FULL PAPER

Self-Cleaning
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Engineering Fully Organic and Biodegradable

Superhydrophobic Materials
Athanasios Milionis, Chander Shekhar Sharma, Raoul Hopf, Michael Uggowitzer,
Ilker S. Bayer, and Dimos Poulikakos*

superhydrophobic materials have been

The development of fully organic (cellulose/wax based), biodegradable, and reported.[12] However, most of these mate-
hierarchically textured superhydrophobic material, inspired by natural, self- rials make use of petroleum derivatives
cleaning plants, like the Lotus leaf is reported. The developed material can and fluorinated compounds,[13] as well
as textured inorganic materials,[14] which
reproduce in a controllable and artificial manner the chemical composition
serve as substrates for surface chemical
and material properties of these natural surfaces. At the same time, the functionalization. These materials are not
fabrication protocol described here enables realization of properties beyond inherently biodegradable and thus pose
the ones found in the natural leaves, by allowing facile tuning of the a challenge in terms of environmental
topographical and mechanical properties. The surface topography consists of impact and recyclability. Especially long-
a micropillar structure assembly with, to the best of the authors’ knowledge, chain fluorinated compounds, which are
used often to obtain liquid repellency, are
the highest to date reported aspect ratio (7.6) for cellulose materials. difficult to degrade and tend to bioaccumu-
Additionally, control and tunability of the material’s mechanical properties late.[15,16] Furthermore, even if these sub-
are also demonstrated, which is rendered softer (down to 227 MPa Young’s stances degrade after a prolonged period,
modulus from 997 MPa base value) by adding glycerol as a natural plasticizer. some of their by-products are known to
Finally, the self-cleaning properties are demonstrated and the biodegradability be toxic, such as perfluorooctanoic acid[17]
and perfluorooctanesulfonate.[18]
of the material is evaluated in a period of ≈3 months, which confirms
Recent studies have reported the use of
full biodegradation. Additionally, water drop and jet impact, and folding more sustainable methods and materials
tests demonstrate that the material can reasonably sustain its wettability to obtain the self-cleaning effect. These
properties. Such a truly bioinspired and biodegradable material system could include the use of biodegradable polymers
find potential use in various bioengineering applications. and natural materials,[19] waterborne spray
approaches,[20] alcoholic solvent environ-
ment,[21] silicone-based biocompatible
materials,[22] reactive polymeric mate-
rials, [23] fluorine-free substances,[24–26] cellulose-based,[27] and
1. Introduction
natural wax-based material compositions.[28,29] The use of the
Superhydrophobicity is recognized as a critical property in a latter two materials (cellulose and wax) is inspired from the
wide range of potential technologies spanning from industrial, fact that they are the main constituents of a broad selection of
healthcare, to military applications such as self-cleaning tex- plants, including the well-known Lotus leaf.[30] Cellulose is the
tiles,[1] water–oil separation,[2] anti-icing,[3] anti-fouling,[4,5] material that mainly constitutes the substrate and is responsible
anti-fingerprint,[6] corrosion resistance,[7] sensors,[8] robotics,[9] for the leaf’s mechanical properties and microroughness (the
and hydrophobization of 3D printed components.[10] Inspired latter in the form of macropapillae) in a wide range of plants.
by the discovery of the self-cleaning properties of the Lotus On the other hand, the wax nanocrystals cover the microtopog-
leaf (Nelumbo nucifera),[11] a large number of artificial raphy and are responsible for the superhydrophobicity, both

Dr. A. Milionis, Dr. C. S. Sharma,[+] M. Uggowitzer, Prof. D. Poulikakos Dr. R. Hopf

Laboratory of Thermodynamics in Emerging Technologies Department of Mechanical and Process Engineering
Department of Mechanical and Process Engineering Institute of Mechanical Systems
ETH Zürich ETH Zürich
Sonneggstrasse 3, 8072 Zürich, Switzerland Leonhardstrasse 21, 8092 Zürich, Switzerland
E-mail: dpoulikakos@ethz.ch Dr. I. S. Bayer
The ORCID identification number(s) for the author(s) of this article Smart Materials
can be found under https://doi.org/10.1002/admi.201801202. Istituto Italiano di Tecnologia
[+]Present Via Morego 30, 16163 Genoa, Italy
address: Department of Mechanical Engineering, Indian Insti-
tute of Technology, Ropar, Nangal Road, Rupnagar, 140 001 Punjab, India

DOI: 10.1002/admi.201801202

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due to their chemical (long hydrocarbon chains) and physical
properties (nanocrystalline structures).[30,31]
Spray-coated wax solutions, pristine or combined with
other organic fillers, can produce superhydrophobic coatings
in a variety of substrates.[28,29] However, their application on
micropatterned cellulose has not been explored. Cellulose has
been used in artificial superhydrophobic surfaces either as a
substrate material or as a component in the chemical mixture
that comprises the superhydrophobic surface.[27,32] A combi-
nation of engineered cellulose and wax holds the potential to
achieve superhydrophobicity as a fully organic, artificial mate-
rial which has not been explored so far, despite the fact that it
is the most common material combination found in natural
plants.
Apart from the material aspect, the surface topography also
determines the overall wettability characteristics of a surface.
While many researchers have focused solely on surface struc-
turing by replicating the micro/nanotopography of the Lotus
leaf to achieve self-cleaning behavior,[33–35] achieving such
replication with cellulose as base material has been proved chal-
lenging. This is due to the complexity of processing cellulose
as a material in lithographic processes. Well-ordered patterned
cellulose microstructures with aspect ratio of only up to 0.2
(defined as ratio (h/d) of height h and diameter d) have been
fabricated in the form of honeycomb, pillars, or grooves with
techniques involving soft molding, guided bacterial assembly
lithography or roll-to-roll imprinting.[36–38] These aspect ratios
are much smaller than those of typical surface features occur-
ring in the natural superhydrophobic plant surfaces wherein,
for example, for Lotus leaf, the micropapillae have an aspect
ratio of ≈1.[39] Such aspect ratio of the surface microstructures
has been shown to be an essential element for achieving a high
degree of water repellence and self-cleaning effects in various
hydrophobic plants, including Lotus, Indian Cress, Californian
Poppy, Gingko Trees, Aroids, and Euphorbia myrsinites.[30,40]
This is due to the well-established fact that the high aspect ratio
of microfeatures ensures that a sessile drop on the surface stays
in the Cassie–Baxter wetting state resulting in low pinning and
thus easy roll-off. The reason for the large shortfall in artificially
achieved aspect ratios with cellulose-based microfeatures, as
compared to natural superhydrophobic plants, lies mostly in
the fibrous nature of the processing material, which is prone
to loss of volume during hydration and dehydration cycles.[36]
In essence, fabricating a fully organic superhydrophobic mate-
rial, based on naturally derived ingredients, has proved elusive
so far.
In this work, we demonstrate the fabrication of a fully
organic, bioinspired superhydrophobic material composed
of green and degradable constituents, similar to the constitu-
ents found in superhydrophobic leaves in nature. The material
consists of a cellulose micropatterned substrate, coated with
a carnauba wax layer which lowers the surface energy of the
substrate and induces a second order of roughness at the same
time, thus attaining superhydrophobicity. Furthermore, we go
one-step beyond by demonstrating control over not only the
wetting properties but also the mechanical properties of the
substrate by the addition of natural plasticizers. We achieve an
enhancement of the aspect ratio of cellulose micropillars by
over an order of magnitude (aspect ratio of 7 compared to the
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highest previously reported of 0.2).[36] Such high aspect ratios
not only allow the creation of a truly bioinspired superhydro-
phobic material, but go beyond the limitations of the natural
plants, allowing this material to be considered in targeted
biomedical engineering applications like sensors, actuators,
or traction force microscopy, where high aspect ratio and flex-
ible microstructures that can easily bend are required, so
that their motion can be easily tracked by optical means.[41–45]
Other applications where high aspect ratio microstructures are
important are microfluidics and tissue engineering,[46] and the
development of dry adhesives, inspired by the properties of the
gecko-foot.[47,48] In the latter case, the surface compliance owed
to the flexible high aspect ratio pillars can enhance the adhe-
sion between solid surfaces, as it has been previously shown
with silicone-based micropillars.[47] Since most of the aforemen-
tioned applications traditionally use silicones or other synthetic
materials to study cell/substrate interactions, a cellulose based
microstructured material can open new possibilities in bioengi-
neering research.
We achieve superhydrophobicity on this material by a facile
spray coating of carnauba wax, a natural wax obtained by Bra-
zilian Copernicia prunifera palm trees. The wax is intended
to act in a similar manner as the wax structures covering the
Lotus leaf and other natural superhydrophobic plant surfaces,
which are responsible for their self-cleaning properties. Bio-
degradation tests showed that the developed material can
be fully degraded within 3 months in seawater environment.
Water drop and jet impact, as well as folding tests showed that
the material is robust enough to maintain its properties for
applications where moderate durability is required. Overall, the
inherent biodegradability of such a material system implies that
it can be further considered for applications were short term
functionality combined with disposability and environmental
friendliness is required (e.g., one time use bioanalytical tests,[49]
cell cultures,[50] drug delivery,[51] foldable and disposable elec-
tronics,[52] etc.).
2. Results and Discussion
2.1. Developing High Aspect Ratio Cellulose Replicas
At first a cellulose solution was prepared as described in the
Experimental Section. Following a soft molding procedure of a
cellulose solution on prefabricated Si masters (as described in
detail in the experimental section), the resulting cellulose micro-
pillars accurately replicated the negative structure of the silicon
wafer microholes. Figure 1 shows scanning electron microscope
(SEM) images at low and high magnification (top-view and side-
view images of pillars with aspect ratio ≈6 are shown in Figure S2
of the Supporting Information). It was observed using perfluoro-
decyltrichlorosilane (FDTS) functionalization of the silicon
masters lead to the successful replication of higher aspect ratio
structures compared to nonsilanized silicon masters. This was
due to the reduction of the surface energy of the Si masters,
which facilitated the peeling off procedure and allowed high
aspect ratio structures to get detached from the masters without
rupture. Specifically, with FDTS treatment, it was possible to
achieve aspect ratio of 7.6, while without FDTS the maximum
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2.2. Obtaining Superhydrophobicity by Wax

Coating

To achieve the hierarchical surface mor-

phology and the self-cleaning properties
similar to a Lotus leaf, the cellulose micro-
pillars should be covered with a hydrophobic
sub-micrometer/nanorough layer, since the
cellulose by itself is a hygroscopic material
and tends to absorb water.[53] In order to
achieve this, we used a simple spray coating
method and the material that was chosen
for spray was a natural wax. Chloroform was
selected as a solvent for two reasons: first due
to its fast evaporation and second due to the
fact that it forms a stable and transparent
solution with the wax upon heating it above
the wax’s melting point. The solution then
Figure 1. Fabricated cellulose micropillars with various increasing aspect ratios (AR). stays stable even when it is cooled down to
a,b) Micropillars with small aspect ratios could be achieved without master silanization. room temperature, thus allowing a suffi-
c,d) Microstructures obtained with soft molding on silanized masters. Maximum AR achieved cient time to be used as spray. Once sprayed,
is 7.6 c). Higher AR than 7.6 could also be achieved but the pillars started to get distorted due chloroform is almost immediately evaporated
to mechanical deformation d).
from the surface due to its high vapor pres-
sure (212 kPa at 20 °C), leaving a dry rough
attained aspect ratio was 1.9. Figure 1c,d shows the difference wax coating behind, that covers homogeneously the cellulose
in the aspect ratio outcome by following these two procedures topography. The resulting material exhibits hierarchical rough-
(with and without silanization of the Si masters used for the soft ness as it can be seen from the SEM images of Figure 2, where
molding). It is worth noting that in our case we did not observe coatings with different concentrations of carnauba wax are
significant shrinkage of the cellulose microstructures, a very depicted. In particular, outcomes from 3 different spray solu-
common problem when using other types of cellulose in the tion concentrations are shown (namely 0.1, 0.2, and 0.3 wt%
form of fibers, like the bacterial grown cellulose for instance.[36] wax dissolved in chloroform).
The aspect ratio values achieved with our method outperform by Figure 3a,b shows the graphs depicting the evolution of
an order of magnitude the aspect ratio achieved by the existing the static contact angle (SCA) and the contact angle hysteresis
cellulose microfabrication approaches.[36–38] (CAH), against the carnauba wax concentration of the spray
coating solution. The green triangles depict
the micropatterned substrate wettability and
the red circles show the corresponding wet-
tability of the flat cellulose substrates. The
cellulose pillared samples that were used
for the evaluation of the wetting proper-
ties were in the form of pillars of diameter
d  = 10 µm, the interpillar spacing was dint  =
25 µm, and the pillar height H = 9 µm. This
corresponds to an aspect ratio of 1, similar
to a Lotus leaf surface. All the samples fab-
ricated in this study were designed in such
a way that, assuming that the drop is in a
Cassie–Baxter state, the fraction of the sur-
face (top of micropillars) in contact with the
drop is always constant, and its arithmetic
value is fSL = 0.26. If fSL = const. and the drop
is on a Cassie–Baxter state, then the pillar
height will not influence the wetting prop-
erties. This specific value of fSL was chosen
as it was found to be relative similar to the
one of the Lotus leaf, based on the analysis
Figure 2.  Cellulose micropillars spray coated with a) 0.1, b) 0.2, and c,d) 0.3 wt% carnauba wax of SEM pictures found in the literature. It is
in chloroform. In the insets are provided macroscopic optical images of sessile drops deposited worth noting that a SCA for the flat cellulose
on the corresponding patterns. is not included in Figure 3 because it cannot

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Figure 3.  Graphs depicting the evolution of SCA a) and CAH b) plotted
against the carnauba wax concentration for flat (red curve) and pillared
surfaces (green curve). Inset: SEM image of the 0.4 wt% wax-coated cel-
lulose micropillars.
be practically defined. Cellulose is a hygroscopic material and it
tends to absorb water when a droplet is deposited on it. There-
fore upon drop placement, the SCA will continuously change
until the water gets fully absorbed by the cellulose. This how-
ever does not occur when the cellulose is coated with wax as
shown in Figures 3a. As it can be observed in Figure 3a, for flat
cellulose substrates coated with different concentrations of wax,
SCAs increased from 94° to 133° for increasing the wax concen-
tration up to 0.3 wt% (red line with circular markers). The wax
prevents the water to be absorbed by the cellulose, thus contact
angles are stable over time. Above the critical concentration of
0.3 wt%, no further enhancement of the anti-wetting behavior
could be observed, likely because the wax coating had fully cov-
ered the cellulose substrate and its random roughness features
showed the same morphology. Figure 3b shows the evolution
of the CAH with increasing wax concentration. The CAH for
the case of the flat substrates coated with wax (red line with cir-
cular markers) equals the values of the advancing angles, since
during their receding motion, the sessile drops were always
pinned on the surface (receding angle was practically zero).
This high CAH can be attributed to the lack of hierarchical sur-
face topography that promotes formation of air pockets beneath
the drop, responsible for lower values of CAH.[39] Therefore, as
a general conclusion, no superhydrophobicity can be achieved
on wax-coated, flat cellulose substrates.
However, when the cellulose micropillar topography was
introduced (green curves with triangle markers in Figure 3a,b),
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a sudden increase in the SCA values could be clearly observed
for all the tested wax coating concentrations. In particular,
the samples with wax concentration ≥ 0.2 wt% satisfy the
conditions for a material to be considered superhydrophobic
(SCA > 150° and CAH < 10°). The sample with wax coating of
0.1 wt% (Figure 2a) seems to be partially covered with wax, or
at least the generated by the spray coating roughness is not suf-
ficient to maintain a Cassie–Baxter state. On the other hand,
the samples with 0.2% wt. and above, show superhydrophobic
performance with SCA up to 165° and CAH down to 2° (values
for the sample with 0.3 wt% wax). Therefore, between the
concentrations of 0.1 and 0.2 wt%, a wetting transition seems
to occur, from a “sticky” Petal-like state to a Lotus leaf-like,
Cassie–Baxter state.[54] Note that the very high CAH values
for low wax concentration (<0.2 wt%) are attributed to the
fact that there is not full surface coverage from wax, there-
fore some hydrophilic spots are exposed. This gives rise to a
phenomenon known as “petal effect,” where we can observe
high static contact angles but also high CAH due to pinning
of the drop during the receding motion (receding angle is
practically zero).[55] Similar to the case of flat cellulose, wax
concentrations above 0.3% did not yield any further improve-
ment in the anti-wetting behavior of the samples. This is
because too high wax concentration may create wax struc-
tures with multiscale and random roughness that completely
diminish the effect of underlying micropillar geometry (see
SEM inset in Figure 3b).
2.3. Self-Cleaning Properties
In order to demonstrate the self-cleaning properties of the
developed material, self-cleaning tests were performed by using
artificial contaminants and allowing water drops to roll on the
surface and uptake the particles. For imaging purposes, the
powder Sudan II (Sigma Aldrich) was selected to demonstrate
the self-cleaning effect (due to its red color). However, also other
powders were tested, including silica particles which are the
main ingredient of common dust and they have already been
used in past works for evaluating self-cleaning properties.[56]
The self-cleaning experiment is shown in Video S1 (Supporting
Information). Figure 4 shows frames of this experiment. It can
be observed that the rolling motion of dispensed water drops
results in the collection and removal of the contaminant along
the drop pathway.
2.4. Biodegradability of Cellulose and Wax
The next step was to evaluate the biodegradability of the devel-
oped material in sea water, inspired by the global environmental
challenge, which is the continuously increasing concentration
of nondegradable plastic materials in the oceans.[57] This was
measured by using a biochemical oxygen demand (BOD)
method. Oxygen consumed through biodegradation reactions
was recorded to detect changes in oxygen levels. The decrease
in the oxygen levels was related to cellulose or wax consump-
tion through stoichiometry of the general aerobic degradation
reaction[74]
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Figure 4.  Video frames from the self-cleaning experiment. a) The surface is contaminated with a powder and a water drop is dispensed on a slightly tilted
(<5°) cellulose/wax superhydrophobic pattern and allowed to roll due to the gravity and the low CAH (drop path depicted with the blue arrow and dashed
line). b,c) During its rolling motion, the drop uptakes the deposited powder from the surface that lies on its path. d,e) More drops are dispensed and
the powder is gradually removed. f) After a few drops have rolled on the surface, all the powder has been removed (Video S1, Supporting Information).

 a b 3c  of carnauba wax. Hence, it can be concluded that the biodeg-

Cn Ha ObN c + n + − −  O2 → nCO2 radation rate of wax is much slower than lignin. This could
 4 2 4
(1)
 a 3c
+  − H2O + cNH3 
2 2 
where CnHaObNc represents the organic compound that would
biodegrade, consuming n + a/4 − b/2 − 3c/4 moles of oxygen.
The moles of consumed oxygen divided by the molecular
weight of the organic compound and multiplied by the mole­
cular weight of oxygen represents the oxygen consumption in
mg of O2 per mg of compound. The results for wax and cellu-
lose are reported in two distinct ways (Figure 5). In the case of
wax the measurements were reported as mg O2 consumed per
gram of wax used as a function of time (days) and for cellulose
as percent biodegradation with reference to microcrystalline
cellulose, which degrades in dark sea water almost completely
after about 60 days. The reason for tracing oxygen in the case
of carnauba wax is that the wax is made up of multiple com-
ponents such as aliphatic esters (≈40%) and cinnamic acid
diesters (≈30%) and other components such as alcohols and
fragrances.[58] Hence, stoichiometric correlation of oxygen with
the total material is impossible when reporting biodegradation
rate in percentage as shown in Figure 5b.
Although experimental conditions are diverse, the BOD
measurements of Figure 6a could be compared with the bio-
degradation rate of lignin in river waters.[59] Lignin, just like
carnauba wax, is a multicomponent natural product. According
to Raabe,[59] within 50 days 2400 mg O2 are consumed per 1 g
of lignin in sweet river waters and at the end of 100 days about
2500 mg O2 are consumed per 1 g lignin. In Figure 5a, at
the end of 50 days ≈200 mg O2 are consumed per 1 g of wax Figure 5. Biodegradation results for a) carnauba wax and b) cellulose
and at the end of 100 days 210 mg O2 are consumed per 1 g used in this study.

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Figure 6.  High speed frames of a) a water drop partial rebound event (impact 601) captured at 4000 fps. Notice the tiny detached droplet depicted
with the red arrow, b) a full drop rebound after 1000 impacts.
be partially related to the hydrophobicity of wax compared to
lignin. However, it is important to note that the sea water may
not include the kind of enzymes and bacteria available in sweet
river waters.[60]
2.5. Evaluation of Mechanical Robustness
The robustness of the developed superhydrophobic materials
was evaluated by performing three different experiments: a)
impact with water drops, b) impact of a water jet, and c) folding
test. Our surface was able to resist ≈600 impact events (from
2.5 cm height) wherein each impact resulted in a full rebound.
Further impacts showed the first signs of degradation as sig-
naled by the partial drop rebound instead of full rebound. Such
a partial rebound is shown in Figure 6a wherein a tiny droplet
was detached from the main body of the rebounded drop and
stayed adhered on the surface (Video S2, Supporting Informa-
tion). It is interesting to notice however, that if this tiny wet
spot would be left to dry out, the subsequent impact event
would result again in full drop rebound, indicating that the
surface, although partially damaged, was still maintaining its
superhydrophobic performance. 1000 drop impact events were
recorded and recovery to full rebound could be obtained upon
drying until the last impact event. Figure 6b shows the 1000th
impact event which was a full drop rebound (Video S3, Sup-
porting Information).
Additionally, the material was exposed to a water jet of
velocity 4.4 m s−1 and jet diameter 0.9 mm. The surface could
repel the jet as shown in the high speed frames in Figure 8a.
The full video can be found in Video S4 (Supporting Informa-
tion). Water impalement was observed after 12 mL of water
were emptied on the surface. Although many robust superhy-
drophobic surfaces have been reported in the literature (mostly
in the form of composite coatings) with considerable greater
performance compared to our material,[61–63] no such durability
levels have been achieved with a pillar-patterned material com-
posed by fully degradable and natural organic components like
the one presented here.
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In order to demonstrate the stability of our material to
common physical manipulation, a folding test was performed.
The material was folded several times and the drop roll off
behavior was recorded on the folded parts. Figure 8b shows
high speed frames from a drop rolling on the surface after 100
folds. It can be clearly observed that no sign of degradation
occurs and that the material maintains its self-cleaning func-
tionality. Especially in the Figure 8b we can observe that the
surface can bend under the weight of the water drop and return
to its initial position upon drop removal, almost like a natural
leaf does (Video S5, Supporting Information).
Additional durability tests included an adhesion test (tape
peeling) and linear abrasion. The results are provided in
Figure S3 (Supporting Information). Our material could with-
stand 5 tape peeling cycles where it showed gradual increase
of the CAH (from 2° to 19°) as shown in Figure S3a (Sup-
porting Information). The tested material which was ≈80 µm
thick (including both cellulose and wax), started to crack
during the 6th tape peeling attempt, due to the gradual wax
coating removal that allowed the highly adhesive tape to
adhere strongly to the cellulose substrate, and therefore induce
damage. Considering however, that 10 cycles of this test have
been considered a good performance for past studies that were
targeting superior mechanical robustness,[64] we may inter-
pret 5 cycles to be a decent performance for our biodegradable
material, which by its nature is not designed to be extremely
durable (disposable use). Finally, our material was exposed
to linear abrasion cycles (under 2.17 kPa applied pressure) as
shown in Figure S3b (Supporting Information), and it was able
to withstand 2 cycles while maintaining good water repellency
(CAH ≈ 10°). This performance indicates that wax coating is
very susceptible to wear and further work should be performed
to render it more wear resistant against solid surfaces.
2.6. Tuning the Mechanical Properties
As the last part of this work, we examined the possibility of
tuning the mechanical properties of the fabricated material.
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Figure 7.  High speed frames of a) a jet impact event captured at 2000 fps (impact velocity is 4.4 m s−1) and b) a water drop rolling on the superhy-
drophobic surface, which has been previously folded 100 times.

Flexibility of superhydrophobic materials could be an extremely 3. Conclusions

important property when it comes to applications like
clothing,[65] flexible electronics[66] food packaging,[67] and bio­ In this work, we demonstrate a fabrication method to construct
engineering applications.[68] In our case, as shown in the a fully organic and biodegradable superhydrophobic material
graph of Figure 7, our cellulose base material that we use for inspired by the Lotus leaf that not only achieves superhydro-
molding has a Young’s modulus of 997 ± 106 MPa). This is phobicity with highly tunable wettability, but also its mechan-
particularly interesting, since the crystalline cellulose powder, ical stiffness can be controlled as well. The resulting material
which is the initial raw material, has a Young modulus of is a combination of microstructured cellulose, covered hierar-
25 GPa, which is 25 times higher compared to the resulting chically with carnauba wax. The developed surfaces can exhibit
cellulose material after the TFA process.[69] This can be attrib- SCA greater than 160° and CAH down to 2°. We demonstrate
uted to the breakage of crystallinity, due to the interaction with the self-cleaning property of the material as well as biodegrada-
the acid. Furthermore, it was possible to control the mechan- bility through quantifiable BOD tests. Going beyond the natural
ical properties of our material, and make it even softer, by properties of the natural Lotus leaf, we also demonstrate the
adding glycerol as a natural plasticizer.[70] In fact, the Young’s possibility to fabricate high aspect ratio (7.6) micropillar arrays
modulus could be reduced by nearly 77%,
down to almost 227 ± 4 MPa, by adding
49 wt% glycerol, which results in a 110 times
softer material than the initial microcrystal-
line powder that we used for the material
composition. Increasing the concentration
of glycerol beyond this level lead to a brittle
film, prone to wear, due to the excess of plas-
ticizer, and therefore such concentrations
were not further investigated. Figure  8a
summarizes the results with different con-
centrations of glycerol that were tested, and
their effect on the substrate mechanical
stiffness. To ensure that the addition of
glycerol on the cellulose substrate does not
influence the superhydrophobic proper-
ties of the wax-coated surface, drop impact
was observed on superhydrophobic sample
with glycerol concentration of 33 wt% in
the cellulose substrate (coated with wax with
spray concentration of 0.4 wt%). The water
drop performed a full rebound like in the
case of pure cellulose, wax-coated substrate
(Figure 8b) indicating that the addition
of glycerol to the cellulose substrate did
not adversely affect the superhydropho- Figure 8.  a) Graph depicting the Young’s modulus against the glycerol concentration inside
bicity of the material (Video S6, Supporting the cellulose. Samples of thickness 70 µm were used. b) Water drop bouncing on a wax-coated
Information). pillared surface. The base material is composed by 33 wt%.

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www.advancedsciencenews.com
made of cellulose, which is more than an order of magnitude
improvement compared to state of the art. We also show that our
cellulose material can be rendered 4 times more flexible with the
addition of glycerol as a natural plasticizer, and 110 times more
flexible compared to the crystalline powder that we used as a
raw material. It was possible to withstand hundreds of impacts
with full drop rebound as an outcome (from 2.5 cm height)
while there was also resistance against water jets (4.4 m s−1).
The material could maintain superhydrophobic properties even
after 100 folding cycles. We envision that these characteristics
will inspire various applications where environmentally friendly
self-cleaning materials are required.
4. Experimental Section
Outline of the Fabrication Procedure: Figure S1 (Supporting
Information) shows a schematic of our fabrication strategy. It involves
3 main steps: a) the Si master fabrication, b) the preparation of the
cellulose solution for the soft molding, and c) the final spray coating
treatment using carnauba wax. Below more details are provided for each
of the three different steps.
Preparation of the Si Masters: First, Si masters were fabricated, in
order to be eventually used for the soft molding of cellulose. These
masters contained the micropatterns to be transferred in cellulose, due
to which their geometrical parameters were important for controlling
the aspect ratio and interpillar spacing dint of the cellulose micropillars.
To fabricate the masters, a combination of UV lithography and
plasma etching was used. Starting with the UV lithography, a positive
photoresist (Microposit S1813) was spin-coated on a silicon wafer at
4000 rpm and baked for 2 min at 115 °C. Subsequently, the coated wafer
was exposed through a photomask containing the micropatterns to be
transferred. The UV exposure was performed using a Karl Suss MA6
mask aligner and a UV exposure dose of 120 mJ cm−2. Following the UV
exposure, the samples were immersed for 30 s in a solution containing
80 wt% water and 20 wt% Microposit 351 developer, in order to remove
the UV exposed material. During the development process the samples
were agitated to facilitate the photoresist removal. The aforementioned
process yielded micropatterns in photoresist, in the form of periodically
aligned circles. Three micropattern designs were fabricated, with circle
diameters d  = 5, 10, and 20 µm, while the ratio of interpillar spacing
to pillar diameter (dint/d) was kept constant at 2.5 for all the designs.
The ratio 2.5 was selected after analyzing various existing SEM images
of the Lotus leaf in the literature, wherein it was found to correspond
on average to the most frequently observed interpapillae distance. The
samples were then etched with the Bosch process to various depths
(up to 60 µm) using a PlasmaPro Estrelas 100 deep Si etcher (Oxford
instruments). The photoresist residues left under the etching process
were subsequently removed by O2 plasma exposure at 600 W for 16 min
(Q235 Microwave Plasma Etcher, Omni Technologies, USA). The Si
wafers were then functionalized with FDTS in order to lower their surface
energy and facilitate the subsequent soft molding procedure. The surface
silanization was performed in nitrogen atmosphere, by immersing the Si
masters for 2 min, in a solution consisting of 1.43 × 10−3 m solution of
FDTS in n-hexane. After the immersion, the masters were rinsed with
hexane, isopropyl alcohol, and deionized water, and subsequently were
dried at 120 °C for 10 min. Note that the step of Si master fabrication is
required only once, since these masters can be reused to create several
cellulose molds.
Soft Molding: The cellulose solution for the subsequent soft molding
was prepared by dissolving 3 wt% cellulose powder (Sigmacell Cellulose)
in trifluoroacetic acid (TFA) (3 wt%).[71] TFA was selected because it is
extremely volatile and this significantly facilitates the molding procedure.
Furthermore, it has been already used in the past for creating robust
cellulose sheets and other bioplastics.[71] Finally, it does not require
Adv. Mater. Interfaces 2019, 6, 1801202 1801202  (8 of 10)
www.advmatinterfaces.de
solvent exchange steps or post processing like other ionic solvents.
Therefore, it is found that it perfectly meets the fabrication requirements
for a soft molding technique like the one here, while at the same time,
its broad use in processing biomaterials can potentially transfer this
fabrication protocol to another natural material system.
The cellulose powder was completely dissolved in TFA after 3 days
and a transparent and homogeneous solution was obtained. However,
the cellulose solution was left for aging for at least one week, since
after the first 3 days it was still relatively viscous. The micropatterned
(in the form of microholes) Si wafers obtained in the previous step
were then used as masters for casting the cellulose solutions. The
casted solution was left overnight for the TFA to evaporate. Due to its
high vapor pressure (11 kPa at 20 °C), TFA quickly evaporates after the
solution is casted. Upon drying, the resulting cellulose material is rigid
and difficult to peel off from the masters. To facilitate its removal, the
samples were soaked for a few minutes in water, so that cellulose could
absorb water and start behaving like a gel. This significantly facilitated
the cellulose peeling off from the masters. After this, the sample was left
to dry and the cellulose micropillar geometries were obtained. Although
TFA is volatile, it is possible that traces can be found in the fabricated
cellulose. To evaluate the presence of such traces two types of analyses
were performed. SEM–EDX analysis did not show any elemental
fluorine signals on the dry films. This may be related to the resolution
of the microscopy or the fact that TFA could be buried within the bulk
of the film. However, direct insertion probe-electrospray ionization-mass
spectroscopy method indicated that dried transparent films can contain
up to 40 mg bound TFA/kg of cellulose. This concentration is low to
raise safety concerns, while past studies have shown that TFA traces do
not impose a bioaccumulation risk and will eventually degrade.[72,73]
Spray Coating with Carnauba Wax: In order to hydrophobize the
cellulose microstructures, a natural wax was used, very similar in chemistry
compared to the wax nanocrystals of the original Lotus leaf. To this
end, flakes of carnauba wax (Sigma Aldrich) were dispersed in
chloroform (Sigma Aldrich). The flakes tend to float in a chloroform
solution, but when heated above their melting point (82 °C) they form
a transparent homogeneous solution that is stable to be processed
through spray. Different concentrations of carnauba wax in chloroform
were prepared (0.1–0.4 wt%) and sprayed using a VL double action,
internal mix, siphon-feed airbrush (Paasche, USA). The spray distance
from the substrate was held constant at ≈10 cm and the air pressure was
set at 430 kPa. A total of 10 mL of the given wax solution was sprayed
over an area of ≈4 cm2.
Characterization of Surface Morphology and Wetting: The surface
morphology was characterized by using a Hitachi SU8200 (Japan) SEM.
To minimize surface charging effects, the samples were coated with
5 nm Pt using a sputtering tool. The wetting properties of all the
samples were evaluated using an automated contact angle (CA)
goniometer system (Dataphysics OCA 35, Germany). The SCA
was measured on each sample by using the sessile drop method.
Additionally, the advancing and receding contact angles were recorded,
in order to estimate the CAH. Specifically, a water drop was placed on
the surface with a dispensing nozzle still attached to it. Subsequently,
water was injected gradually until motion of the contact line was
observed and at this point the advancing angle was measured. Inversely,
gradually retracting liquid through the nozzle leads to shrinkage of the
water drop and eventually the contact line started receding. At the
first moment of this receding motion, the receding contact angle was
recorded.
Demonstration of the Self-Cleaning Effect: The self-cleaning properties of
the samples were evaluated by taking videos with artificial contaminants,
in order to capture in detail the contamination removal upon drop rolling
motion on the surfaces. Sudan II (Sigma Aldrich) powder was spread all
over the sample’s surface to simulate the presence of a contaminant.
The sample was then placed in an inclined position (<5°) and water
drops were carefully dispensed close to the surface of the sample in
order to minimize the effect of drop impact on the surface.
Biodegradation Tests: Biodegradability was measured for both carnauba
wax flakes and amorphous transparent cellulose after TFA treatment. In
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
the case of amorphous cellulose, the standard microcrystalline cellulose
was used as a reference. Biodegradation experiments were conducted
by a standard BOD procedure, which is an indirect and nonspecific
test that evaluates mineralization by measuring the amount of oxygen
consumed during a degradation reaction.[74] For each sample, including
the reference cellulose, three measurements were collected. Carefully
weighed samples (200 mg) were finely minced and immersed in
450 mL bottles containing seawater collected from the Genoa area
shoreline. The bottles were kept in dark and stirred with magnetic
anchors for the duration of the experiments, mimicking the pelagic
marine environment.[74] Oxygen consumed through biodegradation
reactions was recorded at different time intervals by the sealed OxiTop
caps on each bottle that can detect changes in oxygen levels. BOD from
blank bottles filled with only seawater was also measured as a control
case.
Durability Evaluation: The durability of the substrates was evaluated
against repeated impacts of water drops dispensed from a syringe of
0.9 mm nozzle diameter. Water jets were also dispensed, using the same
syringe, with a velocity of 4.4 m s−1. The dispensing height in both cases
was 2.5 cm from the surface.[75] The samples were kept tilted at 8° to
facilitate the directional removal of water for imaging purposes. Finally,
folding tests were performed by folding the material several times and
then capturing the rolling motion of water drops on the surfaces. All
the videos were recorded with a Photron Fastcam PCI1024 high-speed
camera operating up to 4000 fps.
Abrasion and adhesion tests were also performed. A 100 g
cylinder (diameter 13 mm) was dragged on the sample surface with
a velocity of ≈2 mm s−1. The applied pressure from the cylinder to the
sample was 2.17 kPa. For evaluating the adhesion we performed the
ISO standard adhesion tape test (EN ISO 2409). In both cases, after
each cycle of abrasion or tape peeling, the wetting properties were
evaluated.
Characterization and Tuning of Cellulose Stiffness: Glycerol was used
as a plasticizer to tune the stiffness of our cellulose material. Glycerol
was added in aged cellulose solutions and the mixture was agitated
overnight to achieve optimal mixing. The stiffness of the cellulose with
varying glycerol content was determined through uniaxial tensile tests.
The samples were cut to dimensions of 10 mm in width and 60 mm
in length, which corresponds to a chuck width of 40 mm. The cutting
was performed using a dedicated punch-tool. The tests were performed
on a measurement setup consisting of horizontally mounted hydraulic
actuators, a hydraulic power unit, 50 N load cells (MTS Systems, Eden
Prairie, USA) and custom-made clamps with sandpaper that were added
on both faces to improve grip. A nominal strain-rate of ε  = 0.001 s−1
was selected. The stiffness was measured using a secant modulus at 1%
strain, which is used to approximate the Young’s modulus. The sample
thickness was measured to be 70 µm.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors acknowledge financial support from the Swiss National
Science Foundation under Grant 162565. The authors thank Dr. Thi Nga
Tran (IIT) for assistance with the BOD tests.
Conflict of Interest
The authors declare no conflict of interest.
Adv. Mater. Interfaces 2019, 6, 1801202 1801202  (9 of 10)
www.advmatinterfaces.de
Keywords
biodegradable materials, carnauba wax, cellulose microstructures,
self-cleaning, superhydrophobic
Received: August 6, 2018
Revised: September 11, 2018
Published online: October 8, 2018
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