2011 11th IEEE International Conference on Nanotechnology

Portland Marriott
August 15-18, 2011, Portland, Oregon, USA

Development of Photoactivable Nanofiber Membranes for Efficient Metal

Ion Extraction
Jintana Nammoonnoy, Brian K. Fuchs, Myra T. Koesdjojo, Vincent T. Remcho*
Department of Chemistry, Oregon State University, Corvallis, OR 97333
Email: nammoonj@onid.orst.edu, fuchsb@onid.orst.edu, koesdjom@onid.orst.edu, Vincent.Remcho@oregonstate.edu

Abstract
A novel spiropyran nanofiber was developed an applied to the extraction of heavy metal ions from drinking water. The
objective of this work was to capitalize on the high surface area achievable via nanotechnology to develop a high efficiency,
cost effective system to enable analysis for a range of applications including ground, lake and river water monitoring.
Assessment and remediation of heavy metal contamination is of utmost importance in industrial, environmental, and human
water consumption applications. We have developed technology for the removal of heavy metal ions from aqueous solutions
without the need for ancillary reagents in the metal binding-and-release process, as are common in more conventional
methods. As an alternative, we have employed photoactivable compounds, triggered by illumination with light of appropriate
wavelengths, to control binding and release events. This technology has the potential to reduce the high consumption of
ancillary reagents and decrease waste stream volume, not to mention the capacity to reduce the high recurring costs borne by
users.

I. Introduction binding. Spiropyrans, therefore, show great potential as

The removal of metals from water is important in a photo-reversible metal-complexation agents. This spiropyran
chemistry is applicable to extraction of metal ions by first
number of environmental and industrial applications.
chelating the ions by using UV light, and subsequently
Conventional metal removal techniques involve
exposing the metal-spiropyran complex to visible light to
complexation or ion exchange. Although these technologies
elute contaminants efficiently in a concentrated plug (Fig.
are effective and well-established, there are problems
associated with them. One such problem is that 2).
complexation requires the use of organic ligands that often
cannot be reused. In addition, ion exchange requires heat or
caustics to regenerate the resins. Therefore, there is ongoing
interest in the development of reversible metal-chelation
agents in which chelation can be switched on and off by
exposure to light of different wavelengths. Popular
substrates for such studies are the spiropyran system and its
analogues since these have well-documented photochromic
properties. Spiropyrans are organic photochromic
compounds that have been widely studied [1-5]. They are
composed of two heterocyclic parts linked together by a
tetrahedral sp3 spiro carbon atom. Irradiation of a spiropyran
with UV light induces heterolytic cleavage of the spiro
carbon-oxygen bond, producing the open form of the ring,
the intensely colored merocyanine (Fig. 1).

Fig. 2. Semi-continuous extraction of heavy metal ions

generates a continuous stream of purified water; non-binding
form ( ), binding form ( ), targeted metal ions ( ), non-
targeted metal ions ( ).

Fig. 1. Photoconversion of spiropyran to merocyanine.
Metal ions can influence this isomerization process by
associating with the open form through the electron-rich
oxygen atom. In contrast, visible light produces a high
concentration of the closed form, and thus hinders metal
This process can be used in environmental and industrial
processes to remove metals from aqueous solutions. The
metals are released from the ligands upon irradiation with
visible light. The regeneration of the ligands and
concentration of metals is likely to be more facile than is the
case with conventional ion exchange resins. The use of

978-1-4577-1515-0/11/$26.00 ©2011 IEEE 920

light to trigger the chelator offers unique opportunities that
minimize waste generation and power requirements.
Advances in the integration of LED (light emitting diode)
sources in the system hold promise for the production of low
cost miniaturized systems. A key benefit of this approach is
that it provides a means to trigger metal ion binding and
release without requiring any auxiliary reagents.
Various types of media, such as packed sand beds and
woven and nonwoven fibrous meshes, have been widely
employed for metal extraction applications. The selection of
an appropriate extraction medium depends on the application
itself and the properties, performance, and durability of the
extraction sorbent. Materials with large surface areas are
extremely effective for the separation/adsorption of
contaminates. The surface area increases with decreasing
fiber diameter. When the smaller diameter fibers are used in
extraction media, they not only adsorb target pollutants with
a higher total loading capacity, but also retain of small
particles [6] quite effectively. For these reasons, nanofibers
have recently gained popularity as components of filtration
and extraction media, and can be produced via
electrospinning.
Electrospinning (ES) is a convenient method for
synthesizing continuous polymeric fibers with diameters
ranging from a few to several hundred nanometers. This
technique differs from commercial processes for drawing
microscale fibers by the use of electrostatic repulsion
between surface charges (rather than a mechanical or shear
force) to continuously reduce the diameter of a viscoelastic
jet or a glassy filament. Compared to mechanical drawing,
electrospinning is better suited for generating fibers with
much thinner diameters, since the elongation can be
accomplished via a contactless scheme through the
application of an external electric field [7-8]. Similar to
mechanical drawing, electrospinning is also a continuous
process and therefore should work well for high-volume
production. Electrospun fibers can be employed in many
applications impacting a wide variety of fields including
tissue engineering, drug delivery, filtration, textiles, sensors,
optical and electronic devices, and catalysis [9-17]. These
applications are made possible because of the unique
characteristics of the nanofibers, such as a large surface area
per unit mass, high porosity, high gas permeability, and
small interfibrous pore size. In addition, their high specific
surface area leads to a high adsorption rate and capacity
compared to other filter materials, such as resins, foams, and
conventional fibers [18-20].
We report herein on the unique properties of
spiropyrans together with the unique characteristics of
nanofibers for water reclamation using light to gate metal
ion capture and release. Spiropyran-PMMA (SP-PMMA)
nanofibers have been prepared via electrospinning. As lead
(Pb2+) is widely distributed in nature and given its adverse
effects on human health, it was selected as a model divalent
metal cation for the extraction study. The photochromism of
the SP-PMMA nanofibers was also investigated.
II. Experimental
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Chemicals and instrumentation
All reagents were used as received throughout the
experiments. 1´,3´,3´-trimethylindolino-6-nitrospirobenzo
pyrylospiran was purchased from TCI America (Portland,
OR, USA). Polymethyl Methacrylate (PMMA) with average
M.W. of 120000 was purchased from Spectrum Chemical
MFG. Crop. (Gerdena, CA, USA). Dimethylformamide
(DMF) and ethanol were purchased from Aldrich (St. Louis,
MO, USA). Fourier transform infrared (FTIR) spectra were
recorded with a Nicolet 510P FTIR spectrometer (Thermo
Nicolet, Madison, WI, USA). UV-vis spectra were recorded
on a Agilent 8453UV-vis spectrometer (Santa Clara, CA,
USA). The UV irradiation (390 nm LEDs) and visible
irradiation (525 nm LEDs) sources were obtained from V-
LEDs.com (Bellingham, WA, USA). The metal ion
determination was carried out using a JY 2000 inductively
coupled plasma atomic emission spectrometer (HORIBA
Jobin Yvon, Edison, NJ, USA). The nanofibers were
characterized using an SEM (Quanta 600F FEG SEM, FEI
Quanta™, Hillsboro, Oregon, USA) operated at 30 kV.
Electrospinning
The spiropyran and PMMA were dissolved in a
DMF/EtOH (3:2) solution to obtain 20% PMMA solution
containing spiropyran in 1 wt%. For electrospinning, the
solution was placed in a glass syringe (5 mL) bearing a 27
gauge metal needle that was connected with a high voltage
power supply. The target substrate was connected to the
copper net collector. Typically, electrospinning was
performed at 11 kV voltage, with positive voltage of 8 kV
on the needle and negative voltage of 3 kV on the collector.
The distance between the needle and the collector was
maintained at 18 cm. The flow rate of the solution was
controlled by a syringe pump at 0.4 mL/h from the needle
outlet. It usually took 3 min to obtain a sufficiently thick
membrane for use in wettability testing.
Absorption and Desorption of Pb2+ onto the spiropyran
nanofiber mat
5-20 mg dry samples of the SP-PMMA nanofiber mat
were added to 2 mL aliquots of a Pb2+ containing solution
(10 ppm) at room temperature. The samples were irradiated
with UV light (365 nm, 3.8 mW) for 5 min. The nanofiber
mat samples were then filtered out of the sample vessels.
The concentration of Pb2+ in the solution both before and
after UV irradiation was determined using inductively
coupled plasma (ICP) atomic emission spectroscopy.
III. Results and Discussion
While our ultimate goal is to incorporate the spiropyran dye
in-situ in a polymeric nanofiber-based microfluidic device
for water purification, it was important to first study
immobilized spiropyran media ex-situ, to determine their
suitability for metal ion extraction applications. Thus Pb2+
ions were extracted from an aqueous solution using
immobilized spiropyran resins in order to demonstrate that
the spiropyrans retain their photochromic properties when
immobilized on the surface of the resin and can successfully
perform Pb2+ extractions from aqueous solution.
Initially, spiropyran derivatives were synthesized using
previously reported procedures [21]. Placing a nitro group at
position R´ (Fig. 3) stabilized the open form of the
spiropyran. Further, the addition of an electron donor group
on at position L generates an auxiliary ligating group [22].
1a R=CH3, R´= H, L = OH, 1b R=C3H6COOH, R´= NO2, L´= H, 1c
R=C3H6COOH, R´= NO2, L´= OCH3
Fig. 3. Light-modulated transformation from spiropyran
(SP) to merocyanine (MC).
We designed spiropyran derivatives incorporating a
methoxy moiety at the 8-position in which cation-binding
enhancement is expected on photoisomerization to the
corresponding merocyanine form. Sterically-favorable
cooperation of the resulting phenolate anion together with
the methoxy moiety provides a suitable chelator for cations.
In fact, a powerful interaction between the phenolate anion
and methoxy-complexed metal ions, especially lead ions,
was found in the merocyanine isomer spiropyran.
Spiropyrans were then allowed to react with Merrifield
resins or aminate polystyrene resins via carbodiimide
coupling protocols (Fig. 4) to yield a convenient resin for
extraction studies.
1. EDC, CH2Cl2. 2. 50% TFA, CH2Cl2. 3. SP, EDC, CH2Cl2.
Fig. 4. Schematic of the synthesis of photochromic resins.
Changes in the UV absorption spectra of SP-MC in
dichloromethane under irradiation with UV light of  = 365
nm and then subsequently with visible light of  = 525 nm
were examined. Figure 5 shows the measured UV absorption
of SP-MC in dichloromethane after irradiation with UV light
for 5 min and subsequently with visible light for 5 min. A
new absorption peak is found to appear at 526 nm in the
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spectrum on irradiation with UV light, and is assigned to the
merocyanine form. The peak disappears under consequent
irradiation with visible light, and the spectrum returns almost
completely to the original form.
Fig.5. Changes in the UV absorption spectrum of SP-MC in
dichloromethane under irradiation with UV light of  = 365
nm and subsequently with visible light of  = 525 nm. (a)
before irradiation; (b) after irradiation with UV light for 5
min; (c) after subsequent irradiation with visible light for 5
min; [SP-MC] = 1×10-4 mol/L.
The SP-MC resins were also characterized by IR
spectroscopy. Figure 6 shows the IR absorption spectra of
aminated polystyrene resins, Boc-lysine resins, lysine resins,
Bis-SP-lysine, and Bis-SP-lysine modified resins. An
absorption peak at around 1620 cm-1, which is assigned to
the C=O stretch of the amide group, in the spectrum of Boc-
lysine resins is found to decrease with introduction of the
spiropyran moiety. An absorption peak at 1650 cm-1 is
assigned to the carbonyl group from amide, those at 1500
and 1340 cm-1 are assigned to N-O in the nitro group, and a
peak at 1100 cm-1 is assigned to O-C in the methoxy group.
These results confirm the presence of the spiropyran
moieties in Bis-spiropyran-lysine resins.
Fig.6. IR absorption spectra of (a) Aminated polystyrene
resins; (b) BOC-lysine resins; (c) lysine resins; (d) Bis-SP-
lysine and (e) Bis-SP-lysine resins.
The spiropyran modified resins showed spectral changes
similar to those observed solution phase SP-MC in
dichloromethane on irradiation with UV light and
subsequently with visible light. The resins turned from red to
deep purple after irradiation with UV light, and reverted to
red after irradiation with visible light. However, the
isomerization rates (especially the disappearance rates of the
merocyanine forms) for resins were slower than those
observed in solution (Fig.7).
Fig.7. The spiropyran modified resins before and after 5 min
irradiation with UV light.
More importantly, these results show that the
photoisomerization of spiropyran moieties on the modified
resins is reversible. The color change suggests generation of
the open form of the spiropyran-modified resin, which then
complexes Pb2+ ions. The reddish resin reappeared after
irradiation with green LED array. Thus, stabilization of the
Pb2+-complexed open form in an extremely polar solvent
such as water does not prevent isomerization to the closed
form under visible light. Results from initial screening
suggest that spiropyran modified Merrifield resins can
successfully trap lead ions in solution.
Application of the newly modified spiropyran resins to
Pb2+ extraction from aqueous solution was done in triplicate.
A simple, batch technique was used in order to define
optimum conditions including irradiation time. Typically, 20
mg of modified resins were packed in a home-built resin
cartridge as shown in Figure 8.
Fig.8. In-house-designed resin cartridge consisting of a
clamped device equipped with Upchurch nanoports for
fluidic connections, PMMA chip which contains a thin layer
of spiropyran-functionalized resin.
A Pb2+ solution containing 50 ppb Pb2+ was flowed through
the resin bed at 20 µL/min using a peristaltic pump,
described as follows:
1. Start flow of Pb2+ solution at 20 µL/min.
2. Activate UV exposure (390 nm) for 30 min.
3. Collect fractions of solution at 20 second intervals
for measuring Pb2+ quantifications via ICP-MS.
Following the experiments, free unextracted Pb 2+
concentration was plotted as a function of UV irradiation
time as shown in Figure 9. The results show that Pb 2+
contents decreased with increasing the UV irradiation time,
reaching its lowest value at 5 min irradiation, followed by a
steady increase of Pb2+ content past 5 min. Therefore, the
adsorption of Pb2+ was determined to be most effective at 5
min UV irradiation.
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Fig.9. Pb2+ concentrations recorded during UV LED
irradiation (390 nm) showing that the most effective
irradiation time for binding Pb2+ ions is 5 min.
The efficiency of the modified resin for Pb 2+ extraction
is an important indication of the substituent groups effects
on the spiropyran ring. With the optimum UV irradiation
time, the extraction efficiency was calculated by measuring
the Pb2+ content before and after the chelation. A
comparison in Pb2+ uptake in different spiropyran
derivatives indicates that there is a considerable increase of
~70% due to the contribution of the methoxy ligating moiety
in metal binding [23]. Upon exposure to the appropriate
stimuli, these resins display photo-controlled uptake and
release of certain metal ions. Increase in Pb2+ loading
capacity was observed by replacing a functional group on
spiropyran ring. Ongoing work is directed toward the
integration of nanofiber technology and the photochromism
of spiropyran molecule that will allow us to trap Pb 2+ more
efficiently with improved capacity.
First, spiropyran derivatives with highest extraction
efficiency were selected. The addition of a nitro group at
position R´ (Fig. 1) stabilizes the merocyanine form complex
with metal ion [21]. In solution, two spiropyran molecules
can form a complex with divalent metal ion [22]. This
finding indicates the implications for effective metal ion
complexation via surface bound merocyanine ligands in
terms of their ability to rearrange sufficiently to generate the
appropriate conformation. Solution phase chemistry can be
greatly different from solid phase chemistry, especially, if
the stoichiometry requires convergence of multiple ligands
around a single guest species. Therefore, the optimization of
spiropyran concentration has been studied.
The spiropyran-PMMA nanofiber mats were also
characterized by IR spectroscopy. Figure 4 shows the IR
absorption spectra of PMMA and spiropyran-PMMA
nanofiber mats. The absorbance peaks at 1500 and 1340 cm-1
are assigned to N-O in the nitro group, and a peak at 1700
cm-1 is assigned to O=C in the ester group of PMMA. These
results confirm the presence of the spiropyran moieties
nanofiber mat.

Fig. 4. FTIR absorption spectra of (a) PMMA nanofibers,
(b) spiropyran and SP-PMMA nanofibers (c).
In order to maintain the high surface to volume ratio of
the nanofibers, the effect of spiropyran concentration and
size of nanofibers was investigated. We found that the
addition of spiropyran in the mixture solution have little or
no effect in the size of the spun nanofibers (shown in Figure
5). However, having higher spiropyran concentration in the
solution mixture could interrupt the electrospinning process.
We experienced periodic spraying during the electrospinning
process when spiropyran with concentration of 20 wt% and
higher is used.
(a) (b)
Fig. 5. SEM images of electrospun PMMA nanofibers (a)
and 20 wt% of spiropyran in SP-PMMA nanofibers (b).
The SP-PMMA nanofibers showed visible color
changes similar to those observed in the solution phase of
SP-MC in dichloromethane on irradiation with UV light and
subsequently with visible light. The nanofibers turned from
white to deep blue after irradiation with UV light, and
reverted to white after irradiation with visible light. In
addition, the isomerization rates (especially the
disappearance rates of the merocyanine forms) for the resins
were as fast as observed in solution (Fig. 6). Further studies
directed toward the addition of other photochromic ligands
will allow us to target different types of metal ions with
greater specificity and improved efficiency.
(a) (b) (c)
Fig. 6. The serpentine pattern on SP-PMMA nanofiber mat
using UV light (a), nanofibers in water before (b) and after
(c) 30 s irradiation of UV light.
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In conclusion, we have demonstrated that it is possible
to use optically gated spiropyran resins to perform
extractions in a quasi-continuous fashion. We regard these
preliminary results as a starting point towards finding
materials that are capable of performing reversible binding
and release operations on demand. Further investigation of
the metal ion complexation process will allow us to optimize
these media to ensure their applicability in various
environments. The surface chemistry of spiropyran-modified
polymers differs greatly from that of spiropyran-embedded
polymers, most especially in situations where the
stoichiometry of the extraction requires convergence of
multiple ligands around a single metal ion. Therefore, the
concentration of spiropyran in the PMMA nanofiber will
require further optimization for these materials to fully
realized their potential as extraction media.
IV. Acknowledgement
The authors thank Dr. Chris Pastorek for assistance with
ICP and Yuanyuan Wu for SEM images.
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