Reactive and Functional Polymers 121 (2017) 91–100

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Reactive and Functional Polymers

journal homepage: www.elsevier.com/locate/react

Versatile functionalization platform of biporous poly(2-hydroxyethyl MARK

methacrylate)-based materials: Application in heterogeneous supported
catalysis
H.B. Lya, R. Pouparta, B. Carbonniera, V. Monchietb, B. Le Droumagueta,⁎, D. Grandea,⁎
a
Université Paris-Est, Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182 CNRS-UPEC, 2 rue Henri Dunant, 94320 Thiais, France
b
Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Echelle, UMR 8208 CNRS – UPEC – UPEM, 5, boulevard Descartes, 77454 Marne-la-Vallée, Cedex,
France

A R T I C L E I N F O A B S T R A C T

Keywords: This paper highlights the straightforward and versatile functionalization of biporous poly(2-hydroxyethyl me-
Doubly porous polymeric materials thacrylate) (PHEMA)-based networks obtained from the double porogen templating approach, and their sub-
Porogenic agents sequent utilization as efficient catalytic supports in heterogeneous supported catalysis. Advantage of the
Spark plasma sintering availability of hydroxyl groups within the PHEMA-based frameworks was taken through chemical modification
Gold nanoparticles
with carbonyl diimidazole. This key activation led to miscellaneous functionalization reactions of the materials
Supported catalysis
via nucleophilic substitution or thiol-ene/thiol-yne “click” additions of functional organic molecules mainly
containing amino or thiol groups. Further, in-situ generation and immobilization of gold nanoparticles (GNPs) on
selected thiol- or amine-functionalized biporous frameworks allowed for the preparation of innovative GNP@
PHEMA materials. The as-obtained hybrid frameworks could efficiently be used as supported catalysts in NaBH4-
mediated reduction of 4-nitrophenol. The reusability of amine-bearing hybrid catalysts is proved over 5 suc-
cessive 1 h-cycles with stable yields around 90%.

1. Introduction catalyzed azide-alkyne cycloaddition (CuAAC) reaction, also well-

Surface chemistry plays an important role in the field of porous
polymer materials. Over the past decades, investigation in this area has
received much attention and has been oriented toward various appli-
cations [1]. In this regard, the surface modification of porous scaffolds
to promote interactions with cells has been considerably developed, due
to the possibility of altering the ability of cellular response or influen-
cing the rate of tissue regeneration [2,3]. Conversion of non-polar,
hydrophobic surfaces to polar, hydrophilic, water-wettable surfaces by
plasma techniques, [4–6] electrochemical processes, [7] or in-situ
polymerization of hydrophilic monomers, [8] are attractive examples of
surface modification. Furthermore, polymer modification by grafting
chemistry is one of the interesting methods that have widely been used
in the literature for separation science, [9,10] for instance.
In this context, poly(2-hydroxyethyl methacrylate) (PHEMA) has
been the subject of numerous studies as it presents unique biocompat-
ibility properties, while its chemical functionalization can be envi-
sioned through modification of the pendant hydroxyl groups via diverse
surface chemistries. One of these strategies relies on the copper-
known as Huisgen [3 + 2] cycloaddition [11]. In this particular case,
hydroxyl groups were transformed to the corresponding azide moieties
via a two-step process involving the mesylation of the alcohol function
and subsequent substitution of the mesylate leaving group in the pre-
sence of sodium azide. The resulting azido-functionalized PHEMA-
based polymer could thereafter be functionalized by alkynyl biotin
through a straightforward CuAAC reaction in the presence of Cu-
SO4·5H2O/sodium ascorbate as the catalyst. In addition, PHEMA hy-
droxyl pendant chains could be easily turned into the corresponding
carboxylic acid moieties by reaction with bromoacetic acid in con-
centrated sodium hydroxide (2 M NaOH) aqueous solution [12]. Hy-
droxyl groups of PHEMA-based thin films could also be quantitatively
reacted with acyl chlorides, such as acetyl chloride or cinnamoyl
chloride, even with films thicknesses higher than 100 nm, thus de-
monstrating the high reactivity and accessibility of such alcohol side
functions [13]. In a similar fashion, iothalamyl chloride or the acid
chloride of acetylated iopanoic acid were reacted with alcohol moieties
of PHEMA microspheres in the presence of N,N′-dimethyl para-tolui-
dine (DMPT) to afford the two corresponding radiopaque substances for

⁎
Corresponding authors.
E-mail addresses: poupart@icmpe.cnrs.fr (R. Poupart), carbonnier@icmpe.cnrs.fr (B. Carbonnier), vincent.monchiet@univ-paris-est.fr (V. Monchiet),
ledroumaguet@icmpe.cnrs.fr (B. Le Droumaguet), grande@icmpe.cnrs.fr (D. Grande).

http://dx.doi.org/10.1016/j.reactfunctpolym.2017.10.024
Received 4 September 2017; Received in revised form 28 October 2017; Accepted 30 October 2017
Available online 31 October 2017
1381-5148/ © 2017 Elsevier B.V. All rights reserved.
H.B. Ly et al.
clinical uses [14]. Other reported strategies for the functionalization of
PHEMA rely on the pre-activation of –OH groups using various acti-
vating chemicals, such as N,N′-disuccinimidyl carbonate (DSC) [15] or
N,N′-dicyclohexylcarbodiimide (DCC), and subsequent functionaliza-
tion with molecules containing α-amine moieties, such as PEG-NH2 and
C16H32-NH2. Alternatively, PHEMA hydroxyl functions could be reacted
with succinic anhydride in the presence of dimethylaminopyridine
(DMAP) to afford the corresponding carboxylic acid derivatives. A
subsequent step in the presence of DMAP and DCC allowed for the
activation of the carboxylic functions that were in turn reacted with
nucleophilic Nα,Nα-bis(carboxymethyl)-L-lysine hydrate to produce ni-
trilotriacetic acid-based membranes for high-capacity protein-binding
applications [16,17]. Further, surface-immobilized PHEMA brushes
could be reacted with para-nitrophenyl chloroformate (NPC) to gen-
erate the corresponding pendant activated esters that were in turn re-
acted with different RGD-based peptides, namely GGGRGDS, GGGRDGS
or pyrene derivatized GGGRGDSK (GGGRGDSK (Py)) so as to prepare
convenient substrates for integrin specific adhesion of human umbilical
vein endothelial cells (HUVECs) [18]. Finally, PHEMA could also be
activated with carbonyl diimidazole (CDI) to afford the corresponding
activated esters [13]. Successive reaction with a suitable nucleophile
such as N,N-dimethylethylenediamine (DMEDA) afforded the corre-
sponding carbamate quantitatively. A rather similar strategy relied on
the functionalization of PHEMA hydroxyl groups by reaction with
propargyl ester of carbonyl imidazole, the latter being prepared by
reaction of propargyl alcohol with CDI [19].
Last but not least, the use of proper chemical moieties to anchor
metallic nanoparticles has allowed for the formation of (nano)reactors
that can advantageously be used as porous polymer-supported nano-
catalysts [20,21]. In the past years, the immobilization of metallic na-
noparticles on the surface of porous polymers has undergone significant
development for a wide range of applications, [22] such as anti-
microbial [23] or heterogeneous catalysis, which is of crucial im-
portance [24–26]. Besides the nanometals frequently reported in the
literature, including silver, [27] palladium, [28] or platinum, [29] gold
appears to be the most attractive candidate [30]. It is well-known that
gold nanoparticles (GNPs) can be covalently attached to pore surfaces
which bear amine, [31] thiol, [32,33] alcohol, [34] imidazolyl [35] or
amidoxime [36] functions. Miscellaneous catalytic supports have been
used in the literature, such as capillary systems, [31,35,37] monoliths,
[33,38] carbon nanotubes, [39,40] zeolites, [41,42] metal-organic
frameworks, [43,44] graphene, [45] and silica-based materials [46].
Recently, we have developed the fabrication of doubly porous ma-
terials based on PHEMA as model systems [47–49]. Such original ma-
terials with multiple porosity levels may hold relevance in the areas of
civil engineering, soil mechanics or tissue engineering, for instance. The
larger pore sizes would allow macromolecules or large compounds flow
through the materials, while the smaller pore sizes would be dedicated
to the passage of smaller molecules or play an important role regarding
filtration applications. Alternatively, the implementation of such bi-
porous PHEMA frameworks for heterogeneous supported catalysis
should lead to improved reaction yields, mainly due to the increasing of
specific surface area brought by the lower porosity level but also to
increased accessibility of the catalyst due to the presence of the upper
porosity level. More importantly, such PHEMA materials represent a
versatile platform for the fine tuning of the interface chemical com-
position, through the CDI activation pathway. In this way, different
chemical functions can be easily anchored at the pore surface such as
amines, thiols or carboxylic acids, leading to noticeable differences in
the further immobilization of gold nanoparticles.
In the present paper, we describe the synthesis and application of a
new type of catalytic support derived from a suitably functionalized
doubly porous cross-linked poly(2-hydroxyethyl methacrylate)
(PHEMA)-based matrix. Various surface modifications of the matrix are
first addressed by using solely CDI chemistry or by combining CDI
chemistry and subsequent “click” chemistry via either thiol-ene or thiol-
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Reactive and Functional Polymers 121 (2017) 91–100
yne additions of functional organic molecules. In selected cases, the
catalytic response of the resulting functionalized biporous materials is
then examined. As a matter of fact, GNPs are immobilized on the amine-
or thiol- modified surface of PHEMA-based frameworks through in-situ
reduction of corresponding salts. Through GNP-catalyzed hydride-
mediated reduction of 4-nitrophenol, we demonstrate the higher effi-
ciency of the newly synthesized catalytic supports with double porosity
compared to that associated with their monoporous analogues only
possessing either the upper porosity level (larger pore sizes) or the
lower porosity level (smaller pore sizes).
2. Experimental section
2.1. Materials
2-hydroxyethyl methacrylate (HEMA, 97%), ethylene glycol di-
methacrylate (EGDMA, 98%), 2,2′-azobisisobutyronitrile (AIBN, 98%),
ethylenediamine (EDA, ≥ 99%), sodium borohydride (NaBH4, ≥ 99%),
2,2-dimethoxy-2-phenylacetophenone (DMPA, 99%), D,L-dithiothreitol
(DTT, ≥ 98%), and L-glutathione (GSH, ≥ 99% powder) were pur-
chased from Sigma Aldrich. 4-nitrophenol (99%), 1,1′‑carbonyl diimi-
dazole (CDI, 97%), mercaptoacetic acid (thioglycolic acid, 97%+),
allylamine (98%+), propargylamine (98%) and hydrogen tetra-
chloroaurate (III) hydrate (HAuCl4, 99.9%) were obtained from Alfa
Aesar. Cysteamine (≥ 98%) was supplied by Fluka. Sodium chloride
(NaCl) particles with sizes ranging from 50 to 500 μm were purchased
from Prolabo, and were stored under moisture-free conditions. Prior to
use, they were sieved to isolate the particle fraction with average sizes
between 125 and 200 μm. Methanol (MeOH), absolute ethanol (EtOH,
99%), propan-2-ol (i-PrOH, for analysis, ACS-Reag.Ph.Eur), acetonitrile
(ACN, HPLC grade), and acetone were supplied by Carlo Erba. All re-
agents and solvents were used without further purification, except for
AIBN that was recrystallized from methanol and stored at 4 °C, prior to
use. 18.2 MΩ deionized water was filtered through a Milli-Q Plus pur-
ification pack.
2.2. Preparation of porous PHEMA-based materials
Initially, sieved NaCl particles were submitted to a Spark Plasma
Sintering (SPS) treatment so as to obtain a fused NaCl particle phase. A
Sumitomo Dr. Sinter Lab 515S SPS machine from Fuji Electronic
Industrial was used. Experimentally, 125–200 μm sieved NaCl particles
were introduced into a graphite die and heated from room temperature
to 100 °C at a heating rate of 50 °C·min− 1, while applying a 3 kN force
onto the sample under inert atmosphere, as already reported by our
group [47]. After 20 min at 100 °C, the sintered sample was cooled to
room temperature at a rate of 50 °C·min− 1. The mixture consisting of
HEMA, EGDMA (molar ratio: 70/30 mol%), DMPA (2 wt.% with respect
to comonomers), and propan-2-ol (i-PrOH) as the porogenic solvent
(85 vol% with respect to the total volume of comonomers) was added to
the fused NaCl particle template, and the polymerization was con-
ducted in a UV oven for 4 h at 365 nm. NaCl macro-sized particles re-
moval by water extraction took 1 day. After this step, the samples were
washed abundantly with deionized water, and dried at room tempera-
ture under vacuum. Gravimetric analysis confirmed the complete re-
moval of both porogens.
The generation of monoporous analogues was similar to that of
doubly porous materials. In the case of the PHEMA-based macroporous
material only possessing the upper porosity level, 125–200 μm sieved
NaCl particles were solely used and no porogenic solvent was used. In
the case of the porous material only possessing the lower porosity level,
the polymerization mixture (70 mol% HEMA, 30 mol% EGDMA, DMPA
-2 wt.% with respect to comonomers-, and i-PrOH − 85 vol% with re-
spect to the total volume of comonomers-) was directly introduced in a
glass vial, without previously forming the NaCl particle template.
H.B. Ly et al.
2.3. Functionalization of biporous poly(HEMA-co-EGDMA) materials
2.3.1. Activation of PHEMA with CDI
100 mg of porous poly(HEMA-co-EGDMA) (~ 0.66 mmol of hy-
droxyl groups) were immersed in 2 mL of acetone, along with 2 equiv.
of CDI (compared to hydroxyl groups in the porous materials, i.e.
214 mg). The reaction medium was gently stirred on an orbital shaking
plate overnight. The solid was then filtered off, washed abundantly
with acetone, and dried under vacuum. The as-obtained material (CDI-
activated PHEMA, A) was characterized by Raman spectroscopy.
2.3.2. Functionalization of CDI-activated PHEMA material with cysteamine
A sample of porous CDI-activated PHEMA framework (100 mg) was
immersed in 2 mL of absolute ethanol. Cysteamine (102 mg, 2 equiv.
compared to hydroxyl groups in the porous precursor) was then added.
The solution was gently shaken for 24 h at room temperature. After
washing with an abundant quantity of absolute ethanol, the resulting
porous PHEMA-based material was dried under vacuum for 24 h, and
analyzed by Raman spectroscopy. For the sake of comparison, such a
thiol-functionalized PHEMA-based material displaying a double por-
osity was denoted as PHEMA-SH B.
2.3.3. Functionalization of CDI-activated PHEMA material with
ethylenediamine
A sample of CDI-activated PHEMA (100 mg) was immersed in 2 mL
of propan-2-ol (i-PrOH). Ethylenediamine (79 mg, 2 equiv. compared to
hydroxyl groups in the porous precursor) was added. The solution was
then gently shaken for 24 h at room temperature. After washing with an
abundant quantity of i-PrOH, the resulting porous PHEMA-based ma-
terial was dried under vacuum for 24 h, and analyzed by Raman
spectroscopy. For the sake of comparison, such an amine-functionalized
biporous PHEMA-based material was denoted as PHEMA-NH2 C. We
also referred to C1 and C2 for the monoporous analogue with the
corresponding upper porosity level, and the monoporous analogue with
the corresponding lower porosity level, respectively.
2.3.4. Functionalization of CDI-activated PHEMA material with allylamine
A sample of CDI-activated PHEMA (100 mg) was immersed in 2 mL
of acetonitrile (ACN). Allylamine (75 mg, 2 equiv. compared to hy-
droxyl groups in the porous precursor) was added, and the solution was
gently shaken for 24 h at room temperature. The resulting porous
PHEMA-based materials was washed with an abundant quantity of
acetonitrile, then acetone, and dried under vacuum for 24 h before
Raman spectroscopy measurements. The functionalized doubly porous
material was denoted as PHEMA-ene D.
2.3.5. Functionalization of CDI-activated PHEMA material with
propargylamine
A sample of CDI-activated PHEMA (100 mg) was immersed in 2 mL
of acetone. Propargylamine (73 mg, 2 equiv. compared to hydroxyl
groups in the porous precursor) was added, and the solution was gently
shaken for 24 h at room temperature. The resulting porous PHEMA-
based material was washed with an abundant quantity of acetone, and
dried under vacuum for 24 h before being analyzed by Raman spec-
troscopy. The functionalized doubly porous material was denoted as
PHEMA-yne E.
2.3.6. Functionalization of PHEMA-ene and PHEMA-yne with cysteamine
A sample of PHEMA-ene D or PHEMA-yne E (100 mg) was im-
mersed in 2 mL of absolute ethanol. Cysteamine (153 mg, 3 equiv.
compared to hydroxyl groups in the porous precursor) was added and
solubilized. The thiol-ene reaction (or thiol-yne in case of PHEMA-yne)
was conducted at 70 °C in the presence of AIBN (2 wt.% with respect to
the polymer) for 24 h. The samples were then washed with an abundant
quantity of absolute ethanol, and dried under vacuum for 24 h before
Raman spectroscopy analysis. The resulting doubly porous materials
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Reactive and Functional Polymers 121 (2017) 91–100
were denoted as PHEMA-NH2F and PHEMA-(NH2)2H, respectively.
2.3.7. Functionalization of PHEMA-ene and PHEMA-yne with thioglycolic
acid
A sample of PHEMA-ene D or PHEMA-yne E (100 mg) was im-
mersed in 2 mL of absolute ethanol in presence of thioglycolic acid
(182 mg, 3 equiv. compared to hydroxyl groups in the porous pre-
cursor). The thiol-ene reaction (or thiol-yne in case of PHEMA-yne) was
conducted at 70 °C in the presence of AIBN (2 wt.% with respect to the
polymer) for 24 h. The samples were then washed with an abundant
quantity of absolute ethanol, and dried under vacuum for 24 h before
Raman spectroscopy analysis. The resulting doubly porous materials
were denoted as PHEMA-COOH G and PHEMA-(COOH)2I, respectively.
2.3.8. In-situ generation of gold nanoparticles within functionalized
PHEMA-based networks
35 mg of the porous polymeric materials (B, C, C1, C2, and H) were
introduced separately into different vials containing 2 mL of a freshly
pre-prepared 10 wt.% of HAuCl4 aqueous solution, and let to react
overnight. The polymers were then washed several times with deio-
nized water in order to remove the excess of Au3 + ions that were
loosely attached on the surface of the materials. The samples were then
transferred into 2 mL of an aqueous solution of NaBH4 (7 mg in 2 mL
water) for 2 h in order to generate the gold nanoparticles (GNPs). The
hybrid samples based on GNP@PHEMA were washed several times with
deionized water and dried under vacuum.
2.3.9. Reduction of 4-nitrophenol by heterogeneous supported catalysis
10 mg of the gold functionalized monoporous samples with a simple
amine function (GNP@C1, GNP@C2) were separately incorporated into
a freshly prepared solution containing 20 μL of a 4-nitrophenol solution
(4 mg in 10 mL deionized water), 20 μL of a NaBH4 solution (114 mg in
10 mL water), and 4 mL of water. UV–Visible spectra were recorded
before the adjunction of the gold-functionalized samples and 1 h after
their addition. On the other hand, other samples (GNP@B, GNP@C,
GNP@H) were separately introduced into a solution of 20 μL of 4-ni-
trophenol, 60 μL of NaBH4, and 4 mL of water. The yields of 4-ni-
trophenol reduction were evaluated by off-line UV–Visible spectro-
photometry by following the decrease of the intensity of the π → π*
transition band attributed to the 4-nitrophenolate ion at 400 nm.
Experimentally, a small volume (20 μL) of the heterogeneous catalytic
reduction mixture was withdrawn from the reaction vessel, diluted in
4 mL of deionized water and transferred in a UV quartz cuvette. The
relative standard deviation for each measurement was found to stand
within ± 3%. Comparisons were carried out during five successive
cycles of 1 h under the same experimental conditions. A blank experi-
ment in the absence of GNPs was also recorded for a 1 h cycle.
2.4. Instrumentation
Scanning Electron Microscopy (SEM) analyses of the materials were
performed with a MERLIN microscope from Zeiss equipped with InLens,
EBSD (back-scattered electrons) and SE2 (secondary electrons) detec-
tors using a low accelerating tension (2–3 kV) with a diaphragm aper-
ture of 30 μm. Prior to analyses, the samples were coated with a 4-nm
thin layer of palladium in a Cressington 208 HR sputter-coater. Semi-
quantitative Calculations of average pore sizes of PHEMA materials and
gold particle sizes were realized with the ImageJ software. Energy-
dispersive X-ray spectroscopy (EDX) was performed using a SSD X-Max
detector of 50 mm2 from Oxford Instruments (127 eV for the Kα of
Mn). The porosity ratios, pore volumes, and pore size distributions of
the materials were determined by mercury intrusion porosimetry (MIP)
using an AutoPore IV 9500 porosimeter from Micromeritics. The de-
termination of the porosity features was based on the Washburn
equation between the applied pressure (from 1.03 to 206.8 MPa) and
the pore diameter into which mercury intruded. The chemical structure
H.B. Ly et al.
of the polymeric materials was examined using an XPlora One Raman
spectrometer from Horiba Jobin Yvon equipped with a laser emitting at
638 nm. The acquisition time was fixed at 1 min. UV–Visible spectra
were recorded on a Cary 60 spectrophotometer from Agilent
Technologies from 200 to 800 nm. Inductively-coupled plasma optical
emission spectrometry (ICP-OES) analyses were performed using a
Varian Vista-PRO CCD Simultaneous spectrometer. Gold nanoparticle
(GNP) size was determined by dynamic light scattering on a Zetasizer
Nano-ZS (Malvern Instrument) equipped with a He–Ne laser
(λ = 633 nm, scattering angle 173°).
3. Results and discussion
The double porogen templating approach is known to be an effec-
tive and versatile route to control pore size, morphology, and inter-
connectivity of doubly porous polymeric materials [49]. In this paper, a
further step to various applications of our original biporous materials is
proposed. In order to design such porous polymeric materials, 2-hy-
droxyethyl methacrylate (HEMA) was chosen as it has been reported in
previous studies as a monomer of choice for biomedical applications,
especially regarding its biocompatible properties but also because of the
pendant hydroxyl functions that allowed for miscellaneous surface
modification.46 Moreover, this methacrylic monomer is water-wettable
and should permit easy accessibility of reactants within the resulting
porous frameworks in aqueous solutions. The carbonyl diimidazole
chemistry is well-known to activate polyhydroxyl surfaces that allows
for further nucleophilic substitution with amino compounds [50].
Herein, four different molecules, namely cysteamine, ethylenediamine,
allylamine, and propargylamine were proposed. The motivation for the
grafting of the first two molecules onto PHEMA@CDI surface was the
ability to immobilize gold nanoparticles, whereas the last two reactants
allowed for various functionalization reactions based on thiol-ene or
thiol-yne “click” addition (i.e. with cysteamine and thioglycolic acid).
In the cases of cysteamine-based additions, it is interesting to observe
the effect of chelating groups (i.e.eSH, eNH2 or double eNH2) on the
gold nanoparticles morphology. On the other hand, the grafting of
carboxylic acid functions via thiol-ene or thiol-yne “click” reactions
could enrich the possibility of surface modifications for PHEMA-based
porous materials, mainly with the immobilization of metallic ions, for
instance [21,51].
3.1. Characterization of porous PHEMA-based frameworks
The doubly porous PHEMA-based material resulting from the ex-
traction of NaCl macro-sized particles and the porogenic solvent (i-
PrOH) displayed a 92% overall porosity ratio, as determined by mer-
cury intrusion porosimetry (MIP), with a upper to lower porosity vo-
lume ratio of about 85/15 vol.%, the upper and lower porosities arising
from the removal of NaCl particles and i-PrOH, respectively. These
results are consistent with the amounts of the distinct porogenic agents
introduced into the polymerization feed. Indeed, the polymerization
feed was constituted of a monomers/i-PrOH/NaCl particles volume
ratio equal to 5/9.5/85.5 vol%. The experimental volume ratio calcu-
lated after polymerization and subsequent porogen removal was equal
to 8/14/78 vol%, which was in rather good agreement with that ex-
pected from the experimental conditions chosen. The MIP profile as-
sociated with this porous framework indicated a bimodal porosity with
a macroporosity centered around 40 μm and a lower porosity level with
peak size centered at 8 μm (data not shown, see Table 1). It is note-
worthy that the pore size distribution curve presented a bimodal dis-
tribution with an interconnected macroporosity, as previously reported
elsewhere [49]. The use of SPS treatment for sintering NaCl particles
constituted an unprecedented methodology.
This novel route could thus generate materials with controlled
macropore connectivity. Indeed, the threshold (or interconnectivity
window) size could be equal to about 85, 65, or 40 μm, depending on
94
Reactive and Functional Polymers 121 (2017) 91–100
Table 1
Porous features of porous PHEMA-based materials obtained by using 70/30 mol% HEMA/
EGDMA as determined by MIP.
Porosity ratio Peak pore Peak pore Upper to lower
(%) size (μm) size (μm) porosity volume
ratio
Biporousa 92 40 8 85/15
Monoporousb 72 – 9 0/100
Monoporousc 74 42 – 100/0
a
Biporous material obtained by using 85 vol.% i-PrOH and NaCl template derived from
SPS.
b
Monoporous material obtained by using 85 vol.% i-PrOH as porogenic solvent.
c
Monoporous material obtained by using NaCl template derived from SPS.
the NaCl particle size, i.e. 250–400, 200–250, or 125–200 μm, respec-
tively (data not shown). Similar MIP profiles were also observed with
poly(High Internal Phase Emulsion) (HIPE)-based porous materials in
which average pore sizes were usually lower than those measured from
SEM images [52–54]. SEM micrographs of the biporous polymer
showed macropores having NaCl particle imprints with an average size
ranging from 120 to 200 μm. For the sake of comparison, two mono-
porous analogues were also prepared. The monoporous analogue with
only the lower porosity level (i-PrOH as sole porogen) possessed an
average pore size around 9 μm with a 72% porosity ratio. The mono-
porous counterpart with only the upper porosity level (SPS-sintered
NaCl template as sole porogen) possessed an average pore size of 42 μm
and a 74% porosity ratio (data not shown, see Table 1).
These results confirmed an undeniable advantage of the double
porogen approach to generate doubly porous materials: pore size and
connectivity of each porosity level could be independently controlled
via particle size and packing for the upper porosity level, and through
the use of different porogenic solvents along with their volume con-
tents, for the lower porosity level [49].
3.2. Functionalization of porous PHEMA-based materials
The key modification of porous PHEMA-based polymers consisted in
the activation of interfacial hydroxyl groups with CDI, as shown in
Scheme 1. By Raman spectroscopy, characteristic bands were found at
1760 cm− 1 corresponding to stretching vibrations of the imidazolyl
carbamate function, and at 3130 and 3160 cm− 1 corresponding to
stretching vibrations of CeH bonds arising from the imidazole ring,
while the ester functions of PHEMA at 1725 cm− 1 were not impacted
by this chemical modification. This modification was also reported in
our previous work, [47] as a preliminary result for various functiona-
lization reactions herein proposed. The Raman spectra of resulting
functionalized polymers are presented in Fig. 1. Chemical reactions
with the CDI-activated PHEMA A material were accomplished by nu-
cleophilic substitution with miscellaneous amino (eNH2) compounds,
i.e. cysteamine, ethylenediamine, allylamine, and propargylamine
(Scheme 1). The success of all these reactions was testified by Raman
spectroscopy, with the total disappearance of characteristic bands of
imidazolyl carbamate.
Moreover, specific Raman signatures corresponding to the em-
ployed amino compounds could be noticed: for PHEMA-SH B obtained
from reaction of CDI-activated PHEMA A material with cysteamine, the
appearance of a characteristic thiol (eSH) stretching band was ob-
served at 2570 cm− 1. It is noteworthy that in order to obtain such a
signal, after reaction with cysteamine, the sample was treated in a
phosphate buffer solution (pH = 8; 5 mM) containing 1 M DTT to
eventually cleave possible disulfide bridges, visible at 500 cm− 1 by
Raman spectroscopy (data not shown). For PHEMA-NH2C derived from
reaction of CDI-activated PHEMA A material with ethylenediamine, a
weak stretching band of -NH2 was found at 3310 cm− 1. For PHEMA-
ene D resulting from reacting CDI-activated PHEMA A with allylamine,
H.B. Ly et al.
Scheme 1. Miscellaneous synthetic routes used for the functionalization of porous PHEMA-based networks.
Fig. 1. Raman spectra of PHEMA-based porous frameworks: PHEMA-based networks
after activation of native PHEMA with CDI (PHEMA-CDI A), after subsequent functio-
nalization with cysteamine (PHEMA-SH B), ethylenediamine (PHEMA-NH2C), allylamine
(PHEMA-ene D) or propargylamine (PHEMA-yne E), and subsequent functionalization via
thiol-ene reaction of PHEMA-ene D with thiol compounds to afford the corresponding
porous materials PHEMA-NH2F and PHEMA-COOH G, or thiol-yne reaction of PHEMA-
yne E with thiol compounds to afford the corresponding porous materials PHEMA-
(NH2)2H and PHEMA-(COOH)2I.
95
Reactive and Functional Polymers 121 (2017) 91–100
the appearance of a stretching band ν(C]C) at 1640 cm− 1 was de-
tected [21,55]. Finally, for PHEMA-yne E after subsequent coupling of
CDI-activated PHEMA A with propargylamine, the spectrum showed a
characteristic intense band at 2120 cm− 1 ascribed to alkyne stretching
vibrations ν(C^CeH). We then took advantage of the presence of either
alkene or alkyne moieties at the surface of corresponding materials (i.e.
PHEMA-ene D and PHEMA-yne E) to investigate the possibility to use
such materials as a versatile “click” platform.
Raman spectroscopy was used to monitor the thiol-ene “click” re-
actions of the alkene-modified framework with cysteamine and thio-
glycolic acid to afford the resulting PHEMA-NH2F and PHEMA-COOH G
(see Fig. 1). As expected, it was observed that C]C double bonds were
completely consumed through the disappearance of the corresponding
band at 1640 cm− 1. A specific Raman signal corresponding to the
amino groups was observed at ~3310 cm− 1 in the case of the reaction
with cysteamine (PHEMA-NH2F), whereas no further band corre-
sponding to the mercaptoacetic acid was found when reacting PHEMA-
ene D with one such compound (PHEMA-COOH G). Again, Raman
spectroscopy permitted to assess the completion of the thiol-yne “click”
reactions of the alkyne-modified framework with cysteamine and
thioglycolic acid (see Fig. 1). As expected, it was observed that the
ν(C^C) band at 2120 cm− 1 completely disappeared.31 A specific
Raman signal corresponding to the amino group was observed at
~3310 cm− 1, in the case of the reaction with cysteamine31 (PHEMA-
(NH2)2H). In the case of the reaction with thioglycolic acid (PHEMA-
(COOH)2I), no further peak corresponding to one such acid was found.
It is noteworthy that carboxylic acid moieties previously allowed for the
immobilization of various metallic nanoparticles, such as, copper, [21]
silver, [56,57] platinum, [56] palladium, [58] and gold [59].
3.3. Gold nanoparticle immobilization and supported catalytic reduction of
4-nitrophenol
The reduction of nitro compounds can be achieved via the use of
H.B. Ly et al.
miscellaneous metallic nanoparticles, such as silver, [60,61] ruthenium,
[62] and gold [26,30,60,63–65]. Furthermore, gold nanoparticles
(GNPs) are widely known for being able to catalyze a plethora of other
organic reactions, including dye reduction, [33,38] epoxidation, [27]
alcohols oxidations, [41,44,66] hydrogenations, [66] Suzuki CeC cross-
couplings, [45,65,67] or boronic acid CeC homocouplings, [68]
making nanogold the most commonly used metallic nanoparticles [69].
To this purpose, GNPs were in-situ generated and immobilized on the
surface of the functionalized porous PHEMA-based materials. Different
porous structures containing three types of chelating groups, i.e.eSH
(PHEMA-SH B), eNH2 (PHEMA-NH2 C), and two adjacent eNH2 groups
(PHEMA-(NH2)2 H), were investigated in order to compare their effect
on the GNP morphology and catalytic efficiency. The presence of GNPs
in the as-obtained hybrid porous materials was evidenced by SEM
(Fig. 2) and EDX (see Supporting information), while quantification of
gold was achieved by ICP-OES.
The three hybrid samples observed by SEM microscopy arose from
CDI-activated biporous materials functionalized in different ways: (i)
the first one with cysteamine (PHEMA-SH B, Fig. 2a,b), (ii) the second
one with ethylene diamine (PHEMA-NH2C, Fig. 2c,d), and (iii) the third
one through a tandem reaction involving the grafting of allylamine and
subsequent thiol-ene radical addition of cysteamine (PHEMA-(NH2)2H,
Fig. 2e,f). No significant morphological differences between the dif-
ferent polymeric structures were observed by SEM microscopy, as they
arose from the same CDI-activated biporous material. The three of them
displayed both porosity levels, i.e. the upper and lower ones, while gold
nanoparticles were immobilized at their pore surface. More precisely,
the main differences stemmed from the distribution pattern of the gold
nanoparticles immobilized at their surface. The distribution and density
96
Reactive and Functional Polymers 121 (2017) 91–100
Fig. 2. SEM micrographs of doubly porous GNP@PHEMA-
based materials functionalized with different amino mole-
cules: (a), (b) PHEMA-SH B; (c), (d) PHEMA-NH2C; (e), (f)
PHEMA-(NH2)2H.
of GNPs at the pore surface of such porous materials was indeed
function of the chemical nature of the pore surface of the polymeric
material. We thus observed here better GNP immobilization with
amine-functionalized monoliths (Fig. 2c,d vs.Fig. 2e,f) than with thiol-
functionalized ones (Fig. 2a,b). Additionally, the higher the density of
amine moieties at the surface of the biporous materials, the higher the
density of gold nanoparticles at the pore surface (Fig. 2c,d vs.Fig. 2e,f).
Additionally, it was observed that doubly porous PHEMA-SH B and
PHEMA-(NH2)2H possessed two populations of GNPs: “macro-particles”
whose diameter ranged from 3 to 5 μm, and nanoparticles of around
100 nm diameter (high-magnification zoom not shown), with many
particle aggregates. PHEMA-NH2C did not show any noticeable macro-
sized gold particles, and mostly possessed GNPs with sizes between 100
and 150 nm.
On the other hand, the EDX spectrum of sample C revealed the
presence of nitrogen (N) at the surface of the porous material, thus
confirming the successful grafting of EDA onto the CDI-activated
doubly porous material. The presence of nitrogen (N) and sulfur (S)
observed by EDX at the surface of doubly porous materials B and H
again ascertained the efficient covalent grafting of cysteamine through
nucleophilic substitution and thiol-ene addition, respectively.
Finally but more importantly, the observation of gold (Au) signal by
EDX for the three considered biporous materials B, C, H after in-situ
generation of GNPs clearly demonstrated the tight adsorption of these
noble nanometals at the surface of amine- or thiol-functionalized
polymeric matrices.
For the sake of comparison, pristine PHEMA samples were also
analyzed by EDX spectroscopy and did not show any characteristic
signal of N, S, and Au elements (data not shown). One could finally
H.B. Ly et al.
Fig. 3. UV–Visible investigation of 4-nitrophenol reduction catalyzed by GNP@PHEMA porous materials: (a) schematic illustration of the catalytic reduction reaction under investigation.
Spectra for NaBH4/4-nitrophenol solutions before (dashed or solid black trace) and after 60 min (dashed or solid red trace) reaction: (b) PHEMA-NH2 samples C1 and C2 (with 20 μL of
NaBH4), (c), (d) PHEMA-NH2 samples C and C2 (with 60 μL of NaBH4), respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
mention the higher gold content in the case of amine-functionalized
matrices when compared to the thiol-modified material via the in situ
strategy. This could likely be explained by the great propensity of amine
groups to easily chelate metal ions.
The catalytic behavior of functionalized porous GNP@PHEMA-
based materials was then investigated via NaBH4-mediated reduction of
4-nitrophenol as a model reaction (Fig. 3). First, three different types of
porosity features were considered, as defined next: (i) type 1: doubly
porous structure; (ii) type 2: monoporous analogue containing only the
upper porosity level; and (iii) type 3: monoporous analogue containing
only the lower porosity level. The catalytic activities of monoporous
samples PHEMA-NH2C1 and C2 were first examined with a reduction of
20 μL of 4-nitrophenol with 20 μL of NaBH4 in 4 mL of water. These
materials were shown to display approximately the same activity: yield
values as low as 27% and 25% within 1 h reaction were determined by
UV–Visible spectrophotometry for polymer C1 and polymer C2, re-
spectively. Nevertheless, according to ICP-OES analyses, the mono-
porous material with the upper porosity level (C1) contained much
fewer GNPs than that with the lower porosity level (C2) (i.e. 1.3 wt.%
and 4.6 wt.% GNPs for samples C1 and C2, respectively). The similar
catalytic activities of these materials with different pore sizes might be
explained by a better GNP accessibility in the porous material with
larger pore sizes, as fluid flow was probably much higher in one such
material. Due to the low reactivity of the catalytic systems, the quantity
of NaBH4 was tripled in order to increase the catalytic activity (i.e. from
20 to 60 μL of NaBH4). Indeed, various reports indicated that it exists a
linear dependence of the catalysis rate on the NaBH4 concentration
[70,71]. Due to the similar activities between samples C1 and C2, we
then proposed the comparison between samples C and C2 only (Fig. 3).
It was shown that the doubly porous material C was more efficient
to catalyze the reduction of 4-nitrophenol, achieving an 83% yield
97
Reactive and Functional Polymers 121 (2017) 91–100
within 60 min, while the monoporous hybrid material C2 only attained
a 71% yield within the same duration. The much higher GNP quantity
immobilized on the doubly porous sample (i.e., 9.2 wt.% GNPs for Cvs.
4.6 wt.% GNPs for C2), associated with a higher porosity ratio (i.e.,
92% for Cvs. 72% for C2), so in turn a better GNP accessibility, may
account for its higher catalytic efficiency.
Regarding these results, we particularly focused our attention on
doubly porous materials, and decided to investigate the effect of che-
lating functions on the catalysis yield of the hydride-mediated reduc-
tion of 4-nitrophenol. Experiments were conducted to compare thiol-
functionalized B and amine-functionalized C PHEMA-based porous
materials, as well as the polymer resulting from thiol-yne addition re-
action with cysteamine (PHEMA-(NH2)2H). The thiol-containing
sample B exhibited the fastest reduction rate, achieving 86% yield in
only 15 min during the first catalytic cycle (Fig. 4). Despite one such
fast reduction rate, a significant leaching of GNPs was observed as the
expected transparent solution turned into black during the course of the
catalytic reaction. This observation was confirmed by dynamic light
scattering experiments on the resulting solution (data not shown). The
results showed the occurrence of two populations of GNPs with average
diameters of about 100 nm and above 1 μm, as observed by SEM (see
Fig. 2). The important leaching of GNPs led to a dramatic decrease in
the reaction rate for the subsequent catalytic cycles: indeed, an 87%
yield was observed after one extra hour, while three other successive
runs did not show any occurrence of catalytic reaction (Fig. 4). It is
noteworthy that a blank experiment, i.e. the reduction of 4-nitrophenol
with NaBH4 in the presence of doubly porous PHEMA-SH B without
GNPs, was also investigated.
In this case, no catalyzed reaction was obtained either, as the cor-
responding yield was equal to 1% in 1 h. Kinetic experiments through
UV–Visible monitoring were conducted to compare the amine-
H.B. Ly et al.
Fig. 4. UV–Visible investigation of the reduction of 4-nitrophenol catalyzed by functionalized doubly porous GNP@PHEMA-based materials: Time dependence of UV spectra for NaBH4/
4-nitrophenol solutions in the presence of samples PHEMA-SH B (b), PHEMA-NH2C (c), and PHEMA-(NH2)2H (d). The Inset table (a) shows the reusability of the supported catalysts after
five successive runs of the same reduction reaction. (For interpretation of the references to time in this figure, the reader is referred to the web version of this article).
functionalized specimen (PHEMA-NH2C) with the polymer resulting
from thiol-yne addition reaction with cysteamine (PHEMA-(NH2)2H)
(Fig. 4).
Amine-bearing doubly porous PHEMA-based polymers (PHEMA-
NH2C and PHEMA-(NH2)2H) achieved very satisfying reduction yields
(around 90% for both in 60 min) and displayed excellent reusability
over five successive catalytic cycles. It is noteworthy that sample C
possessed 9.2 wt.% of GNPs, and PHEMA-(NH2)2 (H) contained
12.5 wt.% of GNPs, according to ICP-OES analyses. These results were
quite logical as PHEMA-(NH2)2 (H) theoretically possessed a double
quantity of amino groups able to immobilize GNPs.
4. Conclusions
In this work, we reported on the preparation of original biporous
PHEMA-based materials, and their subsequent straightforward and
versatile functionalization with different organic compounds of in-
terest, namely ethylenediamine, cysteamine, and propargylamine,
among others. In the latter case, a subsequent thiol-yne addition of
cysteamine allowed for the preparation of amine-functionalized mate-
rials with a higher density of eNH2 groups at the pore surface than in
the case of ethylenediamine-modified precursor materials. Further
generation of GNPs through an in-situ methodology allowed for the
preparation of hybrid materials consisting of thiol- and amine-functio-
nalized porous PHEMA-based materials on which GNPs were im-
mobilized. It was notably demonstrated that the grafted chemical
function and its density at the pore surface is crucial regarding the
distribution pattern of the further immobilized gold nanoparticles,
diamines being more suitable than amines and much more than thiols.
The efficiency of such innovative functionalized systems as catalytic
supports was proved via the hydride-mediated reduction of 4-
98
Reactive and Functional Polymers 121 (2017) 91–100
nitrophenol that was monitored by UV–Vis spectrophotometry.
Experimentally, a higher efficiency of amine-bearing hybrid systems
was observed when compared to thiol-functionalized analogues. More
interestingly, biporous systems showed a significantly higher catalytic
efficiency than their monoporous counterparts containing either the
upper porosity level or the lower porosity level, likely due to a higher
specific surface area of this doubly porous monoliths when compared to
their monoporous analogues displaying the upper porosity but also to a
higher accessibility of the catalyst when compared to monoliths with
only the lower porosity level. Finally, the catalytic activity could be
easily correlated to the surface developed by immobilized gold nano-
particles in the hybrid materials and thus to the chemical function
grafted at the pore surface.
This investigation paves the way to the design of innovative doubly
porous hybrid materials that could find promising perspectives in het-
erogeneous supported catalysis.
Acknowledgments
This work has benefited from a French government grant by ANR
within the frame of the national program Investments for the Future
ANR-11-LABX-022-01 (LabEx MMCD project).
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