RESEARCH ARTICLE

www.acsami.org

Poly (N-Isopropylacrylamide) Microgels for Organic Dye Removal

from Water
Deepika Parasuraman and Michael J. Serpe*
Department of Chemistry, University of Alberta, Edmonton, AB, T6G 2G2
bS Supporting Information
ABSTRACT: The ability of poly (N-isopropylacrylamide)
(pNIPAm), and pNIPAm-co-acrylic acid (pNIPAm-co-AAc) mi-
crogels to remove an organic azo dye molecule, 4-(2-Hydroxy-1-
naphthylazo) benzenesulfonic acid sodium salt (Orange II) from
aqueous solutions at both room and elevated temperature was
assessed. At room temperature, we found that the amount of
Orange II removed from water (removal eciency) increased
with increasing AAc and microgel concentration. The removal of
Orange II from water was also t by a Langmuir sorption isotherm
model. Furthermore, we found the extent of Orange II removal depended on solution temperature; more Orange II was removed
from water at elevated temperature and as the microgels were held at that temperature for longer durations of time. Additionally, by
increasing the cycles between high and ambient temperature, the removal of Orange II was enhanced, although this was only true for
two temperature cycles. We hypothesize that this is a result of the thermoresponsive nature of pNIPAm-based microgels which
deswell at elevated temperature expelling their solvating water and when the microgels are cooled back down they reswell with the
Orange II containing water. We also hypothesize that the microgels become saturated after the second heating cycle and so the
eciency of removal did not increase further. Finally, we assessed the ability of the microgels to retain the Orange II after it is
removed from the aqueous solution. We determined that the microgels leak 25.6% of the Orange II that was originally removed
from the water.
KEYWORDS: water remediation and contamination, poly (N-isopropylacrylamide) microgels, thermo responsive materials,
azo dyes, NIPAm

INTRODUCTION Relevant to this study are materials composed of responsive

Azo dyes are a class of organic compounds that are used as polymers. Responsive polymers are a class of polymers that
colorants in textile, cosmetics, food and drug industries.1 Azo dye respond to external stimuli by changing their physical and/or
containing euents from these industries has been a major cause for chemical state. Responsive polymers have been made to be
concern, especially in developing countries, due to their ability to sensitive to a variety of stimuli including: temperature, pH, ionic
transform into carcinogenic aromatic amines.1 Additionally, these strength, light, force, and analyte concentration.21
28 Arguably
dyes have been shown to be directly toxic to both human and the most well studied responsive polymer is poly (N-iso-
aquatic life. The textile industry alone uses several thousand dierent propylacrylamide) (pNIPAm).29
37 PNIPAm is fully water-
dyes, out of which about 30% are classied as reactive dyes. Reactive soluble and is thermoresponsive, that is, it exists as a random
dyes have functional groups, for example, azo, anthraquninone, coil in aqueous solution, but transitions to a compact globule
oxazine that get activated and react with the bres of the dyable conformation at T > 32 C, which is pNIPAms lower critical
material. Of these, azo dyes comprise nearly 60% of these reactive solution temperature (LCST).30,31,34,35 This transition is also
dyes, and are mainly employed by the textile industry due to their accompanied by an dissociation of water from the polymer chain.
bright color.2 Many physicochemical and biological methods have It is very well-known that colloidal particles can be synthesized
been used to remove several dyes from industrial euents including from NIPAm.30,31,33,35
39,38
41 These colloids, referred to as
membrane ltration, nanoltration membranes, photo catalytic microgels, are water-soluble, highly porous, and thermorespon-
processes, and combined anaerobic
aerobic bacteria treatment.3
6 sive. That is, pNIPAm microgels decrease in diameter at T >
While this is the case, the techniques are often costly, not easy to 32 C, expelling their solvating water as a result, and reswell at
implement/maintain, and are not ecient.7
11 In recent years, T < 32 C. PNIPAm microgels have also been made to respond to
there have been various hydrogel based systems investigated for a variety of stimuli, by addition of a functional monomer into the
their ability to remove from water a variety of cationic and anionic
dyes such as methyl violet, methylene blue.12
15 In other studies, Received: April 29, 2011
hydrogel composites and polyelectrolytes were explored for water Accepted: June 17, 2011
remediation purposes.16
20 Published: June 17, 2011

r 2011 American Chemical Society 2732 dx.doi.org/10.1021/am2005288 | ACS Appl. Mater. Interfaces 2011, 3, 27322737
ACS Applied Materials & Interfaces RESEARCH ARTICLE

able to retain the majority of the Orange II that is removed from

the water. This fact will allow the microgels to be physically
separated from the contaminated water by ltration, eectively
remediating the water. Future studies of this system will involve
tuning the pNIPAm-based microgel chemical functionality to
specically enhance the uptake eciency for certain contami-
nants, while allowing for the contaminant molecules to be
removed from the microgel structure through treatment after
microgel isolation from the contaminated water. This then will
allow the microgels to be applied and removed from the
contaminated water, treated to remove the isolated dye from
the microgel network, and subsequently reused for remediation.
Figure 1. Chemical structure of Orange II. While this will be the topic of future investigations from the
group, the studies here set the precedent for our future work. The
synthesis as a comonomer.33,36
39,42,43 Among the most com- current study hence highlights an inexpensive, straightforward,
mon comonomer used is acrylic acid (AAc), which has a pKa and ecient method for removing azo dyes from aqueous
4.25, which causes the microgel to swell at pH > pKa, and hinders solutions with extensive future utility.
the thermoresponsivity due to Coulombic repulsion.33,44
46
Previously, hydrogels of pNIPAm modied with polyacrya-
mide have been employed to determine the partition coecient MATERIALS AND METHODS
of Orange II and methylene blue in the system at dierent
temperatures. It was reported that the permeability of Orange II Materials. The monomer, N-isopropylacrylamide was purchased
through the hydrogels increased when temperature was raised from TCI (Portland, Oregon) and purified by recrystallization from
above 32 C.47,48 PNIPAm hydrogels and microgels, and pNI- hexanes (ACS reagent grade, EMD, Gibbstown, NJ). N,N0 -methylene-
PAm-co-methacrylic microparticles have been used in the past bisacrylamide (BIS) (99%), acrylic acid (AAc) (99%), and ammo-
for removal of dyes like Nile red, brilliant green, brilliant cresyl nium persulfate (APS) (98%) were obtained from Sigma-Aldrich
blue, etc. and heavy metal ions like Pb (II) and Cu (II) for water (Oakville, Ontario) and were used as received. Orange II was obtained
treatment applications.49
52 from Eastman Organic Chemicals (Rochester, New York). All the
In this submission, we assess the ability of thermoresponsive phosphate salts used for preparing buffer solutions of pH 7 and pH 3,
pNIPAm-co-AAc microgels to remove the azo dye molecule 4-(2- with ionic strengths of 0.235 and 0.09 M, respectively, were obtained
hydroxy-1-naphthylazo)benzenesulfonic acid sodium salt from EMD and were used as received. Deionized (DI) water with a
(Orange II) from water, Figure 1. While Orange II was chosen resistivity of 18.2 M 3 cm was obtained from a Milli-Q Plus system from
as a model azo dye molecule, and a model molecule for any Millipore (Billerica, MA), and filtered through a 0.2 m filter, prior to
number of potential organic contaminants found in water, use. Microgel samples were lyophilized using a VirTis benchtop
Orange II itself has been considered as a water contaminant. K-manifold freeze-dryer (Stone Ridge, New York)
For example, Orange II has been found in industrial euents Synthesis of Microgels. Microgels composed of poly (N-iso-
and has been treated using many chemical and physical propylacrylamide) were prepared by a surfactant free, free radical
techniques.53
55 We assessed the uptake eciency as a function precipitation polymerization as described previously.32 The total mono-
of AAc and microgel concentration, and how the uptake changed mer concentration was 140 mM, and was 95% N-isopropylacrylamide
as the temperature of the water was varied and the number of (NIPAm) and 5% N,N0 -methylenebisacrylamide (BIS) cross-linker. The
times the microgels were cycled above and below their LCST. monomer, NIPAm (13.3 mmol), and the cross-linker, BIS (0.700
We also determined the ability of pNIPAm microgels to retain mmol), were dissolved in deionized water (75 mL) with stirring in a
the removed Orange II. We found the pNIPAm-co-AAc micro- small beaker. The mixture was filtered through a 0.2 m filter affixed to a
gels to have a reasonable anity for Orange II, removing 29.5% 20 mL syringe into a 250 mL, 3-neck round-bottom flask. An additional
aliquot of deionized water (24 mL) was used to wash the beaker, which
Orange II at room temperature, which was signicantly increased
was filtered and transferred to the round-bottom flask. The flask was
to 56.6% upon heating. Additionally, the microgels are able to
then fitted with a thermometer, a condenser, stir bar, and a N2 inlet. The
retain most of the Orange II that was initially removed from the
temperature was set to 65 C and N2 was bubbled through the solution
water. The data obtained from these experiments will be used to
for 1 h, after which 0.197 mmol of 1 mL aqueous solution of APS
guide our future eorts in water remediation, but will also serve
initiator solution was added to the reaction mixture and was left to stir in
as information for our eorts related to drug delivery.56 For
the flask for 4 h, under N2 atmosphere. The solution was allowed to cool,
example, we are trying to identify microgel based systems that are while stirring overnight.
able to retain small molecules, and release them in a temperature Microgels composed of pNIPAM-co-AAc were prepared in a similar
triggered fashion. way by adding 0.700 mmol, 1.40 and 2.10 mmol of AAc to the reaction
This study represents a comprehensive assessment of pNI- mixture to synthesize pNIPAm-co-AAc microgels that were 5%, 10%, and
PAm-based microgels for water remediation applications. Not 15% AAc, respectively. The AAc was always added just prior to initiation,
only does the study reveal the important factors that need to be and the concentration of NIPAm was adjusted accordingly to maintain
considered when using these systems for this application, but it the monomer/cross-linker concentration constant at 140 mM for all
also may have signicant practical utility. For example, we microgel syntheses. The %AAC in the microgels will be represented
achieve 56.6% uptake eciencies after only 90 min of contact as pNIPAM-co-XAAc, where X = 0, 5, 10, and 15% AAc. The diameters of
with the contaminated water, while other recently reported these microgel systems were determined using dynamic light scattering
systems require many hours of contact time to approach the using a ALV/CGS-3 Compact Goniometer System (Hesse, Germany)
uptake eciencies reported here. Additionally, the system here is and were calculated as 795.4 nm, 945.2 nm, 1.103 and 1.384 m for

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ACS Applied Materials & Interfaces RESEARCH ARTICLE

pNIPAm-co-XAAc where X = 0, 5, 10, and 15%, respectively (see

Supporting Information).
Following stirring overnight, all microgels were ltered through
a type 1 Whatman lter paper, which was then rinsed with deionized
water. To remove unreacted monomer and cross-linker, as well as
linear polymer from the microgels, the microgel reaction solution
was separated into 15 mL centrifuge tubes obtained from Corning
Incorporated (Corning, NY) ( 12 mL microgel solution/tube) and
centrifuged at a speed of 8400 relative centrifugal force (rcf) in a
Baxter, biofuge 17R (Mount Holly, NJ) at 23 C, for 30 min. Cen-
trifugation yielded a pellet of microgels at the bottom of the centrifuge
tube, and the supernatant was removed. 12 mL of fresh DI water was Figure 2. Uptake of Orange II as a function of (a) percentage of AAc
added and the microgel pellet was redispersed using a Fisher Vortex, (0%, 5%, 10% and 15%) present in the pNIPAm microgel system and
Genie 2 vortexer (Pittsburgh, PA). This cleaning protocol was repeated (b) concentration of pNIPAm-co-10AAc. All the solutions were in a total
six times. volume of 3 mL and pH 7 buer. Each point on the plots represents an
Orange II Uptake. Microgels were lyophilized, and 52.1 mg of each average of three replicate experiments of uptake studies and the error
was redispersed in 10 mL of pH 7 buffer solution of 0.235 M ionic bars denote the standard deviation.
strength in a volumetric flask. The concentration of the stock microgel
solution was 5.21 mg microgels/mL. A stock solution of 0.023 M Orange were allowed to incubate for various intervals of times. For example,
II in deionized water was prepared. Using a micropipet, 300 L of immediately following splitting up the original solution, one tube was
microgels and 15 L of Orange II were transferred into a 15 mL centrifuged for 30 min and the supernatant solution removed and
centrifuge tube obtained from Corning Incorporated (Corning, NY). UV
vis performed on the supernatant solution, this was considered
A buffer solution of pH 7 of ionic strength 0.235 M was added to the tube t = 0. We allowed the other tubes to incubate for 10, 20, 30, 40, 50, 60, 80,
to give a total volume of 3 mL (final concentrations of microgels and and 100 min, respectively, before each was centrifuged.
Orange II are 521 g/mL and 114 M, respectively). For all the
experiments the buffer was added only after the dye was exposed to
the microgels. This solution was allowed to sit for five minutes and then RESULTS AND DISCUSSION
centrifuged for 30 min, at 8400 rcf to pack the microgels at the bottom
of the centrifuge tube. This centrifugation time was used to ensure that Uptake Studies at Room Temperature. The ability of
all the dispersed microgels were removed from solution (as confirmed microgels to remove organic azo dyes from aqueous solutions
from differential interference contrast microscopy, data not shown). The of pH 7 with ionic strength of 0.235 M was investigated by
supernatant was carefully removed from the tube without disturbing the exposing them to Orange II. Initially, we investigated the effect of
microgel pellet at the bottom of the centrifuge tube and transferred to a adding the weak acid AAc to the microgel structure. The
quartz cuvette and the absorbance measured using a HP8452A UV
vis experiment was performed by recording an initial absorbance
spectrophotometer with a diode array detector (previously Agilent spectrum of 114 M Orange II before the addition of 300 L of
Technologies, Inc., Santa Clara, CA). The initial concentration of microgels (521 g/mL), and comparing that to the absorbance
Orange II for all the uptake studies was maintained at 114 M and it of the supernatant after the addition of microgels. If Orange II
was also observed that the pH of Orange II solution does not change was removed from the solution a decrease in absorbance will be
when microgels are added to it. The initial absorbance of Orange II observed. The number of moles in the solution before and after
without microgels was also measured as a function of time the solution microgel addition was determined using a calibration curve (see
stayed in the tube. It was confirmed that the tube did not have any effect Supporting Information). The percent of Orange II removed
on increasing/decreasing the absorbance of Orange II, independent from the solution was subsequently calculated. Figure 2(a) shows
of time. the percent uptake as a function AAc concentration in the
Similar studies were performed at room temperature, using a buer microgels. The percent uptake was found to depend critically
solution of pH 3 with an ionic strength of 0.09 M. To study the uptake of on the AAc concentration, increasing from 6.63% for the
Orange II as a function of temperature, the solution of Orange II and pNIPAM-co-0AAc to 31.2% for pNIPAM-co-15AAc microgels.
microgels (only with pH 7 buer solution) was held at 50 C, for
This trend could be due to the increase in the size of the
dierent intervals of time (microgels deswell) and then cooled down to
microgels as the %AAc increases, as determined by DLS, where
room temperature (microgels reswell). This solution was then centri-
the size of the microgel increased from 795.4 nm for pNIPAm-
fuged and the supernatant was used to perform UV
vis studies.
co-0%AAc to 1.384 m for pNIPAm-co-15AAc. The uptake
Orange II Leaking Studies. To evaluate the ability of the
microgels to retain Orange II, the concentrations, and volumes from
percent using pNIPAm-co-10AAc was 29.5% (only about 2%
the previous section were scaled up three times. So in this case, 900 L of less than the 15% AAc system) and these microgels were used
microgels were exposed to 114 M Orange II in a total volume of 9 mL for subsequent experiments. Removal efficiency of microgels in
using the same buffer that was used for the uptake studies. This scaling pH 3 aqueous solution with an ionic strength 0.09 M was also
up was done to get a detectable absorbance signal from the solutions investigated using the same protocol as above. It was observed
after leaking. As for the Orange II removal studies above, the solution that the change in pH did not significantly alter the removal
was allowed to sit for five minutes followed by centrifugation for 30 min. efficiency of the dye (see Supporting Information). While this is
The supernatant solution was then carefully removed without disturbing the case, we chose to maintain the pH of the solutions at 7 for all
the microgels packed at the bottom. To this tube, 9.0 mL of fresh buffer other studies.
solution (the same buffer that was used for the uptake studies) was The eect of microgel concentration on the removal eciency
added and then the microgels were redispersed by vortexing. This was was also investigated, and the results are depicted in Figure 2(b).
immediately divided into nine, one mL samples in 1.5 mL Eppendorf The removal eciency steadily increased from 3.60% to 29.5% as
tubes obtained from Fisher Scientific, (Ottawa, ON) and the solutions the amount of pNIPAM-co-10AAc microgels was increased
2734 dx.doi.org/10.1021/am2005288 |ACS Appl. Mater. Interfaces 2011, 3, 27322737
ACS Applied Materials & Interfaces RESEARCH ARTICLE

Figure 3. Uptake of Orange II as a function of the time the microgels Figure 4. Leaking of Orange II from 10% AAc microgels as a function of
were held at elevated temperature for (9) one and (x) two cycles. Each leak time. Each point on the plot represents an average of three replicate
point on the plot represents an average of three replicate experiments of experiments of leaking studies and the error bars denote the standard
uptake studies and the error bars denote the standard deviation. deviation.

(86.6, 173, 346, and 521 g microgels/mL), but did not increase heating 300 L (521 g/mL) of pNIPAM-co-10AAc microgels
for 693 g microgels/mL). We hypothesize that this behavior is exposed to 15 L of Orange II to 50 C two times, followed by
observed because the removal of dye is an equilibrium process cooling cycles. The heating times were chosen such that the total
and addition of more microgels to the solution, past a certain time the microgels were held at elevated temperature matched
concentration, will not result in extra moles of the dye being the times for the single cycle, the only difference being the
removed. number of times the microgels were heated and cooled. For
Removal Efficiency As a Function of Temperature. 1. example, a solution of microgels was exposed to Orange II for five
Single Heating and Cooling Cycle of Microgels. PNIPAm micro- minutes, brought to 50 C for 10 min, cooled for 15 min, heated
gels are well-known to be thermoresponsive. That is, at T > again for 10 min, followed by cooling for 15 min. Overall, the
32 C they decrease in diameter by expelling their water of microgels were at elevated temperature for 20 and at RT for
solvation, as result they become more hydrophobic. This process 30 min, equivalent to the microgels that were heated 1 time for
is reversible, so at T < 32 C the microgels rehydrate and return 20 min. This was repeated for all the single cycle heating times.
to their initial state. At this pH and ionic strength, the thermo- Figure 3 shows that the uptake of Orange II increased after an
responsivity was still observed, as confirmed from light scattering additional heating cycle. The maximum uptake was increased
experiments (see Supporting Information). from a maximum of 50.3% from one hot cycle to 56.6% for an
For the uptake studies, we exposed 300 L (521 g/mL) extra hot cycle. The uptake also levels off after 90 min, similar to
pNIPAM-co-10AAc microgels to 15 L of Orange II, and cycled the single hot cycle data. We also investigated the effect of the
the temperature above and below 32 C and calculated the cycling the temperature one more time, and did not observe a
percent removal. We hypothesize that when the microgels significant increase in in the removal efficiency (see Supporting
rehydrate, they will absorb excess Orange II from solution. Information).
Additionally, we characterized the uptake eciency as a function Leaking Studies of Orange II. While the maximum removal
of time that the microgels were held at an elevated temperature. efficiency of the microgels was shown to be 56.6%, with two
Specically, the microgels were exposed to Orange II for ve 45 min heating cycles, it is important to evaluate the ability of the
minutes and heated to 50 C for periods of 20, 40, 60, 90, and 120 microgels to retain the Orange II that was removed from the
min. The solution was immediately cooled to room temperature water. To evaluate this, we exposed 900 L of pNIPAm-co-
(23 C) for 30 min and centrifuged. The absorbance of the 10AAc to Orange II for five minutes in a total volume of 9 mL
supernatant solution was then evaluated and percent removal using the same buffer as in the uptake studies, and the solution
determined. Figure 3 shows that the percent of Orange II re- was centrifuged and the supernatant solution removed. The
moved from solution increased from 29.5% (at RT) to 50.3% as resulting microgel pellet was redispersed in 9 mL of fresh buffer
the time the solution was held at elevated temperature increased by vortexing and divided into nine different Eppendorf tubes and
to 120 min. The gure also suggests that no more dye is taken allowed to incubate for various time intervals, from 0 to 100 min
up after the 90 min heating and 30 min cooling experiment. and then centrifuged, as indicated in the Materials and Methods
A control experiment was performed by heating Orange II of the section. The supernatant solution was then evaluated and the
same concentration (in buer) in the absence of microgels. It was percent Orange II leaked calculated. The percentage of Orange II
shown that the absorbance intensity of Orange II decreased by that was leaked was determined by calculating the number of
only 3.5% due to heating alone (see Supporting Information), moles Orange II that was initially removed from the solution and
which conrms that the improved uptake eciency of the micro- then determining how much was expelled after a given incuba-
gels by heating was indeed due to the thermoresponsive nature of tion time interval. The concentrations of Orange II were deter-
the microgels. mined from a calibration curve, as indicated above. For example,
2. Multiple Heating and Cooling Cycles of Microgels. Results the 0 min sample was immediately centrifuged after splitting
from the previous section indicate that temperature affects the the solution up and the supernatant solution evaluated. The
removal efficiency of the microgels, which is hypothesized to be number of moles in this solution was compared to how many
due to the thermoresponsive nature of the microgels. The effect moles were initially in the microgels. Figure 4 shows the trend
of multiple heating cycles was also investigated. This was done by for the percent leaking of Orange II as a function of leaking time.
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ACS Applied Materials & Interfaces RESEARCH ARTICLE

There are reports of pNIPAm microgels and other polymer

systems that adsorb certain organic molecules in a Langmuir
adsorption pattern.57,58 The R2 value was calculated as 0.9518,
which indicates that Langmuir model is a reasonable one to use.

CONCLUSION
We report microgel systems of pNIPAm modied with
varying concentrations of AAc which eciently absorb the azo
dye Orange II, the most ecient of these systems being
pNIPAm with 10%AAc. The results indicate that by exploiting
the thermoresponsive nature of these microgels, the percent
absorption of Orange improved signicantly by heating and
Figure 5. Langmuir adsorption isotherm for the removal of Orange II cooling the microgels for a single cycle when compared with
by the microgels. Cm is the concentration of the dye remaining in the room temperature studies. The control experiments performed
aqueous phase and Cs is the concentration of the dye sorbed to the prove that the decrease in absorbance was due to the uptake
microgels. The goodness of t (R2) value was calculated as 0.9518. Each of Orange II by the microgels and not merely due to any
point on the plot represents an average of three replicate experiments
change in the absorbance of Orange II at higher temperatures.
and the error bars denote the standard deviation.
Furthermore, the leaking studies show that the microgels leak out
25.6% of the Orange II that was originally removed from
The figure indicates that percentage of Orange II that leaked solution, with no more leaking occurring after 50 min. The
from the microgels increased with time up to 50 min and leveled Langmuir coecient of 0.01143 ( 0.00134 was calculated by
off after this time. We calculated that a maximum of 25.6% of the tting a Langmuir isotherm to the data in Figure 5. In the
absorbed dye leaks out of the microgels. This translates to a future, we will use these systems to remove naphthenic acids,
74.4% retention efficiency. We also addressed the possibility of PAHs, PCBs, drug molecules, etc. present in the industrial
Orange II leaking out further with the addition of fresh buffer. euents and of major concern for human and aquatic life.
We removed the supernatant from the sample that was allowed Also, we will use this information to design ecient drug
to incubate for 100 min and added 1.0 mL fresh buffer to this delivery systems.
system and allowed the solution to incubate for 60 min. This was
then centrifuged and the supernatant was removed to record the ASSOCIATED CONTENT
absorbance; no significant increase in leaked Orange II was
observed. Additionally, we studied the possibility of microgels bS Supporting Information. UV
vis spectra for Orange II
leaking out Orange II at elevated temperature. The microgels held at high temperature in the absence of microgels and leaking
deswell by expelling water of solvation when heated above their studies of Orange II at high temperature, calibration plot used for
LCST. In order to test if the microgels leak out more Orange II at calculating the uptake eciency, trend for uptake of Orange II as
higher temperatures, we redispersed the supernatant from the a function of AAc percentage at pH 7 and pH3, trend for uptake
tube that was allowed to incubate for 100 min (at room tem- of Orange II for multiple (three) heating and cooling cycles, light
perature) with the microgels. This solution was then allowed to scattering data for thermoresponsivity of the microgels and DLS
incubate for another 100 min on a hot plate at 50 C and was data for the dierent sizes of the microgels. This material is
immediately centrifuged for 30 min at 50 C by regulating the available free of charge via the Internet at http://pubs.acs.org.
thermostat in the centrifuge. The supernatant was removed and
the absorbance was measured. The results show that leaking is AUTHOR INFORMATION
not affected by temperature, see Supporting Information. Corresponding Author
Uptake Studies As a Function of Orange II Concentration. *E-mail: [email protected].
We also investigated the ability of the pNIPAm-co-10AAc
microgels to remove Orange II from aqueous solution as a func-
tion of Orange II concentration. We exposed 300 L (521 g/ ACKNOWLEDGMENT
mL) of pNIPAM-co-10AAc microgels to 5, 10, 15, 20, 25, 30, and M.J.S. acknowledges funding from the University of Alberta
35 L of Orange II from the stock solution in a total of 3 mL (Department of Chemistry and the Faculty of Science). Funding
buffer (pH 7, 0.235 M ionic strength). The microgels were then through the Natural Sciences and Engineering Research Council
centrifuged for 30 min and the supernatant was analyzed by (NSERC) and the Canada Foundation for Innovation (CFI) is
UV
vis, as explained above. The data (Figure 5) was fit with a also acknowledged. We also thank Prof. John C. Vederas and Prof.
Langmuir isotherm (eq 1), which yielded a maximum concen- Christopher W. Cairo for access to their respective lyophilizers.
tration of Orange II adsorbed on the microgels as 139.9 mol/g
(0.049 g Orange II/g microgels) and a Langmuir coefficient of
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