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Department of Chemical Engineering, Process Engineering for Sustainable Systems (ProcESS), KU Leuven, W. de Croylaan 46,
B-3001 Heverlee, Belgium
School of Bioprocess Engineering, Universiti Malaysia Perlis, Kompleks Pusat Pengajian Jejawi 3, 02600 Arau, Perlis, Malaysia
ABSTRACT: An articial polydimethylsiloxane/polyphenylsulfone (PDMS/PPSU)
membrane, which emulates the hydrophobic behavior of natural membranes, was
synthesized. Hydrophobicity was achieved by coating the membrane surface sublayer
using conventional silicon material, which imitates the character of epicuticular wax (EW)
of Prunus laurocerasus L. leaves. It was then applied as a separation medium in
pervaporation (PV) of diluted mixtures of ethyl acetate and aroma compounds. The
membranes biomimetic characteristics were evaluated using surface morphology analyses,
that is, Fourier transform infrared (FTIR), water contact angle measurements, and SEM
imaging. A comparison of properties of the membranes synthesized in this work against
selected hydrophobic plant leaves indicated a good agreement. PV using these biologically
inspired articial membranes demonstrated preference for the permeation of ethyl acetate.
Besides intrinsic characteristics, it was also observed that the chemical potential is highly
inuential in activating sorption, diusion, and desorption of a specic compound.
cuticle are called epicuticular waxes.3 Jetter et al. further
explained that wax lms from P. laurocerasus consist of a
mixture of alkanes with dierent chain lengths and other
compound classes.4 Typical wax morphologies include thin
lms and three-dimensional structures such as massive crusts,
granules, plates, platelets, laments, rods, and tubules with
hollow center.3 According to several other studies, cuticles
serve as an ecient transport barrier in controlling dehydration
by transpiration, besides managing the plantpathogen
interactions.3,59 Water movement across plant cuticles is
similar to its movement across membranes, which can be
quantied using the rst Ficks Law. Cuticular water
permeability is highly dependent on the cuticular/water
partition coecient, porosity, membrane thickness, tortuosity
factor, self-diusion, and the hindrance factor.10 On the basis of
these ndings, it can be concluded that membranes exhibiting
these curticular properties are extremely useful for industrial
applications, especially for organic traces removal in aqueous
solution through pervaporation. This work aims to transfer
these cuticular wax properties found in plants by introducing
and synthesizing a composite polymer-based membrane.
Polydimethylsiloxane (PDMS) membranes have been frequently used in PV to recover organic solvents from aqueous
mixtures,1113 and also for gas separation.14 As a support
material, a third member of the polysulfone family,
polyphenylsulfone (PPSU), with better properties than
1. INTRODUCTION
Nature has inspired various inventions and technological
solutions to overcome limitations of mankind in life. Various
improved materials, tools, structures, mechanisms, processes,
algorithms, and methods resulted from the understanding of
nature and its phenomena. Flying, for instance, was inspired by
the mechanism used by birds, while divers ns were replicated
from semiaquatic creatures such as seals.1 The word
biomimetics, which rst appeared in Websters dictionary in
1974, is dened as the study of the formation, structure or
function of biologically produced substances and materials (as
enzymes or silk) and biological mechanisms and processes (as
protein synthesis or photosynthesis) especially for the purpose
of synthesizing similar products by articial mechanisms, which
mimic natural ones.2 Biomimetic research resulted in the
understanding of various phenomena such as wettability and
the self-cleaning eect found in natural leaves such as Nelumbo
nucifera gaern (Lotus leaf), Oryza sativa L. (Rice leaf), Colocasia
(Taro leaf), Prunus laurocerasus L. leaves (Cherry laurel), and
Setcreasea purpurea boom (purple setcreasea). Recently, studies
discovered that leaves in general are laminated with organic
lms containing C, H, and O elements. Others believed that the
majority of lower and higher-altitude plants (e.g., owers,
leaves, fruits, stems) consist of a continuous extracellular
membrane known as cuticle, which covers the outer layer of the
epidermal cell.3 In general, cuticles are cutin-based composite
materials with integrated and superimposed lipids known as
waxes. Plant waxes embedded into the cuticle are called
intracuticular waxes, whereas waxes superimposed onto the
2013 American Chemical Society
Langmuir
Article
formula
functional group
MW, g/mol
SG @ 25 C
boiling point, C
Psat (26 C), Pa
solubility in water @ 20 C, g/L
CH3CO2C2H5
ROCOR
88.1
0.901
77.1
13 045
80
C5H10O
RHCO
86.1
0.803
92.5
7035
15
C5H8O2
ROCCOR
100.1
0.957
108
2918
60
C6H12O
RHCO
100.2
0.814
128.3
1540
IS
C5H10O
ROH
86.1
0.839
114.4
1348
IS
C8H16O
ROH
128.2
0.83
8485
65
IS
C6H5CHO
RHCO
106.1
1.046
179
181
0.3
(1)
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Figure 1. Top layers of synthesized PPSU and PDMS membranes at lower to higher polymer concentration: (a) 25 wt % PPSU, thickness 0.55
m; (b) 27.5 wt % PPSU, thickness 0.25 m; (c) 30 wt % PPSU, thickness = 0.32 m; (d) 5 wt % PDMS, thickness = 1.4 m; (e) 10 wt % PDMS,
thickness = 2.74 m; and (f) 15 wt % PDMS, thickness = 4.37 m. Panels ac were reprinted with permission from ref 19. Copyright 2011 Elsevier.
E
P
P
= exp x
l
RT
l
J=
m
P
= (ioLxiLoPisat
o yio Pi l)
At
l
(2)
i =
Wi ,p
Wi ,f
(4)
(3)
Langmuir
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Table 2. Characterization of Natural Leaves and Articial Membrane Using DSLR and SEMa
SEM gure of cherry laurel was adapted from the work of Koch and Ensikat.3
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25
35
45
4.7
6.1
4.3
0
0
0
0.3
0
1.16
0
0
0
0
0
0
2.13
0
0
0
0
0
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4. CONCLUSION
A plant cuticle is a membrane that covers primarily aboveground plants such as leaves, owers, stems, and fruits. The
superimposed waxes onto the cuticle are called epicuticular
waxes. This natural membrane is very ecient as a transport
barrier. Thus, a biologically inspired membrane was engineered,
synthesized, and investigated for application in the recovery of
aroma compounds using pervaporation. The synthesized
hydrophobic PDMS/PPSU was characterized and compared
against three selected natural leaves, and it was observed that
the synthesized membrane was comparable to cherry laurel leaf.
Evaluating PDMS-coated PPSU membrane against the uncoated membrane indicated a 50 contact angle improvement,
besides resembling the complex topography patterns of the
biological leaves. As was proven in previous investigations,
surface structure is not an obligatory condition to enable
hydrophobicity. Instead, the wax-like material that covers the
surface has enabled this feature. Among the seven aroma
compounds used, only ethyl acetate is able to permeate through
the synthesized hydrophobic membrane matrix in pervaporation due to its high hydrophobic property. This will then
improve the selective permeation of less hydrophobic
compounds through the interaction with dierent aroma
species, consequently enabling the developed membranes to
be applicable to a wider variety of chemicals.
that when more than one component tries to cross the barrier,
the resistance of penetration increases, resulting in lower
permeation. It is hypothesized that besides permeation of single
component, there exists the possibility of couple molecule
(water and ethyl acetate) permeation, which could be the
reason for delay in penetration through the membrane matrix
as can be seen in Figure 6.
The decrease of water ux in the permeate side of the
membrane when the feed concentration is 1 ppm of ethyl
acetate is expected due to the higher solubility of ethyl acetate
in the solution. The hydrogen bond between both water and
ethyl acetate has made the couple molecule more hydrophilic,
which easily repels by the hydrophobic membrane. As the
concentration of ethyl acetate increases in the feed stream, the
solubility of the solute decreases, resulting in only water
molecule permeating across the barrier.
Considering the importance of feed temperature in PV, its
eect on the biologically inspired membrane was studied.
Burggraaf33 has related both of the activated microscopic
models based on the conguration and surface diusion with
temperature dependence in the classical adsorptiondiusion
model as shown in eq 5:
EJ = Hs + E D + H vap
(5)
AUTHOR INFORMATION
Corresponding Author
*E-mail: nora.jullok@cit.kuleuven.be.
Notes
(6)
ACKNOWLEDGMENTS
Financial support from the Malaysian Ministry of Higher
Education (MOHE) is gratefully acknowledged.
REFERENCES
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(22) Van de Witte, P.; Dijkstra, P. J.; Van den Berg, J. W. A.; Feijen, J.
Phase separation processes in polymer solutions in relation to
membrane formation. J. Membr. Sci. 1996, 117, 131.
(23) Reuvers, A. J.; Van den Berg, J. W. A.; Smolders, C. A.
Formation of membranes by means of immersion precipitation:: Part
I. A model to describe mass transfer during immersion precipitation. J.
Membr. Sci. 1987, 34, 4565.
(24) Benyus, J. M. Biomimicry: Innovation Inspired by Nature; William
Morrow and Co. Inc.: New York, 1997.
(25) Cortese, B.; DAmone, S.; Manca, M.; Viola, I.; Cingolani, R.;
Gigli, G. Superhydrophobicity due to the hierarchical scale roughness
of PDMS surfaces. Langmuir 2008, 24, 27122718.
(26) Tserepi, A. D.; Vlachopoulou, M. E.; Gogolides, E. Nanotexturing of poly (dimethylsiloxane) in plasmas for creating robust
super-hydrophobic surfaces. Nanotechnology 2006, 17, 3977.
(27) Guo, Z.; Liu, W. Biomimic from the superhydrophobic plant
leaves in nature: Binary structure and unitary structure. Plant Sci. 2007,
172, 11031112.
(28) Caponigro, M. A.; Eriksen, C. H. Surface film locomotion by the
water strider, Gerris remigis Say. Am. Midl. Nat. 1976, 268278.
(29) Cassie, A. B. D.; Baxter, S. Wettability of porous surfaces. Trans.
Faraday Soc. 1944, 40, 546551.
(30) Bhushan, B. Biomimetics: lessons from nature - an overview.
Philos. Trans. R. Soc., A 2009, 367, 1445.
(31) Wosten, H. A. B.; Ruardy, T. G.; van der Mei, H. C.; Busscher,
H. J.; Wessels, J. G. H. Interfacial self-assembly of a Schizophyllum
commune hydrophobin into an insoluble amphipathic protein
membrane depends on surface hydrophobicity. Colloids Surf., B:
Biointerfaces 1995, 5, 189195.
(32) Martinez, R.; Sanz, M. T.; Beltran, S. Concentration by
pervaporation of representative brown crab volatile compounds from
dilute model solutions. J. Food Eng. 2011, 105, 98104.
(33) Burggraaf, A. J. Single gas permeation of thin zeolite (MFI)
membranes: theory and analysis of experimental observations. J.
Membr. Sci. 1999, 155, 4565.
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