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Materials Today: Proceedings 00 (2018) 0000–0000 www.materialstoday.com/proceedings

ICCSE 2018

Polyethyleneimine-capped silver nanoparticles as antifouling

photocatalyst for wastewater treatment
Maxine Swee-Li Yeea*, Poi-Sim Khiewa, Wee Siong Chiub, Yuen-Fen Tanc,d, Chee-Onn
Leongc,d
a
Centre of Nanotechnology and Advanced Materials, Faculty of Engineering, University of Nottingham Malaysia Campus, Jalan Broga, 43500
Semenyih, Selangor, Malaysia
b
Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University Malaya, 50603 Kuala Lumpur, Malaysia
c
School of Pharmacy, International Medical University, 126 Jalan Jalil Perkasa 19, Bukit Jalil, 57000 Kuala Lumpur, Malaysia.
d
Center for Cancer and Stem Cell Research, Institute for Research, Development and Innovation (IRDI), International Medical University, Bukit
Jalil, 57000 Kuala Lumpur, Malaysia

Abstract

Water pollution is one of the most urgent challenges of the 21st century, with water security having widespread consequences on
society and the global economy. Methylene blue (MB) is a toxic by-product of textile and dye industries which has polluted
wastewaters. Biofouling of man-made surfaces is a longstanding issue with serious consequences in the maritime and water
treatment industries. Ag and its compounds are historically well-known as antibacterial agents, whilst polyethyleneimine (PEI) has
good stabilizing and adsorption properties. In this work, colloidal Ag nanomaterials (diameter ~2.6 ± 1.1 nm) produced using PEI
as the capping agent demonstrated potential as antifouling photocatalysts for water treatment applications. The photocatalytic effect
of Ag-PEI was studied using UV-visible spectrophotometry on the decomposition of methylene blue, with a 90.2% peak reduction
of its UV-visible spectral peaks and decoloration recorded after 90 minutes of UV-irradiation. Separately, Ag-PEI demonstrated a
63% reduction of biofilm formation by Halomonas pacifica, a model marine-biofilm bacterium, through a static biofilm assay.
© 2018 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and
Engineering: Advance and New Materials, ICCSE 2018.

Keywords: Ag-PEI; Antifouling; Biofilm inhibition; Halomonas pacifica; Photocatalyst; Methylene blue

1. Introduction

According to UNESCO, water quality is one of the most urgent challenges of the 21st century threatening humanity,
with annual estimates of up to 400 megatonnes of industrial waste being discharged into water bodies [1]. The

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and
Engineering: Advance and New Materials, ICCSE 2018.
2 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

deterioration of water quality affects human health and causes environmental problems. Water pollutants are classified
as organic (e.g. dyes, pesticides), inorganic (e.g. metals, nitrates, phosphates) and microorganisms [2]. Increasing
manufacturing activity in developing countries, especially from synthetic textiles and plastics industries, has resulted
in significant discharge of polluted wastewater, containing high concentrations of toxic organic dyes, e.g. methylene
blue, rhodamine. In particular, textile production requires extremely large amounts of water, which is discharged as
wastewater containing high concentrations of reactive dyes (e.g. methylene blue, rhodamine B), chemical residues and
low-biodegradable materials [3]. Without wastewater treatment, these pollutants accumulate in rivers, lakes and large
bodies of water, causing a decrease in water quality by incurring high levels of chemical and biochemical oxygen
demand (COD and BOD, respectively). Conventional wastewater treatment methods including biological treatment,
coagulation, adsorption, radiation, and oxidation do not completely resolve the problem [3]. Membrane-based
technology is highly promising, however, issues with membrane fouling still need to be effectively addressed [3,4].
Therefore, more effective and affordable wastewater treatment methods are continually being sought.
Marine fouling is an accumulation of diverse organisms ranging from microscopic bacteria to macroalgae,
barnacles, mussels and tubeworms [5]. The fouling process is preceded by the formation of a biofilm on a wetted and
conditioned surface [6]. Once the non-reversible adhesion of bacteria commences in the biofilm build-up phase, the
stage is set for the eventual settlement of larger organisms attracted to the conducive and nutrient-rich environment
provided by the biofilm.
The global shipping industry is deeply interested in eradicating fouling of ship hulls due to the high cost of heavy
fouling on the speed and performance of vessels [7]. It has been estimated that the antifouling industry is worth
approximately USD 4 billion in 2009 [8]. The US Navy estimates the overall costs related to hull fouling of their entire
DDG-51 class to be USD 1 billion over 15 years [9]. Commercial antifouling technologies are based on biocidal
coating formulations containing copper metal oxides and organic booster compounds including TCMS pyridine
(2,3,5,6-tetrachloro-4-(methyl sulphonyl) pyridine), TCMTB (2-(thiocyanomethylthio) benzothiazole) and
dichlofluanid [10,11]. However, exposure and accumulation of these and other booster biocide compounds pose
general aquatic toxicity to algae and marine animals [11,12].

1.1. Silver nanomaterials

Silver nanomaterials have attracted intense interest due to their size-dependent properties, which can be tailored for
various applications, ranging from antimicrobial medical devices [13], printed electronic components [14], membrane
technology [15], chemical sensors [16], photoimaging [17], catalysis [18]. Its history in medical use has been
documented as far back as 750 A.D. [19], with better antimicrobial properties reported for smaller, nano-sized particles
compared to bulk silver [20]. The bottom-up approach in the synthesis of nanomaterials is especially useful in the
formation of quantum dots and nanocrystals [21]. Various synthetic routes for the formation of nanostructured Ag
have been reviewed [22] and classified under wet chemistry [23], biological [24], and physical methods including
microwave-assisted method [25] and laser irradiation [26]. Wet chemical processing has distinct advantages over other
methods in terms of powder morphology and better scale-up efficiency [27], while reaction conditions should be
optimized to achieve control over morphology and monodispersity of the AgNPs [22].
The synthesis of NPs through wet chemical processing often results in an unstable product [28]. Due to the high
surface energy to volume ratio of NPs, particle agglomeration occurs, causing polydispersity of the product, and thus
restricting their functional efficiency [29]. Lyophilization has been proposed as a storage method to preserve Ag NPs
into solid powder with long term stability without undergoing solution-based chemical changes [19]. However, the
stability of Ag NPs are most commonly extended through the use of capping ligands or stabilizing agents such as
citrate [30], polyvinyl pyrrolidone (PVP) [23], polyvinyl alcohol (PVA) [31,32], polyethyleneimine (PEI) [20] or
polysaccharides eg. dextran [33]. Stabilizers prevent the aggregation of NPs and controls the size of the final product
through Coulombic repulsion (electrostatic stabilization), the presence of large pendant groups (stearic stabilization),
or a combination of both [34].
Although AgNPs has been extensively research as an antimicrobial agent [35], its potential as a marine
antimicrofouling agent has had limited exploration. Ag NPs were found to have anti-biofilm activity against several
strains of bacteria with clinical consequence, including Pseudomonas aeruginosa [36] while water filtration
membranes incorporated with Ag NPs inhibited the growth of Escherichia coli [37]. The antibiofilm activity of Ag
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 3

NPs against several marine bacteria isolated from off the coast of Chennai were reported, with promising positive
results [38]. Our group has reported on the enhanced biofilm inhibition activities of various Ag-nanocomposites
including Ag-polymer microbeads [39], Ag-graphene nanosheets [40], Ag-zeolite powders [41] and Ag-TiO2
nanotubes [42]. In the present study, we examine the influence of PEI of various molecular weights and concentrations
in controlling the size of the Ag NPs and thus, their capability to restrict biofilm development by the marine bacteria
Halomonas pacifica. We also evaluate the photocatalytic effect on the degradation of the organic dye methylene blue.
PEI is a cationic polymer consisting of secondary amine groups along the polymeric backbone and tertiary amine
groups at the side chains that are able to form chelates with metal ions [43]. It enhances the stability of nanomaterials
through electrostatic repulsion by conferring a positive charge to NPs. It has been used as an effective capping ligand
in AgNP syntheses [20,44,45]. The effect of different molecular weight of PEI on the Ag NPs property has not been
explored comprehensively, to the best of our knowledge. H. pacifica has been used as a model bacterium for biofilm
inhibition studies [46,47]. In addition, PEI also exhibits antimicrobial properties [48,49], which synergizes with the
properties of AgNPs for potential antifouling coating applications as well as photocatalysts in the degradation of
organic dyes such as methylene blue.

2. Materials and methods

2.1. Materials

Analytical grade silver nitrate (AgNO3) 99.9999% metals basis granules, sodium borohydride (NaBH4) 99.99%
granules and branched polyethyleneimine (PEI) with various average molecular weights (Mw ranging from 800 to
750,000) were purchased from Sigma-Aldrich. Methylene blue trihydrate (Mallinckrodt, 99%) was used as the model
organic dye for the evaluation of photocatalytic activity. A marine bacterium, Halomonas pacifica (Baumann et al.)
Dobson and Franzmann (ATCC® 27122) was purchased from American Type Culture Collection (ATCC) and
cultured in Zobell Marine Broth 2216 (HiMedia Laboratories, India). All materials were used as received. All reagents
were prepared with Millipore ultrapure water (18 M/cm).

2.2. Preparation of Ag-PEI

Ag-PEI was synthesized by adaptation of a technique reported by Lee et. al [20]. Stock solutions of AgNO3 of 1 x
10-3M and NaBH4 of 2 x 10-3M were prepared fresh for each sample. To investigate the effect of the molecular weight
of PEI on the Ag NPs, PEI with molecular weights of 800, 2000, 10000 and 750,000 were added to 5 ml silver
precursor and stirred for 15 minutes before the addition of 15 ml sodium borohydride. The PEI constitutes a weight
fraction of 2.5 wt% of the total weight of the AgNO 3-NaBH4 system.
To investigate the effect of the PEI concentration on the Ag NPs, PEI with molecular weight of 750,000 was
dissolved in ultrapure water to form a PEI-750K solution of 0.02 % w/v. The PEI-750K stock solution of various
weight fractions were added to 5 ml of AgNO3 solution and stirred for 15 minutes. 15 ml of NaBH4 solution were then
added to the mixture at room temperature under stirring for10 minutes. The PEI weight fractions were varied between
2.0 – 52.5 wt% of the total weight of the AgNO3-NaBH4 system. The mixture changed from a colourless solution to
yellow or brown, indicating the reduction of silver cations into metallic Ag NPs in a colloidal form. Ag-PEI were kept
in glass vials and stored in the dark prior to physical characterization and evaluation for biofilm inhibition and
photodegradation of MB organic dye.

2.3. Instrumentations and characterisations

The surface plasmon excitation of colloidal Ag-PEI was measured through a Varian Cary 50 Conc UV-visible
spectrophotometer. To adjust the absorbance maximum between 0.5 – 2 units, the samples were diluted with ultrapure
water. Two ml of diluted sample is pipetted into a 10 mm quartz cell and subjected to incident light from the ultraviolet
4 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

and visible wavelengths of 800 – 200 nm emitted from a Xenon lamp. The dried sample morphology was observed
through an FEI Quanta 400F FESEM under high vacuum at 20 kV. A drop of sample was carefully placed on carbon
tape attached to a SEM sample stub and dried at 70 C for 10h before the analysis. Samples were also observed under
transmission electron microscopy (TEM) on a JEOL JEM-2100F at an operating voltage of 200 kV. Particle size
analysis was conducted through analysis of a minimum of 70 points to calculate the mean diameter and standard
deviation.

2.4. Static biofilm assay for antimicrofouling activity

To assess the efficiency of Ag-PEI in biofilm inhibition, we used a general static biofilm inhibition assay protocol
involving H. pacifica, a marine bacterium used as a model biofilm-causing organism [46,47]. A similar protocol was
successfully used in our previous works [39–42]. Briefly, H. pacifica was cultured overnight in marine broth, and then
subcultured at an optical density 600 nm (OD 600) of 0.01 into marine broth along with a suspension of the Ag-PEI
samples (concentration of 10 %v/v). Samples were incubated under stationary conditions at 26 C overnight. Biofilm
inhibition was quantified by using a Tecan Infinite 200 microplate reader to measure the optical density at 540 nm
(OD540). The readings are then compared with a positive control (containing bacteria only in culture medium) and a
negative control (medium only) for a comprehensive quantification study.

2.5. Photodecomposition of MB organic dye

Photodecomposition studies of MB organic dye was carried out using a method adapted from our previous work
[50]. Briefly, 10.0 mL of MB aqueous solution with an initial concentration of 5.00 ppm in the presence of Ag-PEI
were conducted in a heavy-duty Schott soda-lime test-tube (GL-18) under consistent UV irradiation. Prior to
irradiation, the samples were sonicated for 2.0 min. Then, the samples were irradiated by using UV-crosslinker (UVP-
CL1000, Cambridge), which is operating at a power of 8.0 W and equipped with high-pressure mercury lamp of 4.0
cm placed above the test-tube to provide irradiance wavelength of 254 nm. The average intensity of UV irradiance
reaching the samples was measured to be ca. 100 μJ/cm2. Once the irradiation duration was completed, the sample
was transferred into quartz cuvette (optical path length of 1 cm) to monitor MB concentration at wavelength of 665
nm (dominant peak for MB) by using UV–visible spectrophotometer.

3. Results and discussion

The synthesis of PEI-capped AgNPs comprises of 2 steps and proceeds via the reduction of silver ions from the
silver nitrate precursor. In the first step, Ag ions are complexed with PEI, as according to Reaction 1. In the second
step, silver ions are reduced to its metallic form (Ag0), by electrons donated from the BH4- anions in the reducing
agent, as indicated in Reaction 2.
• Reaction 1: PEI + AgNO3 ⇄ PEI-Ag+ + NO3-
• Reaction 2: PEI-Ag+ + NO3-+ NaBH4→PEI-Ag + ½H2 + ½B2H6+ NaNO3
Figure 1 shows a schematic diagram of the reaction PEI-Ag complex reduced by sodium borohydride to form PEI-
capped AgNPs. It is possible to achieve electrostatic-stabilized Ag NPs using only sodium borohydride as reductant
and stabilizer, however previous researchers have reported on the challenges to prolong the stability beyond a few
hours [51]. Apart from synthesis in ice-cold conditions, the ratio of reactants need to be of high precision, the stirring
speed and time have to be carefully controlled; all these factors contribute to variability in the AgNPs obtained. Due
to the challenges in using only borohydride as both reductant and stabilizer, stable molecules with large pendant
groups, such as PEI, have been used widely as electrostearic-stabilization agents to control the growth of nanomaterials
[52]. If complexation is performed before the addition of the reductant, the shelf-life of the Ag NPs can be prolonged
to months or years [20]. Furthermore, the addition of PEI to a borohydride reduction method allows the synthesis to
be conducted at room temperature. Previous researchers [51,53,54] have always recommended ice-cold conditions for
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 5

chemical reduction using sodium borohydride. As sodium borohydride is a strong reducing agent and causes an
exothermic reaction, the energy released from the reaction will encourage the growth of larger Ag NPs. Therefore,
prior complexation of AgNO3 with PEI is a useful step allowing the synthesis to be conducted at room temperature.
Lee et al.[20] had a different perspective on the synthesis of PEI-capped Ag NPs. They stated that PEI may be used
as a reducing agent and capping ligand. However, the process requires heating, which also generates larger Ag NPs,
therefore, NaBH4 was used to allow room temperature synthesis [20]. In addition, the presence of PEI as a capping
agent ensures the size control of Ag NPs. Homogeneous and monodispersed AgNPs appear yellow in solution, while
aggregated silver in solution appear greyish in colour [51].

Fig. 1. (a) Schematic of PEI complexed Ag undergoing chemical reduction to obtain PEI-capped AgNPs; (b) colloidal Ag-PEI sample with clear
yellow colour.

Fig. 2(a) shows the UV-visible absorption spectra of various AgNPs prepared with PEI of different molecular
weights, with the characteristic surface plasmon resonance (SPR) for AgNPs detected around 400 nm. AgNPs display
the SPR effect when the free conduction electrons on the surface of the particles oscillate at the same frequency as the
frequency of the lightwave which it absorbs [55]. Aggregation and particle size growth correspond to a red shifting
and broadening of the maximum absorption peak [56,57]. The sample prepared with PEI of the highest MW=750,000
displayed a narrow and intense maximum absorption peak at 405 nm, while the full width at half maximum (FWHM)
is 48 nm. Samples prepared with lower PEI molecular weights displayed increasingly broader absorption peaks, with
noticeable red shifting of the maxima. AgNPs prepared with PEI MW=10,000 had a maximum absorption peak of
432 nm and a much larger FWHM of 95 nm, while the maximal absorption peaks of Ag NPs prepared with PEI MW
=2,000 and PEI MW =800 red shifted even further to 454 nm and 485 nm, respectively. The position of the absorption
maximum is dependent on the size and shape of the particle, as well as the surface charge of the particle [58], with
particles stabilized with positively-charged polymers demonstrating the red shift [59].
These results are found to correlate well with the PEI molecular weight, in accordance to its effective capping
capability. PEI with larger molecules and longer chains provided better stabilization of Ag NPs compared to those
with shorter and smaller polymer fragments. In addition, the optimal amount of PEI (MW = 750,000) that was adopted
to produce stable AgNPs was also evaluated.
By varying the weight content of PEI (M w=750,000) between 2 – 53 wt%, the maximum absorption wavelength
(lambda max) of samples were found to range between 404 – 440 nm. Fig. 2(b) shows the relationship between the
maximum absorption wavelength and the PEI content. Ag NPs prepared with a low PEI content of 2.0 – 2.5 wt% PEI
had absorption maxima of 406 nm and 405 nm respectively, while the absorption maxima of Ag NPs that is produced
with 5.1 wt% of PEI was red-shifted to 440 nm. Nevertheless, further increasing the PEI content from 10 wt% to 53
wt% caused a blue-shifting of the maximum absorption to ~ 410 nm instead. Although PEI is primarily used as a
capping agent or stabilizer of nanoparticles, it possesses a reducing capability as well [20]. While the stabilizing effect
of PEI was weakened at very low concentrations, the availability of excess borohydride anions was able to provide a
temporary effective stabilizing effect, contributing to the blue shifting of the lambda maximum.
6 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

Fig. 2. (a) The UV-visible absorption spectra of Ag-PEI prepared with PEI of various molecular weights. (b) The maximum absorption
wavelength of various Ag-PEI prepared with PEI (Mw=750,000) of increasing content.

It was found that low amounts of PEI (~5 wt%) can cause nucleation at a faster pace and drive rapid aggregation
of Ag NPs. This led to the formation of larger particles, causing the red-shifting for this particular sample, as noted in
Figure 2(b), and similarly reported earlier [20]. Nevertheless, when higher amounts of PEI were employed, the capping
effect seems to begin to dominate, restricting the agglomeration of Ag NPs and to effectively stabilize the silver
colloidal solution. This is likely due to the presence of extra protective pendant amine groups with higher PEI loading,
preventing the coalescence and aggregation of Ag NPs into larger particles, leading to the blue-shift phenomenon
when PEI content was increased to 10 wt% and above. Further increase in the PEI wt% up to 53 wt% did not shift the
maximum absorption wavelength to below 400 nm, indicating that the further excess presence of PEI was not
necessary.
The samples of Ag-PEI prepared with various amounts of PEI MW=750,000 were observed under FESEM (Fig.
3) and compared with AgNPs prepared without complexation with PEI [Fig. 3(a)]. This particular sample was only
stabilized with excess borohydride anions. The sample prepared from 1 wt% PEI showed the presence of large cubic
particles measuring ~ 600-700 nm dispersed amongst smaller spherical particles [Fig. 3(b)]. Figs. 3(c) & 3(d) showed
the presence of several large cubic and triangular particles measuring up to 1000 nm and above, dispersed amongst
smaller spherical particles formed from the presence of 5 wt% PEI. In contrast, the samples prepared with 10 wt% of
PEI [Figs. 3(e)-(f)] and the samples prepared with 25 wt% PEI [Figs. 3(g)-(h)] displayed more spherical particles
exhibiting a smaller size distribution, compared to samples prepared with lower amounts of PEI. Particles measuring
~ 50 nm were observed in Fig. 3(h). EDX spot analysis was performed, confirming the presence of Ag in the sample.
C, N and O were also detected, which could be attributed to PEI, which is an organic polymer containing C and N,
while O is likely adsorbed onto the sample from the atmosphere. In addition, C is also likely to be detected from the
use of the carbon tape to support the sample for SEM and EDX analysis.
Ag-PEI sample prepared with PEI MW=750,000 was observed under transmission electron microscopy to elucidate
their morphology and structure. Fig. 4 (a) shows the as-synthesized Ag-PEI, with a spherical shape and a size range
between less than 1 – 6 nm. The average particle diameter was 2.57  1.08 nm, calculated from at least 70 points. At
high resolution analysis, the fringe spacing of approximately 0.204 nm corresponding to the (2 0 0) lattice plane for
FCC Ag crystal was able to be discerned in Fig. 4(b).
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 7

Fig. 3. FESEM images of AgNPs prepared with (a) only NaBH4, without complexation with PEI, (b) 1 wt% of PEI (c)-(d) 5 wt% of PEI, (e)-(f)
10 wt% of PEI, (g)-(h) 25 wt% of PEI, and (i) 2.5 wt% of PEI MW=750,000 and spot analysis with EDX.

Fig. 4. (a) HRTEM image of Ag-PEI with the AgNP size distribution; (b) HRTEM image of Ag-PEI reveals the lattice spacing corresponding to
the (2 0 0) lattice planes of face-centered cubic Ag.
8 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

Figs. 5(a) and 5(b) shows that the concentration of MB decreased by 87.9% and 90.2% when irradiated in the UV-
crosslinker as the effects of photodegradation initiated by AgNPs stabilized by 1 wt% and 2 wt% of PEI MW=750,000
respectively. AgNPs stabilized by 2 wt% of PEI caused photodegradation of MB in half the time (90 minutes)
compared to 180 minutes for the sample with 1 wt% of PEI. The colour of MB changed from a deep blue to a clear
liquid. Absorption occurring between the range of 600 – 700 nm wavelengths is attributed to the conjugated-π system
of MB, therefore, a decrease in the peak intensities signifies disruption of the MB chemical structure [50,60].

Fig. 5. Changes in MB concentration after irradiation at various timepoints with AgNPs stabilized by (a) 1 wt% PEI; (b) 2 wt% PEI. Dashed
line indicates 50% photodegradation of MB.

Biofouling in marine environments is a temporal process which involves the initial development of a microbial
slime or biofilm occurring within a few hours, culminating in the eventual colonization by larger organisms including
algae and invertebrates [61]. Although there exists differing views on whether marine fouling follows a ‘successional
model’ or a ‘dynamic model’, the disruption of the formation of the microbial biofilm is an important step in
antifouling strategy [62]. Fig. 5 shows the Ag-PEI materials with a concentration of 10 % v/v inhibit the attachment
of biofilm from H. pacifica, after an incubation period of 24 hours. Fig. 6(a) shows a decrease in the average optical
density of the crystal violet dye for for the Ag-PEI samples, in contrast to the control and blank samples. The surface-
associated dye attaches to biofilm mass, therefore, a higher optical density reading indicates a higher quantity of
bacterial attachment [40]. Fig. 6(b) revealed that Ag-PEI-4 prepared with 25 wt% of PEI had the highest average
inhibition of 63.11.3% (P < 0.01, Student’s t-test).
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 9

†
Fig. 6. (a) Crystal violet assay results for anti-biofilm activity of Ag-PEI materials at 10 %v/v. indicates the average OD measured at 570 nm;
(b) H. pacifica bacteria biofilm inhibition byAg-PEI materials at 10 %v/v. Bars represent mean ± s.d. of three independent experiments.
*indicates statistical significance compared to control (P < 0.01, Student’s t-test).

4. Conclusion

AgNPs capped with PEI were successfully synthesized through a rapid chemical reduction process at room
temperature. This was indicated by the formation of a clear yellow colloidal specimen, corroborated by UV-visible
spectrophotometry displaying the characteristic SPR phenomenon of AgNPs with the absorption peak corresponding
to the maximum absorption wavelength near 400 nm. Electron microscopy revealed that increasing the amount of PEI
produced smaller particles with a narrow size distribution. The samples exhibited promising photocatalytic properties
by photodegradation of methylene blue, a common pollutant of wastewater. The samples also exhibited promising
biofilm inhibition properties against the marine bacterium H. pacifica.

Acknowledgements

This research was supported by the Ministry of Science, Technology & Innovation (MOSTI) of Malaysia through
the Sciencefund program (04-02-12-SF0149), the National Nanotechnology Program Grant (NND/NA/(1)/TD11-
002), HIR-Chancellery (UM.C/625/1/HIR/079), (J-21002-73810) and HIR-MOHE
(UM.C/625/1/HIR/MOHE/SC/06). Yee is grateful to the Ministry of Higher Education (MOHE) Malaysia and the
University of Nottingham Malaysia Campus (UNMC) for scholarship and financial support. Mr. Andrew Yakin Sinit
and Ms Filzah Mohd. Fauzi from the UNMC Faculty of Engineering Analytical Unit are gratefully acknowledged for
their assistance in operating the XRD and SEM respectively.

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