ngerprint spectral
system. An irreversible nature of association was also observed
window for comparison with the bare MNPs. Magnetite has 5
in MNPs–dextran and MNPs/CTAB–dextran system as the ratio
phonon modes (A1g + Eg + 3T2g) that are Raman active.34 However
of anodic and cathodic peak current was above 1 for both
these peaks are very sensitive to various parameters, including
systems. The peak shape and peak separation also denotes
laser power and acquisition time. Hence, the Raman spectra of
a slow electron transfer in dextran system. The potential sepa-
MNPs oen show peaks corresponding to mix phases of more
rations (DEp) observed for the MNPs–dextran and MNPs/CTAB–
stable iron oxide forms like maghemite and hematite.35,36 In
dextran systems were 35.5 mV and 170 mV, respectively.
particular, the laser power was shown to induce the transition of
magnetite to hematite for bulk surfaces.37 In this study, we
Effect of scan rate towards BSA and dextran observed the transition to hematite phase even for laser power as
All the four systems with the modied electrodes were scanned low as 100 mW under near-infrared excitation (785 nm). Here we
at different scan rates from 5 to 200 mV s 1. The value of DEp exploit this situation to study the impact of different organic
was seen to increase with the increasing sweep (scan) rate coatings on the magnetite/hematite phase transition.
in MNPs/CTAB–BSA and MNPs/CTAB–dextran. Further, the Raman spectra for MNPs/CTAB, MNPs/CTAB–BSA and MNPs/
peak currents obtained were plotted as a function of the square CTAB–dextran were compared with pristine MNPs displaying the
root of scan rate (Fig. 2A). The MNPs/CTAB–BSA nanoparticles typical spectra of hematite as shown in the normalized spectra in
exhibited linearity only above 20 mV s 1 which indicates Fig. 3. The spectra are characterized by the two A1g and the ve Eg
a diffusion controlled mechanism only at higher scan rates. modes of hematite. The broad background at 670 cm 1 can be
However, MNPs/CTAB–dextran (Fig. 2B) showed a linear attributed to the remaining magnetite phase which also features
response of peak current indicating diffusion controlled a lower Raman cross-section than hematite. The most remark-
mechanism for all the scan rates investigated herein. able differences for the nanoparticles with different coatings

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Table 1Diffusion coefficient of various nanoparticles as evaluated by appears in the Raman spectra as a broadening of the phonon
Randle–Sevcik equation modes and down shi. This could be related to a decrease in the
electronic contribution to heat conductivity in agreement with
Diffusion coefficient
System (cm2 s 1) the results observed in the electrochemical results in the section
above. We also observed that the intensity ratios for the different
MNPs 1.27  10 4
samples correlate with the diffusion coefficients determined by
MNPs/CTAB 0.40  10 4
cyclic voltammetry (see Table 1). The systems with lower diffu-
MNPs–BSA 3.11  10 4

MNPs/CTAB–BSA 0.90  10 4 sion coefficient show large A1g/Eg ratios (and vice versa) and
0.88  10 4 hence comparative information on the diffusion coefficients can
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MNPs–dextran
MNPs/CTAB–dextran 0.21  10 4
be obtained with an optical method (Raman). In either case,
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CTAB proves to be instrumental in the bridging of the MNPs with

the coating material with BSA preserving more the pristine state
relate to the intensity ratios and peak positions as shown in as compared to dextran. This implies that BSA has a different
Fig. 3. Shiing of peaks towards lower or higher wavenumber is interaction with CTAB possibly taking CTAB's place around the
representative of changes in chemical bonds and crystal nanoparticles which is in agreement with the electrochemical
symmetry due to external perturbations from the coating present results and SERS results discussed below.
on the nanoparticle. Therefore, under same experimental To have further insight into the mode of interaction with the
conditions, Raman peak changes can be attributed to change in coating materials, Raman-active skeletal modes were studied
nanocrystal structure due to molecular association with biomol- from 1100 cm 1 to 3000 cm 1 which are mainly due to the
ecules. In this context, we observed that in presence of CTAB the carbon stretching and bending vibrations. The Raman bands
intensity ratio A1g/Eg changed by +275% with respect to the ratio from head group vibrations of CTAB molecule also appear in the
of the pristine sample. The situation changes, when BSA is added 2800 to 3000 cm 1 region. Analysis of the samples by conven-
to the CTAB coated particles resulting in a decrease of the A1g/Eg tional Raman spectroscopy did not yield much information in
ratio closer to the pristine case (only 50% increase). However, this spectral window and the required information was only
when dextran is included along with CTAB the changes in possible to access with surface-enhanced Raman spectroscopy
intensity ratio are similarly high as with CTAB alone (+175% with (SERS) see Fig. S2† for individual comparison of samples in this
respect to pristine nanoparticles). An additional effect for the range. The thin organic coating around the magnetic nano-
CTAB–dextran sample is the decrease in heat dissipation which particles was not in a quantity large enough to be observed
without SERS. And hence without the impact of using plas-
monic enhancement to investigate minute quantities of mate-
rial, it would go undetected. Using SERS (surface-enhanced
Raman spectroscopy), this region was enhanced quite well as
observed in Fig. 4. For MNPs/CTAB, peak at 2848 cm 1 can be
assigned to the C–H symmetric stretching mode of CH3. The
bands at 2875 cm 1 and 2931 cm 1 can be assigned to CH3
asymmetric stretching and –N+(CH3)3 symmetric stretching
vibrations,38 while the band at 1670 cm 1 comes from C]N
vibrations. The Raman band at 1441 cm 1 can be ascribed to
the –CH2 bending mode. In MNPs/CTAB–dextran system, the
CH3 asymmetric stretching and –N+(CH3)3 symmetric stretching
vibrations modes appeared at 2881 cm 1 and 2936 cm 1
signifying deformations in that region due to the interaction of
dextran with the head group of CTAB.39,40 Also, there is a change
in the intensity ratio of these bands. In case of the MNPs/CTAB–
BSA system, the signals were enhanced 100 fold and the peaks
in the region 1100 cm 1 to 1800 cm 1 were comparable with the
SERS spectra for BSA.41–43 The 100 fold enhancement is observed
when BSA has an intercalative binding with metal surfaces.42 In
this case the BSA tends to diffuse through the CTAB interface
with minor secondary structural modication to associate with
MNPs.12 SERS of only BSA did not show such enhancement in
this region, and hence conrming the above hypothesis.

Fig. 3 (A) Schematics of the different sample combinations studied Stability studies and magnetic properties of coated MNPs
with Raman spectroscopy, (B) (magnified portion of (C)) shows Raman
spectra of MNPs, MNPs/CTAB, MNPs/CTAB–BSA and MNPs/CTAB– Zeta potential measurements helps to investigate the colloidal
dextran irradiated with 2 mW laser of 785 nm. stability of the nanoparticles formulation, with an insight into

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M versus H plots for bare MNPs, MNPs/CTAB–BSA and MNPs/

Fig. 5
CTAB–dextran nanoparticles.
Fig. 4 SERS spectra for MNPs/CTAB, MNPs/CTAB–BSA and MNPs/
CTAB–dextran at 532 nm.
presence of BSA calculated using the Randle–Sevcik equation
were reduced in presence of a surfactant.45 The CTAB surfactant
interface thus acted as a diffusion barrier for the electroactive
the relative surface charge due to the interaction of nano-
species to reach the electrode surface. The increase in potential
particles.44 The stability of the MNPs/CTAB–BSA and MNPs/
separation for MNPs/CTAB–BSA indicates slow electron transfer
CTAB–dextran solutions were monitored for a period of more
and can be attributed to the structural changes occurring due
than 2 months by recording the zeta potential measurements
to hydrophobic binding of BSA to nanoparticles.46 The peak
at an interval of two weeks (Table 2). The MNPs/CTAB–BSA
shape obtained and large DEp around 280 at 50 mV s 1 sug-
system exhibited a nominal change in zeta potential from
gested slow kinetics involved in the association as a result
+41 mV to +36.6 mV in two months, whereas MNPs/CTAB–
of complex processes.30 In addition, for the dextran system,
dextran remained unchanged.
diffusion coefficients were reduced in presence of CTAB.
Hence, both systems were electrostatically stabilized by the
Nevertheless, MNPs/CTAB–dextran followed a diffusion
virtue of the positively charged cationic surfactant. Thus
controlled mechanism.
a stable colloidal system can be expected using the as prepared
Raman spectra of the system added further insights to the
coated nanoparticles.
structural changes due to molecular association. Shis in peak
The magnetic properties of the samples were evaluated by
intensity and wavenumber conrmed the inuence on nano-
recording their magnetic moment against the magnetic eld as
particles chemical bond length due to association with BSA and
shown in Fig. 5. The curve demonstrated a superparamagnetic
dextran through the CTAB interface. The Raman spectroscopy
behavior with zero coercivity and no remanence. The saturation
analysis in the low wavenumber region shows that MNPs/CTAB–
magnetizations of MNPs/CTAB–BSA and MNPs/CTAB–dextran
BSA had an upscale shi, while MNPs/CTAB–dextran had
were found to be 56 and 45 emu g 1, respectively. Hence, the
a downscale shi with respect to MNPs/CTAB signifying the
inherent magnetic properties of MNPs were found to be
difference in the pattern of association in both systems.
retained in coated MNPs.
These investigations also showed the increased MNPs stability
offered by the coating. The SERS effect normally stems from the
Possible interaction mechanism
increased inelastic light scattering due to electromagnetic and
The interactions of MNPs with BSA and of the dextran system in chemical enhancement. Among them electromagnetic
presence of CTAB were studied using cyclic voltammetry. In enhancement is considered to play the dominant role, it occurs
case of MNPs/CTAB, the presence of a surfactant interface as a result of localized surface plasmon resonance (LSPR) origi-
shows a characteristic electrochemical behavior of magnetite nating from the surface of metal nanostructures.47 The silver
nanoparticles towards the biomolecules. In CV, the shi in peak substrate used for the SERS analysis provides the required
potential indicates the mode of interaction and in this case, the plasmon effect. In SERS analysis of the samples, it was noted
involvement of CTAB in bridging the interactions can be well that the head group of the CTAB surfactant comprising of the
noted. The diffusion coefficients for MNPs and MNPs/CTAB in –N+(CH3)3 was effectively involved in a hydrogen bonding inter-
action with the dextran molecule in the MNPs/CTAB–dextran
system. In case of the MNPs/CTAB–BSA arrangement, the 100
Table 2 Zeta potential measurements of BSA and dextran system over
two months fold enhanced SERS spectra signies the BSA binding with CTAB
at the hydrophobic tail. Hence the plasmon coupling effect
Zeta potential values (mV) facilitates lesser enhancement in MNPs/CTAB–dextran sample
compared to MNPs/CTAB–BSA, as dextran molecules occupy
System Day 0 Day 60
supercial position while covering the MNPs/CTAB whereas BSA
MNPs/CTAB–BSA +41 +36.6 molecules diffuse through the polar head of CTAB to associate
MNPs/CTAB–dextran +18.1 +17.4 with the underlying hydrophobic tail and thereby establishing

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