www.nature.

com/scientificreports

OPEN Synthesis and Characterization of

Superhydrophobic, Self-cleaning
NIR-reflective Silica Nanoparticles
received: 16 August 2016 Deepa Sriramulu1, Ella Louise Reed1, Meenakshi Annamalai2,
accepted: 10 October 2016 Thirumalai Venky Venkatesan2,3,4,5,6 & Suresh Valiyaveettil1
Published: 08 November 2016
Multifunctional coatings offer many advantages towards protecting various surfaces. Here we apply
aggregation induced segregation of perylene diimide (PDI) to control the surface morphology and
properties of silica nanoparticles. Differentially functionalized PDI was incorporated on the surface
of silica nanoparticles through Si-O-Si bonds. The absorption and emission spectra of the resultant
functionalised nanoparticles showed monomeric or excimeric peaks based on the amounts of perylene
molecules present on the surface of silica nanoparticles. Contact angle measurements on thin films
prepared from nanoparticles showed that unfunctionalised nanoparticles were superhydrophilic with a
contact angle (CA) of 0°, whereas perylene functionalised silica particles were hydrophobic (CA > 130°)
and nanoparticles functionalised with PDI and trimethoxy(octadecyl)silane (TMODS) in an equimolar
ratio were superhydrophobic with static CA > 150° and sliding angle (SA) < 10°. In addition, the near
infrared (NIR) reflectance properties of PDI incorporated silica nanoparticles can be used to protect
various heat sensitive substrates. The concept developed in this paper offers a unique combination
of super hydrophobicity, interesting optical properties and NIR reflectance in nanosilica, which could
be used for interesting applications such as surface coatings with self-cleaning and NIR reflection
properties.

Silica nanoparticles are used in medical, biological and chemical industries owing to their low toxicity, chemical
inertness, optical transparency and biocompatibility1,2. Dye-doped silica nanoparticles are designed and tested
for potential uses in biomedical and coating applications3,4 due to their highly desirable properties that include
excellent photostability, tunable optical properties, controllable size, thermal and environmental stability and a
large surface area to volume ratio5.
Perylene derivatives have been identified as fluorophores with high fluorescence quantum yield, good pho-
tostability6 and a high molar extinction coefficient (105 M−1 cm−1 for isolated perylene bisimide chromophores)7
owing to a planar and highly conjugated structures. Furthermore, the high reflectance in the NIR region of the
electromagnetic spectrum allows the incorporation of thermal insulating properties into materials8. Organic
NIR absorbers have a wide range of applications such as invisible inks, NIR readable bar codes, laser-welding
of plastics, laser induced thermal curing9, and energy saving applications10. The origin of the NIR reflectance is
due to the high refractive index of the perylene derivatives incorporated on various coatings8,10. NIR fluorescent
nanoparticles are useful as they provide negligible background fluorescence, low-inner-filtration interference in
complex biological systems such as whole blood11 and used as substrates for the characterization of enzymatic
processes12.
The observed hydrophobicity of the lotus leaf surface has led to extensive research into the development of
hydrophobic surfaces with hierarchal architectures13. For example, fabrics coated with dye incorporated sil-
ica nanoparticles were tested for the durability and wash fastness14, along with change in hydrophobicity with

1
Department of Chemistry, 3 Science Drive 3, National University of Singapore (NUS), 117543, Singapore. 2NUSNNI-
NanoCore, National University of Singapore, 117411, Singapore. 3Department of Physics, National University of
Singapore, 117542, Singapore. 4Department of Electrical and Computer Engineering, National University of
Singapore, 117576, Singapore. 5Department of Material Science and Engineering, National University of Singapore,
117575, Singapore. 6NUS Graduate School for Integrative Sciences & Engineering, National University of Singapore,
117456, Singapore. Correspondence and requests for materials should be addressed to S.V. (email: chmsv@nus.
edu.sg)

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 1

www.nature.com/scientificreports/

Figure 1.  Cross sectional view of the conceptualized structures of the three silica nanoparticles prepared
during this study. Full composition of each of these nanoparticle is given in the experimental section.

time15–17. Additionally, the degree of hydrophobicity to surface coating also reduced bacterial attachment leading
to antimicrobial nanoparticles18.
Inorganic materials such as aluminum, zinc and titanium based metal oxides with NIR reflectance property
and super hydrophobicity have been synthesized and reported in literature19,20. Organic fluorophores with high
reflectance in the NIR region are rare and incorporation of these into a nanoparticle lattice offers many advan-
tages such as low cost, biocompatiblity and easy accessibility. Consequently, the unique combination of hydro-
phobicity and NIR reflectance of such nanoparticles has led to the production of a diverse and multifunctional
materials with interesting applications.
Herein, we explore the relationship between molecular organizations on the surface with the overall prop-
erties of the particle (Fig. 1). We report surface functionalization of silica nanoparticles with perylene deriva-
tives and octadecyl groups to understand the significance of molecular arrangement on hydrophobic and optical
properties of the particles. Three types of functionalised silica nanoparticles are used in this study, the first one
involving particles with different concentrations of perylene molecules (P-1, P-2 and P-3), the second series with
both perylene and octadecyl groups at different molar ratios (PT-1, PT-2) and the third one with only octadecyl
groups (T1) on the surface. The questions addressed in this paper include, is it possible to control surface mor-
phology using aggregation of perylene, which in turn influence the properties of the particles? Also, what would
be the role of mixture of perylene and aliphatic long chain molecules towards the structure-property relationship
of the nanoparticles? It is conceivable that flexible octadecylsilyl molecules fill the gaps between the perylene
aggregates on the surface (PT-1, PT-2) and achieve complete coverage on the particle surface (Fig. 1).

Results
Synthetic Strategy and Characterization of Functionalised Silica Nanoparticles.  Silica nano-
particles were synthesised using a reverse microemulsion method (see Supplementary Method S1) and fully
characterised. Monodispersed silica nanoparticles were obtained with a narrow size distribution of around 40 nm
(Fig. 2a).
PDI precursors were synthesised using a reported procedure21 (see Supplementary methods S2 and S3) and
covalently attached to the surface of the silica nanoparticles. Different molar ratios of PDI and TMODS were
functionalised onto the silica nanoparticle surface (Table 1). SEM images showed no difference in surface mor-
phology before (pristine, Fig. 2a) and after functionalisation (P-3, Fig. 2b) on silica nanoparticles.
The FTIR spectra of the functionalised silica nanoparticles were recorded in the range of 500–4000 cm−1
in KBr matrix (Fig. 2c). Pristine silica nanoparticles were used as a control. The peaks observed at 3448 cm−1
and 1630 cm−1 corresponds to stretching vibrations of surface O-H groups of the silica nanoparticles. The peaks
1096 cm−1, 950 cm−1 and 795 cm−1 corresponds to Si-O-Si, Si-OH and Si-O bonds, respectively. Compared to
pristine silica nanoparticles, octadecyl groups incorporated particles PT-2 (1:1 molar ratio PDI to TMODS) and
T1 showed additional peaks at 2929 cm−1 and 2855 cm−1 which correspond to –CH stretching vibration of alkyl
groups. The perylene incorporated particles (P-1 to P-3 and PT-1, PT-2) showed peaks at 1691–1644 cm−1 for
imide C=​O stretching and 1596 cm−1 for aromatic C = C stretching vibrations. These results suggest that the
perylene and octadecyl moieties were successfully functionalised onto the surface of the silica nanoparticles.
Thermogravimetric analyses of the functionalised silica nanoparticles were carried out under nitrogen atmos-
phere with a heating rate of 10 °C/min in the temperature range of 50–800 °C (Fig. 3) and the results are sum-
marised in Supplementary Table S1. All TGA traces exhibit a three stage degradation process. The first step of
degradation was observed below 150 °C corresponding to the loss of adsorbed water molecules. The second mass

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 2

www.nature.com/scientificreports/

Figure 2.  SEM image of monodispersed silica nanoparticles before (a) and after (b) functionalisation with
perylene diimide molecules. FTIR spectra (c) of (i) SiO2 NPs, (ii) T1 (TMODS), (iii) P-1 (5 wt% PDI), (iv) P-
3 (21 wt% PDI), v) PT-2 (1:1 molar ratio of PDI to TMODS) functionalised silica nanoparticles. The marked
region in (c) is expanded and given in (d) to show corresponding peaks clearly. IR spectra of P-2 and PT-1 NPs
are given in the Supplementary Fig. S1a.

PDI TMODS λabs Absorbance TGA (%wt.

Sample (mg) (μL) % Ratio (nm) λemi (nm) ratio loss )
P-1 5.0 0 5 523 534 1.04 6%
P-2 10.0 0 10 490 530, 628 0.99 5%
P-3 21.0 0 21 494 650 0.78 8.2%
PT-1 18.0 0.13 1:0.01 491 638 0.75 9%
PT-2 18.0 12.8 1:1 490 630 0.89 11.3%
T1 — 18.0 18 — — — 10.5%
PDI silane
— — — 526 530 1.6* —
precursor

Table 1.  Amount of reagents used for the synthesis of different batches of functionalized nanoparticles
and the intensity ratios for the first and the second absorption peaks of perylene silica nanoparticles as
compared to reference PDI silane precursor dissolved in THF. (*) values from solution measurement, for all
cases, 100 mg of silica particles were used to start the reaction.

loss observed in the range of 150–400 °C, which can be assigned to the decomposition of organic groups
and loosely bound Si-(OR) groups. The third mass loss observed in the range of 400–800 °C was due to
degradation of both the organosilicate framework and the PDI groups on the surface of the particles 22.
TMODS functionalised (T1) and PDI functionalised P-1, P-2 and P-3 nanoparticles showed a 4%, 6%, 6%
and 5% weight loss, respectively, below 150 °C as compared to the pristine silica nanoparticles (8%). The
observed weight loss for the functionalised silica nanoparticles can be explained by the fact that the surface
functionalization of silica nanoparticles reduces the adsorption of water. When the temperature was further
increased from 150–800 °C, T1 and P-3 nanoparticles showed a 10.5% and 8.2% weight loss, respectively,
which can be explained as the loss of organic moieties grafted on the silica surface. Further, PT-1 and PT-2
showed weight loss of 9% and ~11%, respectively. These results are also supported by the elemental analysis
(see Supplementary Table S1).

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 3

www.nature.com/scientificreports/

Figure 3.  TGA traces of un-functionalised (◼) and functionalised ( ) T1, ( ) P-1, ( ) P-3, ( ) PT-2 silica
nanoparticles. Please see TGA traces of P-2 and PT-1 NPs in the Supplementary Fig. S1b.

Figure 4.  Normalised absorbance (a,c) and emission spectra (b,d) of ( ) PDI silane precursor, (◼) P-1 (5 wt%
PDI), ( ) P-2 (10 wt% PDI), ( ) P-3 (21 wt% PDI), ( ) PT-1 (1:0.01 molar ratio PDI to TMODS), (◆) PT-2
(1:1 molar ratio PDI to TMODS) functionalised silica nanoparticles dispersed in THF. Excitation wavelength
used was 350 nm.

Photophysical Properties of PDI Functionalised Silica Nanoparticles.  The absorption and emission
spectra of PDI and TMODS functionalised silica nanoparticles dispersed in THF are shown in Fig. 4.
The PDI silane precursors showed characteristic absorption peaks around 459, 489, and 526 nm correspond-
ing to the S0–S1 transition with a well resolved vibronic structure from 0–0, 0–1, 0–2 and 0–3 transitions, respec-
tively23. The absorption spectra of the PDI functionalized silica nanoparticles were broad with an inversion in
peak intensities of 0–1 and 0–0 transition, compared to free PDI silane precursor in THF solution (Fig. 4a). The
ratio of absorbance intensities of the 0–0 and 0–1 transitions are often used as an indication to determine the
extent of aggregation24. The A0-0/A0-1 ratio from the absorption spectra of PDI silane precursor in THF was found
to be ~1.6, which suggest the presence of free monomeric molecules in THF solution25. On functionalization
of PDI onto the surface of the silica nanoparticles, the A0-0/A0-1 ratio was found to decrease with an increase in
concentration of perylene on the surface and was 1.04 for P-1 (5 wt% PDI), 0.99 for P-2 (10 wt% PDI) and 0.79
(21 wt% PDI) for P-3 nanoparticles. Strong vibronic coupling of H-aggregates results in an increase in intensity

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 4

www.nature.com/scientificreports/

of the (0–1) vibronic band relative to the (0–0) transition band. Based on the absorbance intensity ratio, the PDI
molecules on the surface of the P-3 particles are more aggregated when compared to P-2 and P-1 particles. This
is expected owing to the higher concentration of PDI molecules present on the surface. Introduction of PDI and
TMODS in molar ratio of 1:0.01 (PT-1) and 1:1 (PT-2) led to changes in aggregation of the PDI molecules on the
surface (Fig. 4c). The A0-0/A0-1 ratio from the absorption spectra of the PT-2 was found to be 0.89, slightly higher
than that for PT-1 nanoparticles (0.75).
In order to understand the aggregation and arrangement of molecules on the surface, emission spectra of all
particles were analyzed and compared with the solution spectra of PDI. The emission spectrum of PDI silane
precursor in THF showed characteristic non-aggregated multiple maxima at 530, 568 and 618 nm (see Fig. 4b).
Significant changes in the emission spectra of PDI molecules were observed after functionalization on the sur-
face of silica nanoparticles (Fig. 4b). The nanoparticles with low concentration of PDI (P-1) showed an emis-
sion spectrum similar to the PDI silane precursor in solution. Upon increasing the concentration of PDI on the
surface of the silica nanoparticles a new broad peak with a maximum around 650 nm was observed from P-3
nanoparticles, which is similar to aggregated PDI dyes in solution (650 nm)26. This suggests that the variations
observed in the emission maxima of particles with different PDI concentrations is related to aggregation of mol-
ecules on the surfaces, which then allows fine tuning of the color of emission from yellowish green to bright pink
(see Supplementary Fig. S2). The emission properties of the PDI on the surface of silica nanoparticles arise from
the formation of distorted H-aggregates with an increase in concentration27.
Interestingly, the PT-1 (λ​emiss =​ 638 nm, Δ​P-3-PT-1 =​ 12 nm) and PT-2 (λ​emiss =​ 630 nm, Δ​P-3-PT-2 =​ 20 nm,) parti-
cles functionalized with both PDI and alkyl groups showed blue shift in emission peaks with respect to P-3 parti-
cles (λ​emiss =​ 650 nm) indicating higher distortion of H-aggregates caused by the presence of long octadecylsilane
groups (TMODS) on the surface as shown in Fig. 4d.

Characterization of Superhydrophobic properties.  The wetting ability of surfaces coated with func-
tionalised silica nanoparticles can be visualised by using highly polar substrates such as filter paper or silica-gel
TLC plate (Fig. 5). The choice of the commercially available TLC plate was made to represent a highly hydrophilic
rough surface. As expected, when the water droplet was placed on the unmodified commercially available silica
TLC plate, complete absorption and spreading on the surface was observed indicating a superhydrophilic surface.
In contrast, the P-3 coated TLC plate surface was hydrophobic (CA~137.2°, Fig. 5a) and the PT-2 coated surface
was superhydrophobic and repelled the water droplet completely (CA~156°, Fig. 5b).
In order to further demonstrate the superhydrophobic effect of silica nanoparticles, a concentration gradient
dependent hydrophobicity model was developed. One end of a long piece of filter paper of known length was
dipped in THF solution of the dispersed PT-2 NPs to achieve a concentration gradient effect across the filter
paper. The concentration gradient was formed through a combination of capillary force mediated wetting of the
paper and movement of solution upward from the solution front, along with continued evaporation of the solvent
THF from the surface of the paper. After drying at room temperature, the hydrophobicity was measured using
water drop test method (Fig. 5c).
It was observed that lower part of the filter paper exhibited superhydrophobic character, where the water
droplet completely rolled off from the surface of the coated filter paper when tilted (Fig. 5d). But other regions,
where concentration of the nanoparticles are low, water droplet stayed on the surface even when the paper was
tilted owing to the low concentration of the nanoparticles and strong interaction of water molecules with the
paper surface. Finally, at the region where the surface is completely hydrophilic, water is absorbed upon contact.
The changes in hydrophobicity and the wettability with water is directly proportional to the presence of PT-2 NPs
on the surface of paper.
Superhydrophobicity depends on the surface energy and surface roughness of the sample. SEM images of the
paper after coating of nanosilica (PT-2) showed uniform distribution of PT-2 nanoparticles on the surface of the
paper (Fig. 5f), when compared to pristine filter paper (Fig. 5e). In general, superhydrophobicity is significantly
enhanced when the hydrophobic surface has a hierarchal structure with a combination of both nanometre and
micrometre-sized roughness28.
Contact angle measurements were performed using two types of substrates, namely, cleaned glass cover slip
and silica TLC plate using goniometer measurements and summarised in Fig. 6a. Changes in contact angle were
observed on glass surface when coated with functionalised silica nanoparticles. Bare clean glass surface pro-
vided a contact angle of only ~55.7°, and coating with octadecyl silanes increased the contact angle to ~105°.
Coating with PT-2 NPs led to the formation of superhydrophobic surface with a water contact angle of >​150°.
The increase in contact angle can be attributed to the formation of rough micro-nanomorphological pattern on
these surfaces and reduction in surface energy of the particles.
Also, values of contact angle measured for the nanoparticle coated TLC plates were higher than the coated
glass substrates. SEM micrographs of TLC plate showed random distribution of silica clumps of size around
8–22 μ​m with random pores (see Supplementary Fig. S3a) and coating of the functionalized silica nanoparticles
led to a relatively less porous surface (see Supplementary Fig. S3b). As expected, commercially available TLC
plate is superhydrophilic with complete absorption or spreading of water with a contact angle (CA) of ~0°. Upon
coating with functionalised silica nanoparticles, an increase in the contact angle value was observed similar to
particles coated on paper. T1 particles showed a contact angle (CA) of 144° and a sliding angle of 25°. Similarly,
PDI functionalised silica NPs (P-3) coated TLC plate also showed a CA of ~137°. Thus PT-2 coated TLC plates
showed different behaviour as compared to T1 and P-3 coated TLC plates. This could be due to the arrangements
of molecules on the surface of silica particles T1 and P-3, which could trap water droplets and thus reduces the
contact angle (See Supplementary Fig. S4). PT-2 coated TLC plates exhibited non-sticky, water repellent proper-
ties with CA of ~156° and sliding contact angle (SA) less than 10° indicating superhydrophobicity.

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 5

www.nature.com/scientificreports/

Figure 5.  Image of water drop on the surface of (a) P-3, (b) PT-2 coated silica TLC plate. Inset shows
corresponding image of water drop taken during contact angle measurements, where drop does not stick to the
surface coated with PT-2 NPs. Effect of concentration gradient of PT-2 (1:1 molar ratio PDI to TMODS) silica
nanoparticles coated on filter paper held parallel (c) and perpendicular (d) to the surface in the presence of
water droplet. SEM images of paper before (e) and after (f) coating with PT-2 silica nanoparticles.

Video footage taken using a high speed camera was used to further demonstrate the water repellent properties
of the nanoparticle coated surface. The kinetic energy of the droplet was transformed into vibrational energy on
touching the PT-2 coated surface leading to the anisotropic bouncing of the water droplet without allowing it to
rest in the Cassie state (Fig. 6b)29. As a control, the same experiment was performed with a T-1 (TMODS) coated
surface (Fig. 6c). In contrast to the PT-2 system, when the water droplet fell on the T-1 coated surface it did not
rebound from the surface.
The wettability of a material is often attributed to a low surface free energy and a high degree of roughness30.
The ‘Lotus effect’ explains how hierarchal structures with micro- and nanoscale roughness can lead to supe-
rhydrophobicity and an extreme non-stick and water-repellent surface28. Higher magnification SEM images
(see Supplementary Fig. S3b) of both P-3 and PT-2 coated TLC plates showed similar distribution of silica nano-
particles on the surface of TLC plate. Thus, hydrophobicity observed for all functionalised silica NPs (T1, P-3 and
PT-2) coated TLC plates is due to micro-nanoroughness achieved by the assembly of functionalised silica nano-
particles on silica clusters. The distribution of nanoparticles may increase the amount of trapped air in between
the particles, which then enhances the hydrophobicity, as described in the Cassie-Baxter model31. In addition,
micro-nanoscale roughness was formed by the assembly of multiple layers of nanoparticles (Fig. 7a). Similar to
the lotus leaf, the PT-2 coated surface possess a hierarchical structure from multiple layers of surface functional-
ised silica nanoparticles with hydrophobic groups (i.e. PDI and TMODS).

NIR reflectance of PDI functionalised nanoparticles.  Approximately 52% of ultraviolet radiation that
reaches the Earth is in the near infrared region (700–2300 nm) of the electromagnetic spectrum. Absorption of
radiation in this region will eventually lead to heat gain in many objects32. As a counter measure, NIR reflective
colorants are used as an effective means of reflecting such radiations. Since perylene derivatives have shown NIR
reflectance8,10, it is conceivable that PDI functionalised silica nanoparticles will also exhibit such properties.

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 6

www.nature.com/scientificreports/

Figure 6. (a) Contact angle and sliding angles (CA and SA) of glass slide and silica TLC plate substrates coated
with functionalised silica nanoparticles (#Control samples are bare glass cover slips and silica TLC plate, P-3, PT-2,
functionalised silica nanoparticles, T1 refers to TMODS functionalised silica nanoparticles. *As per ref. 34). Selected
stills showing the anisotropic bouncing of a water droplet on a PT-2 (b) and T1 (c) coated TLC plate in a 30 ms time
frame.

The diffuse reflectance results obtained from PDI functionalised silica nanoparticles (P-3) coated on glass
substrate using Teflon as a reference is shown in Fig. 7b. A narrow 1100 nm wavelength radiation was chosen for
our experiment19. From the data obtained (Fig. 7c), PDI functionalised silica nanoparticles showed NIR reflec-
tance up to 52% compared to pristine silica nanoparticles (28%). Also, glass substrate coated with PDI showed
maximum reflectance (80%) in accordance with previous literature8,10. Such increase in NIR reflective properties
after functionalisation of nanoparticle with PDI could be used to reduce the build-up of heat in materials from
the absorption of NIR radiation.

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 7

www.nature.com/scientificreports/

Figure 7. (a) Cartoonistic representation of water droplet on the surface of the PT-2 nanoparticle coated
TLC surface. (Objects are not in scale). (b) % NIR reflectance of (i) glass cover slip, (ii) unfunctionalised silica
nanoparticles, (iii) P-3 (21 wt% PDI), (iv) perylene diimide (PDI) drop cast on a glass cover slip in the range of
800–2200 nm. (c) The plot of (%) NIR reflectance of different materials and (d) different concentrations of SiO2
and PT-2 (1:1 molar ratio PDI to TMODS) nanoparticles drop casted on glass cover slip.

The concentration dependent NIR reflectance studies were carried out on PT-2 silica nanoparticles and com-
pared to pristine silica nanoparticles coated on a glass substrate as a control (Fig. 7d). The maximum reflectance
(50%) was obtained from PT-2 NPs compared to bare silica nanoparticles showing only 15% reflectance for the
same amount (0.75 mg) dispersed on glass cover slip. Further optimization of experimental variables such as the
size of nanoparticles, concentration of PDI on the surface, coating processes, is currently in progress to optimize
the NIR reflective properties. From the preliminary experiment, it is noted that PDI functionalised on silica nan-
oparticles do exhibit NIR reflective property.

Discussion
Six functionalised silica nanoparticles were synthesised, fully characterised and properties were investigated.
The absorption and emission spectra of the samples showed correlation with the amount of perylene diimide
(PDI) groups incorporated on the surface of the silica nanoparticles. Increasing the concentration of PDI, for
example, led to a red shift in absorption maxima, changes in peak intensities and loss of vibrational fine structure
demonstrating the aggregation induced formation of excimeric state. By using a mixture of PDI and TMODS on
silica nanoparticle surface, the aggregation of PDI and organic molecule coverage on the particle surface were
modulated. Among the six types of nanoparticles prepared, PT-2 showed the maximum coverage and fascinating
properties. Pristine silica nanoparticles were hydrophilic (CA =​ 0°) and PDI functionalised nanoparticles showed
hydrophobicity (CA =​ 137.2°). However, co-immobilization of the PDI and TMODS on the surface of particles
led to superhydrophobic nanoparticles (PT-2) with a CA of >​150° and a sliding contact angle (SA <​  10°). The
high hydrophobicity of the PT-2 is explained based on the effective coverage of the surface with organic mole-
cules. Furthermore, the high NIR reflectance of PDI derivatives was used towards developing silica nanoparticle
coatings with more than 80% NIR reflectance. In conclusion, here we report the successful synthesis of a fluo-
rescent, superhydrophobic, self-cleaning NIR-reflective silica nanoparticles for coating on sensitive instruments.

Methods
Materials.  Tetraethylorthosilicate (TEOS), (3-aminopropyl)triethoxysilane (APTES), perylene-3,4,9,10-tet-
racarboxydianhydride and trimethoxy(octadecyl)silane (TMODS) were obtained from Sigma Aldrich. Aqueous
ammonia solution (25%) was obtained from Merck. All chemicals and solvents used were AR grade and used
without further purification.

Characterization Methods.  Nuclear magnetic resonance (1H NMR) spectra were recorded on Bruker
Avance AV300 (300 MHz) NMR instrument using CDCl3 as the solvent. Absorption and emission spectra were
measured on a UV-1601PC Shimadzu spectrophotometer and RF-5301PC Shimadzu spectrofluorophotometer.

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 8

www.nature.com/scientificreports/

Bruker ALPHA FT-IR spectrophotometer was used for records Fourier transform infrared (FT-IR) spectroscopy
analysis. Thermogravimetric analyses (TGA) were conducted using a SDT 2960 TA instrument. All samples were
heated under nitrogen atmosphere from 25 °C to 800 °C using a heating rate of 10 °C/min. FT-IR spectra were
recorded in the range of 3800–400 cm−1 using a Varian Excalibur 3100. Samples were mixed with KBr powder and
grounded in an agate mortar before being pressed into a disk for recording the spectrum.

Contact Angle Measurement.  The macroscale contact angle measurements were carried out using
the video-based fully automated data physics optical contact angle microlitre dosing system (OCA 40 Micro,
Germany). Deionised water drops (1 μ​l/drop) with known surface tension were dispensed using Teflon coated
motor driven syringe. The contact angles were measured at be measured at 22 °C and 45% RH conditions and a
video was recorded (72 frames/second) for every dispensed solvent droplet. Any dynamic changes to the droplet
on the surface could be precisely observed through this method33.
Functionalised silica nanoparticles (0.005 g) were dispersed in THF (2 ml) and sonicated for 10 minutes. TLC
plates were dip coated in the dispersion of silica nanoparticles in THF and left to dry at room temperature. This
procedure was repeated several times until a uniform coating was achieved.
For coating on glass cover slips, aqueous NaOH solution (10%) was used to clean the surface and dried prior
to drop casting the solution of silica nanoparticles in THF.
Finally, a gradient coating of functionalized silica nanoparticles on a strip of filter paper (0.5 ×​1.0 cm) was
achieved by touching one end of the paper to the nanoparticle solution and letting the capillary action draw the
solution to the paper. During the rise of solution through the paper, the solvent THF tends to evaporate and
deposit the particles on the paper. This process allowed us to create a gradient with more nanoparticles at the end
of the paper closer to the solution and less particles at the other end. Since the nanoparticles are red in color, the
capillary gradient coating is visible with the naked eye. Three sections with high, medium and low concentrations
of nanoparticles on coated filter paper were then tested to demonstrate how the degree of hydrophobicity was
dependent on concentration of the particles adsorbed.

NIR Reflectance Measurement.  The NIR diffuse reflectance of the silica nanoparticles coated glass sub-
strate was measured using UV-Vis-NIR spectrophotometer (Shimadzu, UV-3600) with an integrating sphere
attachment, ISR-3100. The NIR reflectance measurements of the samples were performed within the wavelength
range of 700–2200 nm.

General Procedure for Functionalization of Silica Nanoparticles.  Silica nanoparticles (100 mg) dis-
persed in dry toluene (10 ml) under nitrogen atmosphere were treated with PDI silane precursors and/or TMODS
at different ratios to functionalise the surface (see Table 1). The mixture was refluxed under constant stirring at
90 °C for 24 hours, centrifuged to obtain the solid and washed with THF to remove unreacted silane precursors
before drying.
A summary of the amounts of reagents used for the synthesis of functionalised nanoparticles is given in
Table 1, where P-1, P-2 and P-3 refers to 5, 10 and 21 wt% of PDI, respectively, in solution, and PT-1 and PT-2
refers to a 1:0.01 and a 1:1 molar ratio of PDI to TMODS reagents, respectively, and T1 refers to silica nanoparti-
cles functionalized with TMODS only.

References
1. Knopp, D., Tang, D. & Niessner, R. Bioanalytical applications of biomolecule-functionalized nanometer-sized doped silica particles.
Anal. Chim. Acta. 647, 14–30 (2009).
2. Montalti, M., Battistelli, G., Cantelli, A. & Genovese, D. Photo-tunable multicolour fluorescence imaging based on self-assembled
fluorogenic nanoparticles. Chem. Soc. Rev. 50, 5326–5329 (2014).
3. Ruedas-Rama, M. J., Walters, J. D., Orte, A. & Hall, E. A. H. Fluorescent nanoparticles for intracellular sensing: A review. Anal.
Chim. Acta. 751, 1–23 (2012).
4. Hong Nhung, T. et al. Dye-doped silica-based nanoparticles for bioapplications. Adv. Nat. Sci.: Nanosci. Nanotechnol. 4, 043001
(2013).
5. Sreenivasan, V. K. A., Zvyagin, A. V. & Goldys, E. M. Luminescent nanoparticles and their applications in the life sciences. J. Phys.
Condens. Matter. 25, 194101 (2013).
6. Ma, Y. et al. A water-soluble fluorescent pH probe based on perylene dyes and its application to cell imaging. Luminescence. 31,
102–107 (2016).
7. Gallaher, J. K., Aitken, E. J., Keyzers, R. A. & Hodgkiss, J. M. Controlled aggregation of peptide-substituted perylene-bisimides.
Chem. Commun. 48, 7961–7963 (2012).
8. Kaur, B., Bhattacharya, S. N. & Henry, D. J. Interpreting the near-infrared reflectance of a series of perylene pigments. Dyes Pigm. 99,
502–511 (2013).
9. Qian, G. & Wang, Z. Y. Near-infrared organic compounds and emerging applications. Chem. Asian J. 5, 1006–1029 (2010).
10. Kaur, B., Quazi, N., Ivanov, I. & Bhattacharya, S. N. Near-infrared reflective properties of perylene derivatives. Dyes Pigm. 92,
1108–1113 (2012).
11. Deng, T., Li, J., Jiang, J., Shen, G. & Yu, R. Preparation of near-IR fluorescent nanoparticles for fluorescence-anisotropy-based
immunoagglutination assay in whole blood. Adv Funct Mater. 16, 2147–2155 (2006).
12. Freschauf, L. R., McLane, J., Sharma, H. & Khine, M. Shrink-induced superhydrophobic and antibacterial surfaces in consumer
plastics. Plos One 7, e40987 (2012).
13. Parhizkar, M., Zhao, Y., Wang, X. & Lin, T. Photostability and durability properties of photochromic organosilica coating on fabric.
J. Eng. Fiber. Fabr. 9, 65–73 (2014).
14. Liu, B. et al. Synthesis and characterization of photoreactive silica nanoparticles for super-hydrophobic cotton fabrics application.
Text. Res. J. 85, 795–803 (2015).
15. Hirashima, H., Imai, H. & Fukui, Y. Structure of Hybrid Silica Gels Incorporated with Hydrophobic Dye Molecules. J. Sol-Gel Sci.
Technol. 26, 383–388 (2003).
16. Lin, J., Chen, H., Fei, T. & Zhang, J. Highly transparent superhydrophobic organic–inorganic nanocoating from the aggregation of
silica nanoparticles. Colloids Surf., A. 421, 51–62 (2013).

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 9

www.nature.com/scientificreports/

17. Lee, J. H., Park, E. J., Kim, D. H., Jeong, M. G. & Kim, Y. D. Superhydrophobic surfaces with photocatalytic activity under UV and
visible light irradiation. Catal. Today. 260, 32–38 (2016).
18. Weir, E., Lawlor, A., Whelan, A. & Regan, F. The use of nanoparticles in anti-microbial materials and their characterization. Analyst.
133, 835–845 (2008).
19. Soumya, S., Mohamed, A. P., Mohan, K. & Ananthakumar, S. Enhanced near-infrared reflectance and functional characteristics of
Al-doped ZnO nano-pigments embedded PMMA coatings. Sol. Energ. Mat. Sol. Cells. 143, 335–346 (2015).
20. Xu, Q. F., Liu, Y., Lin, F. J., Mondal, B. & Lyons, A. M. Superhydrophobic TiO2–Polymer Nanocomposite Surface with UV-Induced
Reversible Wettability and Self-Cleaning Properties. ACS Appl. Mater. Interfaces 5, 8915–8924 (2013).
21. Huang, H., Che, Y. & Zang, L. Direct synthesis of highly pure perylene tetracarboxylic monoimide. Tetrahedron Lett. 51, 6651–6653
(2010).
22. Wahab, M. A., Hussain, H. & He, C. Photoactive Perylenediimide-Bridged Silsesquioxane Functionalized Periodic Mesoporous
Organosilica Thin Films (PMO-SBA15): Synthesis, Self-Assembly, and Photoluminescent and Enhanced Mechanical Properties.
Langmuir 25, 4743–4750 (2009).
23. Ribeiro, T., Baleizão, C. & Farinha, J. P. S. Synthesis and Characterization of Perylenediimide Labeled Core−​Shell Hybrid Silica−​
Polymer Nanoparticles. J. Phys. Chem. C. 113, 18082–18090 (2009).
24. Li, X., Sinks, L. E., Rybtchinski, B. & Wasielewski, M. R. Ultrafast aggregate-to-aggregate energy transfer within self-assembled light-
harvesting columns of zinc phthalocyanine tetrakis(perylenediimide). J. Am. Chem. Soc. 126, 10810–10811 (2004).
25. Gómez, R. et al. Energy and electron transfer in a poly(fluorene-alt-phenylene) bearing perylenediimides as pendant electron
acceptor groups. Macromolecules 40, 2760–2772 (2007).
26. Neuteboom, E. E., Meskers, S. C. J., Meijer, E. W. & Janssen, R. A. J. Photoluminescence of Self-organized Perylene Bisimide
Polymers. Macromol. Chem. Phys. 205, 217–222 (2004).
27. Chen, Z., Baumeister, U., Tschierske, C. & Würthner, F. Effect of core twisting on self-assembly and optical properties of perylene
bisimide dyes in solution and columnar liquid crystalline phases. Chem. Eur. J. 13, 450–465 (2007).
28. Barthlott, W. & Neinhuis, C. Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta. 202, 1–8 (1997).
29. Huang, J. Y. et al. Robust superhydrophobic TiO2@fabrics for UV shielding, self-cleaning and oil-water separation. J. Mater. Chem.
A. 3, 2825–2832 (2015).
30. Terpiłowski, K., Rymuszka, D., Goncharuk, O. V., Sulym, I. Y. & Gun’ko, V. M. Wettability of modified silica layers deposited on glass
support activated by plasma. Appl. Surf. Sci. 353, 843–850 (2015).
31. Chu, Z. & Seeger, S. Superamphiphobic surfaces. Chem. Soc. Rev. 43, 2784–2798 (2014).
32. Levinson, R., Berdahl, P. & Akbari, H. Solar spectral optical properties of pigments - Part I: Model for deriving scattering and
absorption coefficients from transmittance and reflectance measurements. Sol. Energ. Mat. Sol. Cells. 89, 319–349 (2005).
33. Annamalai, M. et al. Surface energy and wettability of van der Waals structures. Nanoscale 8, 5764–5770 (2016).
34. Wu, Y. et al. Patterned hydrophobic–hydrophilic templates made from microwave-plasma enhanced chemical vapor deposited thin
films. Thin Solid Films. 515, 4203–4208 (2007).

Acknowledgements
The authors acknowledge funding support from National University of Singapore and technical support from
Department of Chemistry, National University of Singapore. Deepa Sriramulu thanks Ministry of Education and
National University of Singapore for a research scholarship towards her PhD program.

Author Contributions
D.S. and E.R. conducted experiments, wrote manuscript and analyzed results; S.V. designed, analyzed results
and revised manuscript; M.A. and T.V. conducted contact angle measurement. All authors reviewed manuscript.

Additional Information
Supplementary information accompanies this paper at http://www.nature.com/srep
Competing financial interests: The authors declare no competing financial interests.
How to cite this article: Sriramulu, D. et al. Synthesis and Characterization of Superhydrophobic, Self-cleaning
NIR-reflective Silica Nanoparticles. Sci. Rep. 6, 35993; doi: 10.1038/srep35993 (2016).
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and
institutional affiliations.
This work is licensed under a Creative Commons Attribution 4.0 International License. The images
or other third party material in this article are included in the article’s Creative Commons license,
unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license,
users will need to obtain permission from the license holder to reproduce the material. To view a copy of this
license, visit http://creativecommons.org/licenses/by/4.0/

© The Author(s) 2016

Scientific Reports | 6:35993 | DOI: 10.1038/srep35993 10