Accepted Manuscript

Incorporation of pyrene in polypyrrole/polystyrene magnetic beads

Paulina Głowala, Adam Budniak, Pamela Krug, Barbara Wysocka, SylwiaBerbeć, Robert Dec, Izabela Doł ęga, Kamil Kacprzak, JarosławWojciechowski, Jakub Kawałko, Paweł Kępka, Daria Kępińska, KrystynaKijewska, Maciej Mazur

PII: S1386-1425(14)00711-2DOI: http://dx.doi.org/10.1016/j.saa.2014.04.138Reference: SAA 12102

To appear in: Spectrochimica Acta Part A: Molecular and Biomo-lecular Spectroscopy

Received Date: 27 November 2013Accepted Date: 22 April 2014

Please cite this article as: P. Głowala, A. Budniak, P. Krug, B. Wysocka, S. Berbeć, R. Dec, I. Doł ęga, K. Kacprzak,J. Wojciechowski, J. Kawałko, P. Kępka, D. Kępińska, K. Kijewska, M. Mazur, Incorporation of pyrene inpolypyrrole/polystyrene magnetic beads, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy(2014), doi: http://dx.doi.org/10.1016/j.saa.2014.04.138

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1

Incorporation of pyrene in polypyrrole/polystyrene

magnetic beads

Paulina Głowala, Adam Budniak, Pamela Krug, Barbara Wysocka, Sylwia Berbeć, Robert

Dec, Izabela Dołęga, Kamil Kacprzak, Jarosław Wojciechowski, Jakub Kawałko, Paweł

Kępka, Daria Kępińska, Krystyna Kijewska and Maciej Mazur

University of Warsaw, Department of Chemistry, Pasteura 1, 02-093 Warsaw, Poland

Abstract

Pyrene, a fluorescent dye, was incorporated into polystyrene particles coated with

polypyrrole. The incorporation was achieved by treating the polypyrrole/polystyrene (PPy/PS)

beads in a tetrahydrofuran (THF) solution of the pyrene fluorophore followed by rinsing with

methanol. The polystyrene cores of the beads swell in THF, allowing penetration of pyrene

molecules into the polystyrene structure. The addition of methanol causes contraction of the

swollen polystyrene, which encapsulates the dye molecules inside the beads. It is shown that

the polypyrrole coating is permeable with respect to both the dye and the solvent, allowing the

transport of molecules between the polystyrene cores and the contacting solution. The

polypyrrole adlayer can be used as a matrix for the incorporation of magnetic nanoparticles.

Embedded particles provide magnetic functionality to the PPy/PS beads. It is demonstrated

that the pyrene-loaded beads can be manipulated with an external magnetic field.

Keywords:

Pyrene fluorescence, core-shell particles, polystyrene beads, magnetic nanoparticles.

corresponding author; phone: +48 22 822 02 11 ext. 361, fax: +48 22 822 5996, e-mail:

mmazur@chem.uw.edu.pl

2

Introduction

Polymeric core-shell structures have recently gained considerable interest due to their

remarkable applications in medicine as drug delivery carriers, in chemical analysis as sensing

devices and in cosmetics as smart micro/nanocontainers.1-5

These structures are typically synthesized through the deposition of one polymeric material

onto a spherical particle consisting of another polymer. A number of polymeric beads have

been used as the core in core-shell structures, including but not limited to polystyrene,1,6,7

polyacrylates,5 and melamine formaldehyde.

8 These particles act as templates onto which

another material can be deposited, forming a thin adlayer on the surface.

One of the most effective and facile methods to coat various substrates is in situ

polymerization.9-17

This method was successfully employed to deposit several conducting

polymers,18-21

such as polyaniline and polypyrrole, onto solid or liquid surfaces. The substrate

is placed in a polymerization bath that contains a monomer and an oxidant. The monomer is

oxidized by the oxidant, which yields oligomeric and polymeric species which are

accumulated on the surface in form of a thin film. The polymer is also produced in the bulk

phase of the polymerization solution, but this process is usually preceded by deposition on the

surface.22

In situ polymerization has been demonstrated to be equally effective for deposition

onto macroscopic planar substrates, as well as onto colloidal species such as solid particles,23-

26 liquid droplets

27-37 and gaseous bubbles.

38

Herein, we study the in situ deposition of polypyrrole onto polystyrene colloidal

particles and demonstrate that the polypyrrole layer can be employed as a support for mixed

zinc-nickel-ferrite nanoparticles.39

The incorporation of these nanoparticles imparts magnetic

properties to the core-shell structures, and therefore, they can be manipulated with an external

magnetic field. On the other hand, the polymeric beads can be loaded with hydrophobic

fluorescent dyes, such as pyrene,40

through simple conditioning in an organic solvent. We

3

demonstrate that even though the fluorophore strongly interacts with the polystyrene core

material, it retains its fluorescent properties after incorporation into the beads.

Experimental

Chemicals

All chemicals were of the highest quality that are commercially available and were used as

received: polystyrene latex beads (Aldrich, 3 μm mean particle size); pyrrole (Aldrich, 98%);

iron (III) chloride (Aldrich, 97%); pyrene (Aldrich, 99%); Fe(NO3)3·9H2O (reagent grade,

Chempur, Poland); Ni(NO3)2·6H2O (reagent grade, Sigma Aldrich); Zn(NO3)2·6H2O (reagent

grade, Chempur, Poland); and NaOH (reagent grade, Chempur, Poland).

Aqueous solutions were prepared using high-purity water (Milli-Q Plus).

Instrumentation

Scanning electron microscopy and EDS (Energy-Dispersive X-ray Spectroscopy)

measurements were performed using a Zeiss Merlin field emission SEM. Transmission

electron microscopy was performed with a Zeiss Libra 120 EFTEM.

Optical microscopy was performed using a Nikon Eclipse LV 100. The microscope was

operated in fluorescence mode (excitation with a mercury lamp) or in transmission mode

(halogen lamp).

Fluorescence steady state and time-resolved data were collected with a Fluorolog 3 (Horiba

Jobin Yvon) equipped with a time-correlated single photon counting (TCSPC) module.

UV-VIS absorption spectra were acquired with a Lambda 25 (Perkin-Elmer)

spectrophotometer.

Fourier transform infrared data were collected with a Nicolet 6700 Continuμm FTIR

microscope (Thermo Electron Corporation).

4

Raman data were acquired with a LabRAM HR spectrometer (Horiba Jobin Yvon). A LION

semiconductor laser (Sacher Lasertechnik) operating at 784.7 nm was used as the excitation

source.

Thermogravimetry was performed with a TGA Q50 (TA Instruments). The measurements

were conducted under an oxygen atmosphere.

Experimental procedures

Preparation of PPy/PS beads

The polymerization solution was prepared by mixing 1 mL of aqueous pyrrole (0.22 M) with

1 mL of aqueous ferric chloride (0.09 M). Forty microliters of this solution was added to 30 μl

of polystyrene beads. This polymerization mixture was allowed to sit for 30 min. After the

reaction was complete, the resulting beads were separated by centrifugation.

Synthesis of magnetic nanoparticles

The synthesis of mixed zinc-nickel-ferrite nanoparticles with the formula Zn0.5Ni0.5Fe2O4 was

previously described elsewhere.36

Incorporation of magnetic nanoparticles into PPy/PS beads

The procedure for incorporating magnetic nanoparticles is similar to that for the preparation

of PPy/PS beads described above. The only difference is that prior to mixing the monomer

and oxidant solutions, 15 μl of an aqueous nanoparticle suspension (ca. 180 mg/ml) was

added to the monomer solution.

Loading the PPy/PS (and MNPs/PPy/PS) beads with pyrene

For loading of the PPy/PS nanoparticles (with or without incorporated magnetic

nanoparticles), a solution of pyrene in THF (5 mM) was added to the beads for 20 minutes.

After conditioning, the beads were centrifuged and rinsed with methanol. The centrifugation

and rinsing (now with deionized water) was repeated three times.

5

Results and discussion

The preparation of polypyrrole/polystyrene (PPy/PS) core-shell structures was

achieved by oxidative polymerization of pyrrole onto the surface of PS beads. The beads were

added to a polymerization mixture that contained pyrrole (monomer) and FeCl3 (oxidant),

which resulted in the deposition of polypyrrole onto the surface of the polystyrene

microbeads.

Figure 1. a) SEM image of PPy/PS beads. (inset: magnification of the structures) b) TEM

image of PPy/PS beads.

Fig. 1a presents a scanning electron microscopy image of PS particles coated with

PPy. The surface of the PPy-modified beads is very smooth (see magnification in the inset of

Fig. 1a). Moreover, the size of the beads is ca. 3 μm, which is nearly identical to the diameter

of the non-coated particles (SEM image not shown). We also studied the polymer structures

with transmission electron microscopy (TEM). Fig. 1b presents a TEM image of PPy-coated

polystyrene particles. One can see spherical particles; however, the polypyrrole adlayer is not

6

discernible in the image. This suggests, that the PPy layer (if exists) is thin, smooth and

adheres well to the PS particle.

Figure 2. a) Raman spectra of (i) PPy/PS beads and (ii) PS particles. b) FTIR spectra of (i)

PPy/PS beads and (ii) PS particles.

To detect and identify the polypyrrole layer, we used Raman spectroscopy. Fig. 2a

presents a Raman spectrum of PPy/PS beads. Several characteristic modes attributable to

polypyrrole are observed in this spectrum.41,42

The band at 1596 cm-1

is assigned to C=C

stretching in the pyrrole ring. The modes at 1376 and 1247 cm-1

are attributable to

antisymmetrical C-N stretching and C-H in-plane vibration, respectively. The bands at 1075,

1032, 969 and 916 cm-1

are due to vibrations of polaron and bipolaron structures.

Interestingly, few signals attributed to polystyrene are observed in the spectrum. Polystyrene

has bands at 619, 1002 and 1603 cm-1

, which are assigned to ring deformation, ring breathing

and ring stretching modes, respectively.7 However, in the spectrum of PPy/PS beads, only a

very weak peak at 1002 cm-1

is observed. This result can be explained as follows. Polypyrrole

absorbs light within a broad spectral range, with absorption bands located at ca. 400 and 1000

7

nm (Fig. S1, Supplementary data). The tail of the band at 1000 nm overlaps with the laser line

used to excite the Raman spectrum (785 nm). Therefore, the light scattered by the polystyrene

core is immediately absorbed by the polypyrrole coating. Consequently, only the signals

attributable to polypyrrole are clearly observed in the spectrum.

A completely different situation is observed in the infrared spectroscopy data. Fig. 2b

presents an FTIR spectrum of PPy/PS beads. The spectrum reveals only the signals

attributable to polystyrene. The infrared spectrum of PS is well known,43

and the most intense

signals are found at 3026, 2927, 1601, 1493, 1452 and 1028 cm-1

. No vibrational modes due

to polypyrrole44

are detected. This observation can be explained assuming that the amount of

polypyrrole is very small with respect to polystyrene. Because FTIR provides information on

the whole volume of the sample, the spectrum is dominated by polystyrene. This is an

interesting finding. Our results show that by using both Raman and FTIR spectroscopy, one

can gain complementary information on the composition of PPy/PS core-shell structures.

We were also interested in whether the PPy/PS beads could be loaded with other

molecules. To investigate this issue in more detail, we used a highly fluorescent dye, pyrene.

Pyrene is a hydrophobic chromophore with a relatively high quantum yield, long fluorescence

lifetime and sensitivity to its immediate environment. The emission band of pyrene reveals a

vibronic structure with vibrational bands that are sensitive to local polarity.40

To load the PPy/PS beads with pyrene, they were conditioned in THF. Fig. 3a presents

an optical microscopy image of PPy/PS beads suspended in pyrene-containing THF. The size

of the beads is approximately 3.5 μm, which is slightly higher than the starting diameter of the

PPy/PS structures. Once the beads are rinsed with methanol, the fluorophore becomes

entrapped within the cores. Fig. 3b presents a fluorescence microscopy image of PPy/PS

structures with incorporated pyrene. One can see that light is emitted only from the PPy/PS

particles, while no fluorescence is observed from the aqueous solution.

8

Figure 3. a) Optical microscopy image of PPy/PS beads suspended in pyrene-containing

THF. b) Fluorescence microscopy image of pyrene-modified PPy/PS beads suspended in an

aqueous phase.

Next, we used electron microscopy to image the PPy/PS beads after loading with

pyrene. Fig. 4a presents a SEM image of the structures. One can see that the surface of the

beads is highly wrinkled. The corresponding TEM image (Fig. 4b) confirms this observation.

The above data suggest that PPy/PS particles become swollen in THF solvent. On the

other hand, PS is not swollen in methanol. Therefore, rinsing the sample with methanol results

in the removal of the THF molecules from the PS core, and the polystyrene material collapses,

entrapping the dye molecules. An interesting observation is that the polypyrrole coating does

not significantly affect the transport of solvent and dye molecules to/from the PS core. This is

an important finding. Our data reveal that polypyrrole is permeable with respect to small

organic molecules. At the same time, the PPy adlayer may be used to incorporate magnetic

nanoparticles, which will be further illustrated in this paper.

9

Figure 4. a) SEM and b) TEM image of PPy/PS beads loaded with pyrene.

To identify pyrene molecules incorporated within the PPy/PS beads, we used

fluorescence spectroscopy. Fig. 5a presents excitation and emission spectra of the polymer

structures. The excitation spectrum reveals a typical pattern characteristic of pyrene with

bands at 275, 310, 323 and 338 nm. On the other hand, the emission spectrum exhibits a band

centered at ca. 390 nm with a well-developed vibronic structure. One can distinguish five

characteristic vibronic bands at 373, 378, 383, 388 and 393 nm. The I/III band ratio is

frequently used as a polarity probe of the medium.40

In our case, this ratio is 1.09, which

suggests a relatively hydrophobic environment. For comparison, the II/IIII value is 1.87 for

water, 1.35 for methanol and 1.35 for THF.45

While we have no data for styrene (or

polystyrene), the value of 1.05 for benzene45

is close to that determined for the PPy/PS beads.

Thus, we conclude that there are no large amounts of water, tetrahydrofuran or methanol

incorporated within the beads together with pyrene as the II/IIII value is relatively low.

10

Figure 5. a) Excitation and emission spectra of pyrene incorporated in PPy/PS beads. b)

Time-resolved fluorescence decays of pyrene incorporated in PPy/PS beads and pyrene

solutions in water, THF and methanol.

We investigated the incorporated pyrene with time-resolved fluorescence

spectroscopy. Fig. 5b presents fluorescence decay curves for pyrene incorporated in PPy/PS

beads and the same dye dissolved in bulk water, THF and methanol. For the solution-phase

results, the curves are mono-exponential with relatively large time constants of 99.6 ns

(water), 21.3 ns (THF) and 15.9 ns (methanol). However, for incorporated pyrene, the curve

decays very rapidly with the time constant well below 1 ns (due to the limitations of our

TCSPC instrument, we were unable to precisely determine the fluorescence lifetime). This

drastic shortening of the lifetime is likely due to a strong interaction of the fluorophore with

the polystyrene core of the beads. This result confirms that there is no bulk residue of THF or

other solvents within the PPy/PS beads. This finding is consistent with the steady state data.

11

Figure 6. PPy/PS beads modified with magnetic nanoparticles: a) SEM image, b) TEM image

(the edge of the bead), c) EDS map of carbon, d) EDS map of iron.

Our next goal was to incorporate magnetic nanoparticles (MNPs) into the polypyrrole

shells coating the PS cores. This was achieved by adding zinc-nickel-ferrite nanoparticles to

the polymerization mixture. The hypothesis was that the nanoparticles would be mechanically

trapped within the forming polypyrrole layer.

Fig. 6a presents a SEM image of the PPy/PS bead with incorporated ferrite

nanoparticles. One can see that the surface of the bead is covered with irregular granular

deposit. The corresponding TEM image (Fig. 6b) reveals that the deposit consists of dark

spots embedded in an amorphous material. These spots are attributable to the magnetic

nanoparticles incorporated in polypyrrole. The size of the MNPs is ca. 12 nm, which is in

perfect agreement with the size of the bare nanoparticles (TEM data not shown). We also

recorded EDS maps of carbon (Fig. 6c) and iron (Fig. 6d) elements for the MNPs/PPy/PS

beads. Comparing the C and Fe maps, one can see that the increased concentration of Fe

12

elements (due to MNPs) coincides with the bead structures visible on the carbon image. Thus,

it can be concluded that the magnetic nanoparticles are incorporated within the PPy/PS beads.

To estimate the quantity of incorporated nanoparticles, we performed

thermogravimetric analysis. Fig. 7 presents a thermogram of MNP-modified PPy/PS beads.

The sample was heated under an oxygen atmosphere. The intention was to decompose the

organic material (PS and PPy) while leaving the ferrite particles intact. One can see that the

mass starts to decrease at ca. 270 ºC and then reaches a constant value of ca. 8.5%. On the

basis of the above data, we estimate that the nanoparticles constitute ca. 8.5% of the mass of

MNP-modified PPy/PS beads.

Figure 7. Thermogram of PPy/PS beads modified with magnetic nanoparticles.

The MNPs/PPy/PS structures can be further loaded with pyrene molecules by

conditioning in a THF solution of the dye followed by rinsing with methanol. Fig. 8 presents a

fluorescence spectrum of MNPs/PPy/PS beads loaded with pyrene. The spectrum is nearly

identical to that without nanoparticles. Thus, we conclude that incorporation of magnetic

nanoparticles does not affect the encapsulation of the fluorescent dye within the beads.

We were also interested in whether the magnetic beads loaded with pyrene could be

manipulated with an external magnetic field. To demonstrate this phenomenon, we introduced

a solid magnet near the suspension of the beads squeezed between two microscope slides and

observed migration of the carriers under fluorescence microscopy. Included in the

supplementary data is a video clip (Video.avi) demonstrating movement of the beads toward

13

the magnet and, at the same time, the emission of light after optical excitation with a UV

source (the timescale of the video is accelerated 10 times). These data clearly confirm that the

magnetic beads with incorporated dye can be manipulated with an external magnetic field.

Figure 8. Emission spectrum of pyrene incorporated in MNPs/PPy/PS beads.

Conclusions

Polypyrrole was deposited onto the surface of polystyrene particles, which yielded

spherical core-shell structures. The presence of a polypyrrole adlayer was confirmed by

Raman spectroscopy. The Raman spectrum exhibits vibrational bands assigned exclusively to

polypyrrole, while the signals of polystyrene core are almost completely absent in the

spectrum. This effect is likely due to the absorption of light scattered on polystyrene by a

polypyrrole layer. On the other hand, the infrared spectroscopy reveals only the signals

attributable to the polystyrene core. This result is explained by the relatively low amount of

polypyrrole deposited on the surface.

The resulting core-shell structures can be loaded with pyrene, a hydrophobic

fluorescent dye. This can be performed through conditioning of the beads in a THF solution

of the fluorophore, followed by rinsing with methanol. The PS cores swell in THF, which

affects the penetration of the dye into their structure. Rinsing with methanol results in

contraction of the PS core and entrapment of pyrene molecules. The encapsulated pyrene

retains its fluorescent properties; however, due to interactions with the polystyrene matrix, its

14

fluorescence lifetime is considerably shortened. We also show that the incorporation of mixed

zinc-nickel-ferrite nanoparticles imparts magnetic properties to the beads. Consequently, the

beads with an encapsulated fluorophore can be manipulated with an external magnetic field.

Acknowledgements

This work was supported by the National Science Centre, project nos. 2011/03/N/ST4/00750

and 2012/07/N/ST4/01836. The Ministry of Science and Higher Education grant Iuventus

Plus (0161/IP3/2013/72) is also acknowledged.

Special thanks are owed to Dr. Marianna Gniadek (Department of Chemistry, University of

Warsaw) for TEM and SEM measurements.

The SEM, TEM and FTIR measurements were conducted using the research equipment

purchased for the CePT project, which was co-financed by the European Union from the

European Regional Development Fund under the Operational Programme Innovative

Economy 2007-2013.

Steady-state and time-resolved fluorescence measurements were conducted at the Structural

Research Laboratory (SRL) at the Department of Chemistry, University of Warsaw, Poland.

The SRL was established with the financial support of the European Regional Development

Fund under the Sectoral Operational Programme "Improvement of the Competitiveness of

Enterprises, years 2004-2006", project no: WKP_1/1.4.3./1/2004/72/72/165/2005/U.

15

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Highlights

Pyrene was incorporated into polystyrene beads coated with polypyrrole through facile

conditioning process in THF solution.

The incorporated dye strongly interacts with the core material of the beads but retains

its fluorescent properties.

Modification of pyrene-containing polymer beads with magnetic particles allows

manipulating them with an external magnetic field.