Synthesis of ecofriendly copper oxide nanoparticles for fabrication over textile fabrics: Characterization of antibacterial activity and dye degradation potential

Synthesis of ecofriendly copper oxide nanoparticles for fabrication over textile fabrics: Characterization of antibacterial activity and dye degradation potential

Journal of Photochemistry & Photobiology, B: Biology 191 (2019) 143–149 Contents lists available at ScienceDirect Journal of Photochemistry & Photob...

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Journal of Photochemistry & Photobiology, B: Biology 191 (2019) 143–149

Contents lists available at ScienceDirect

Journal of Photochemistry & Photobiology, B: Biology journal homepage: www.elsevier.com/locate/jphotobiol

Synthesis of ecofriendly copper oxide nanoparticles for fabrication over textile fabrics: Characterization of antibacterial activity and dye degradation potential

T

Seerangaraj Vasantharaja,1, Selvam Sathiyavimalb,1, Mythili Saravanana, Palanisamy Senthilkumara, Kavitha Gnanasekaranc, Muthiah Shanmugaveld, ⁎ Elayaperumal Manikandane, Arivalagan Pugazhendhif, a

Department of Biotechnology, Hindusthan College of Arts and Science, Coimbatore 641 028, Tamil Nadu, India Department of Biotechnology, Kongunadu Arts and Science College, Coimbatore 641 029, Tamil Nadu, India Post Graduate & Research Dept. of Physics, A M Jain College, University of Madras, Meenambakkam, 600 114 Chennai, Tamil Nadu, India d Biological Material Laboratory, CSIR-Central Leather Research Institute (CLRI), Chennai 600 020, Tamil Nadu, India e Department of Physics, Thiruvalluvar University, Vellore, Tamil Nadu, India f Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam b c

ARTICLE INFO

ABSTRACT

Keywords: Ruellia tuberosa Copper oxide nanoparticles Green synthesis Antibacterial Photocatalytic activity

Growing concerns over the toxicity of metallic nanoparticles synthesized using physical and chemical techniques seems to be a major hurdle for researchers. Green synthesis of nanoparticles is one of the promising, ecofriendly and safer methods. Utilizing plant sources as reducing agents will replace the use of toxic chemicals for nanoparticle synthesis. Among the various nanoparticles, copper has been theoretically and practically proved for its antimicrobial properties. However, to reduce the risk of copper toxicity, Ruellia tuberosa (R. tuberosa) aqueous extract is used for the synthesis of CuONPs in the present study. Nonetheless, till date no work has been reported on the use of R. tuberosa aqueous extract for the synthesis of CuONPs. In the present study, aqueous extract of R. tuberosa has been used for the synthesis of CuONPs. The synthesis of CuONPs was confirmed by the absorption peak at 327 nm representing the nanorods with an average size of 83.23 nm. Further, the CuONPs revealed antimicrobial effects against clinical pathogens such as Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae. Embedding CuONPs on cotton fabrics showed bactericidal activity against the bacterial pathogens. In addition, the photocatalytic property of the CuONPs was divulged by their crystal violet (CV) dye degradation potential. Thus, the green synthesized CuONPs using R. tuberosa could provide a remedy against bacterial pathogens in hospital and industrial environments.

1. Introduction In the current scenario, nanotechnology is the growing area of science, which has been providing promising technologies useful for the development of human race. Nanotechnology led to the synthesis of metallic or non-metallic nanoparticles having wide range of applications in all disciplines of science [1–4]. Specifically, nanoparticles are being introduced in pharmaceutical industries, photocatalytic applications, biomedical applications, biosensors or biomarkers [2,5,6]. Both metallic and non-metallic nanoparticles are used in a variety of applications though metal based nanoparticles are the most stable and

efficient candidates [7]. Recently, copper oxide nanoparticles (CuONPs) have gained significant importance due to their distinctive properties. CuONPs possess a wide range of applications in batteries, catalysis, gas sensors, electrical, optical and solar energy exchange tools [8–10]. Copper oxide nanoparticles synthesized using plants are compatible, stable, biologically safe and cost effective method involving wide range of bioactive molecules [11–14]. Till date, biological syntheses of CuONPs have been performed using number of extracts [15–20] In recent trends, CuONPs have been used as antibacterial, antifungal, antibiofilm and coating agents in biomedical instruments [6,11,12]. Bactericidal effects of CuONPs can be attributed to the size and surface

Corresponding author at: Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam. E-mail address: [email protected] (A. Pugazhendhi). 1 The authors contributed equally as first author to this work. ⁎

https://doi.org/10.1016/j.jphotobiol.2018.12.026 Received 22 November 2018; Received in revised form 28 December 2018; Accepted 30 December 2018 Available online 31 December 2018 1011-1344/ © 2018 Elsevier B.V. All rights reserved.

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volume ratio of the nanoparticles with unusual crystal morphology, which allows the close interaction of CuONPs with the bacterial membrane and kills bacteria by the release of metal ions inside the cell [5,13]. Apart from these factors, CuONPs are cheap, easily miscible with polymers and relatively stable (physical and chemical properties) [14]. Microorganisms are known to damage products or devices causing discoloration, corrosion, fouling and mechanical strength weakening [15]. Fabrication of textile products with antimicrobial potential is also being practiced to avoid microbial damage [16]. Owing to nanoparticle toxicity, green synthesized nanoparticles are being used to develop microbe resistant textiles. Dyes and its derivatives are known to cause numerous health concerns such as skin irritation, kidney and liver problems, poisoning of central nervous system in living organisms [17]. Photodegradation of crystal violet and methyl violet B using CuONPs is a strategy, which prevents their bioaccumulation in the environment. Therefore, considering all these aspects, the present study has aimed at the synthesis of CuONPs using Ruellia tuberosa (Minnie root or Snapdragon root), potential plant rich with secondary metabolites and biological applications [29–31]. Furthermore, CuONPs synthesized using R. tuberosa were explored for their potential as antibacterial agents, coating materials over cotton fabrics and for photodegradation of crystal violet (CV) dye.

were analyzed by DLS (Malvern Instruments Ltd., Malvern, UK). Finally, the thermal behaviour of the surface capped CuONPs was determined using a Differential Scanning Calorimeter (DSC, Model Q200, TA Instruments). 2.4. Antimicrobial Efficiency of the Biosynthesized CuONPs The antibacterial efficacy of R. tuberosa mediated CuONPs was performed using disc diffusion method against various pathogenic bacterial strains; Gram-positive (Staphylococcus aureus) and Gram-negative (Klebsiella pneumoniae, Escherichia coli). The fresh overnight bacterial cultures were uniformly swabbed all over the surface of Muller Hinton agar (MHA) plates. Each plate contained different concentrations (25, 50 and 75 μg/mL) of CuONPs, the plates were kept in incubation at 37 °C for 24 h [18]. In this study, Streptomycin antibiotic was used as the control. After 24 h of incubation, the zones were measured in millimeters and analyzed for antibacterial activity. All the tests were performed in triplicates. 2.5. Antibacterial Activity of CuONPs Incorporated Cotton Fabrics Cotton fabrics of size of 2 × 2 cm were rinsed and autoclaved at 121 °C for 15 min. The fabrics were then treated with green synthesized CuONPs and were allowed to dry at 50 °C for 30 min. The NPs treated cotton fabrics were placed over the culture plates. Untreated cotton fabrics were placed as controls. After drying, the cotton fabrics were analyzed using FE-SEM (CARL ZEISS, EVO 18 model instrument).

2. Materials and Methods 2.1. Plant Sample Collection and Maintenance of Bacterial Strains Fresh sample of R. tuberosa plant leaves were picked from Central Leather Research Institute (CLRI), Chennai, India. The collected plants samples were taxonomically identified by Botanical Survey of India (BSI) (No. BSI/SRC/5/23/2016/TECH/282), Coimbatore. All the chemicals and glasswares were purchased from Sigma-Aldrich and Borosil, India, respectively and used as received. All the solutions were prepared with double distilled water. In this study, Gram-positive (Staphylococcus aureus) and Gram-negative (Klebsiella pneumoniae, Escherichia coli) bacterial strains were used, which were maintained in a nutrient broth at 30 °C.

2.6. Photocatalytic Activity The nanocatalytic activity of the CuONPs was determined using the degradation of toxic dye (crystal violet) [19]. 100 mL of CV and 10 mgL−1 of CuONPs were mixed for the test sample while the control contained only the dye. The suspension was stirred thoroughly using a magnetic stirrer for 30 min, then, kept in direct sunlight irradiation. At specific intervals, the samples were spun at 10,000 rpm for 10 min and the optical density was estimated using a UV spectrophotometer. 3. Results and Discussion

2.2. Bioextract Preparation and Green Synthesis of Copper Oxide Nanoparticles

3.1. UV–Visible Spectra of CuONPs

The freshly collected leaves of R. tuberosa were washed thoroughly with running tap water to remove dirt and dust. They were cut, separated and then air dried at room temperature. About 5 g of the leaf samples were chopped and allowed to boil in deionized water for few minutes. The solution was made to pass through a filter paper (Whatman) and the extract was maintained at 4 °C for further experiments. Copper sulphate (CuSO4) was used as the precursor for the preparation of CuSO4 solution using deionized water. Briefly, to this solution, 50 mL of R. tuberosa leaf extract was added and mixed under continuous stirring at 100 °C for 7–8 h. The colour of suspension was gradually changed from yellowish green to brownish black. The reaction was collected and cooled to room temperature. The mixture was centrifuged and the precipitate was washed with deionized water and dried at 90 °C for 7 h. After drying, the final product was collected and used for further experiments.

The aqueous copper sulphate solution was added to the leaf extract of R. tuberosa forming a pale yellow to brownish black colour mixture indicating the formation of CuONPs (Fig. 1a). This result was similar to other studies on the synthesis of CuONPs using biological [20] and chemical methods [11]. Further analysis was performed using UV–vis analysis, which showed a distinct peak at 327 nm as confirmed by the surface plasmon resonanace (Fig. 1b). Mie's theory states that the number of SPR bands depends upon the shape of the nanoparticles; usually, spherical nanoparticles have a single SPR band [21]. 3.2. Chemical Characterization of CuONPs The synthesized CuONPs were exposed to FT-IR transmittance analysis for the determination of the functional groups. Characteristic peaks were observed at 452 cm−1, 612 cm−1, 794 cm−1, 893 cm−1, 1120 cm−1, 1652 cm−1 and 3184 cm−1, respectively between the range of 500–4000 cm−1 (Fig. 1c). Bands at 3184 cm−1 represented OeH stretch due to carboxylic acids, those at 1652 cm−1 confirmed eC]Ce bending due to alkenes. Strong bands at 1120 cm−1 indicated the existence of CeO stretch due to alcohols and esters. The peak at 893.62 cm−1 denoted CeH bending due to aromatic groups. Prominent peaks at 452 cm−1, 612 cm−1 and 794 cm−1 manifested the presence of CueO vibrations in the synthesized CuONPs. Thus, FT-IR study clearly confirmed the availability of carboxylic acids, alkenes, esters, alcohols

2.3. Characterization of CuONPs Initial characterization of the synthesized CuONPs was performed using Shimadzu UV 2450, Japan. The identification of functional groups was done using a FT-IR spectrophotometer (JASCO FT-IR 4700). The size, morphology and elemental composition of CuONPs were examined using FE-SEM, EDAX (SIGMA, CARL ZEISS, Germany), and TEM (PHILIPS), respectively. Z-average size and potential of the CuONPs 144

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and aromatic compounds in the biosynthesized CuONPs. In biological synthesis, phytocompounds would usually aids in the conversion of Cu+ to CuONPs [22]. 3.3. Morphological Characterization of CuONPs The structural characterization of CuONPs was carried out using FESEM-EDX and TEM analyses. FESEM-EDX analysis revealed the presence of nanorods with some agglomeration due to the sticky nature of the plant extract (Fig. 2a). The aggregation of Cu might have been due to the thermodynamic stability of CuO preventing oxidation, without proper protection of the Cu ions. Previous reports on synthesis of CuONPs using plant extract showed the presence of spherical, cylindrical and cubical shapes. However, till date no report has suggested the synthesis of CuONPs nanorods using the aqueous extract of R. tuberosa [23–25]. The energy dispersive X-ray (EDX) and elemental mapping analyses confirmed the presence of copper oxide nanoparticles (Fig. 2b,c,d). The purity levels of the particles were examined, which indicated that R. tuberosa mediated CuONPs had 83.30% of Cu and 16.70% of oxygen, respectively, thus, confirming the formation of CuONPs [26]. The size and shape of CuONPs were further confirmed by TEM analysis and SAED patterns. The typical transmission electron micrographs of the phyto mediated CuONPs are shown in Fig. 3a–c. TEM analysis confirmed the presence of rod shaped CuONPs with size ranging from 20 to 100 nm. The nanorods were in a polydispersed form, which confirmed the presence of the phytochemical compounds from R. tuberosa (Fig. 3a–c). The agglomeration of the CuO nanorods was due to the presence of thin coating of R. tuberosa aqueous extract over the nanorods. This result could be supported by a recent work done by Nagar et al. [27], showing a thin coating of Azadirachta indica leaf extract around the CuO nanocubes. The crystalline nature of the synthesized CuONPs were confirmed by SAED (Fig. 3d). The average size distribution of CuONPs using DLS analysis was 82.32 nm (Fig. 4a) with a negative zeta potential of −11.9 mV, respectively (Fig. 4b). It suggested that the size and charge

Fig. 1. (a) Colouration of biosynthesized CuONPs, (b) SPR UV–visible spectrum, (c) FTIR spectrum of CuONPs synthesized using R. tuberosa leaf extract.

Fig. 2. (a) FESEM images of CuONPs, (b) EDX spectrum, (c,d) Elemental mapping analysis of CuONPs synthesized using R. tuberosa leaf extract. 145

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Fig. 3. (a-c) TEM image of CuONPs, (d) SAED pattern of CuONPs.

Fig. 4. (a) Particle size distribution of CuONPs, (b) Zeta potential value of CuONPs.

distribution of the synthesized nanoparticles promoted or enhanced the biological property of CuO nanorods [28]. In DLS analysis, the higher negative zeta potential denoted the strong repulsion force between the particles causing an amplification or enhancement of stability [21]. The DSC curve of CuONPs indicated the formation of an endothermic peak at 110.20 °C. This proved that the denaturation temperature of CuONPs was in good agreement (Fig. 5). Therefore, the overall results of the physical and chemical characterizations suggested the reduction of CuONPs by a thermally less stable compound from the aqueous extract of R. tuberosa, which was in good agreement with the previous report on the synthesis of gold nanoparticles using R. tuberosa [29]. 3.4. Antimicrobial Activity of CuONPs The antimicrobial activities of the CuONPs were evaluated against Gram-negative (E. coli, K. pneumonia) and Gram-positive bacteria (S. aureus) using agar disc diffusion method. The results clearly showed that CuONPs formed distinct zones around the bacterial strains as

Fig. 5. DSC curve of CuONPs. 146

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Fig. 6. Antibacterial activities of CuONPs against (a) E. coli, (b) K. pneumoniae, (c) S. aureus, and (d) Zone of inhibition in mm.

electrostatic attraction, the Cu+ ions are released causing the damage of cell walls and finally, death of the bacterial cells [31]. Hence, the biosynthesized CuONPs can be used as active antibacterial materials. In agreement with the present study, plant synthesized CuONPs have proved to exhibit potential antibacterial activity in previous reports [12]. Apart from these studies, a recent report on Sida acuta mediated CuO synthesis has displayed antibacterial effects of CuO against Gram negative and Gram positive bacteria [5]. Therefore, application of CuO in nanoforms would yield a new remedy for treating infections and diseases resulting from bacterial pathogens. 3.5. Antibacterial Activity of CuONPs Incorporated Cotton Fabrics The CuONPs treated fabrics showed higher antibacterial activities against S. aureus and K. pneumoniae and a lesser antibacterial activity against E. coli compared to the standard antibiotics (Fig.7a–c). Only few works has been reported so far about using plant mediated CuONPs for coating over cotton fabrics to promote antibacterial activity. Some of the works done with different metallic nanoparticles such as Ag, Zn, Au and Cu are illustrated in Table 1. Incorporation of CuONPs in cotton fabrics or textiles would guide the manufacturers to develop bacterial resistant fabrics. Moreover, incorporation of CuONPs could also prevent the growth of other organisms such as fungi, molds and other germs. Coating of CuONPs over textiles and fabrics would produce potential active surfaces for antimicrobial activity, UV blocking, water and oil repellence, self-cleaning properties, wrinkle resistance and flame retardation [27]. In the present study we have tested with 24 h assay against pathogenic

Fig. 7. Antibacterial activities of CuONPs treated fabrics against (a) E. coli, (b) K. pneumoniae and (c) S. aureus.

shown in Fig. 6 a-d. Among those, CuONPs exhibited maximum bactericidal activity against the Gram positive S. aureus (15.5 mm) followed by Gram negative strains of E. coli (11 mm) and K. pneumonia (13.5 mm), respectively at the highest concentration of 75 μg/mL. CuONPS are proposed to have high reactivities due to their large surface areas permitting them to interact with the bacterial cell walls [30]. After attachment of the CuONPs to the bacterial cell walls by 147

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Table 1 Various metallic nanoparticles fabricated over textile fabrics showing antimicrobial activities. S.no

Reducing agent/synthesis method

Nanoparticles

Biological application

Reference

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12

Water and soluble starch Fusarium oxysporum (Fungi) Ultrasound radiation Cassia roxburghii DC. aqueous extract Alternaria alternate (Fungi) Sonochemical/enzymatic process Acorus calamus rhizome Silver carbamate Date seed extract polycarboxylic acids Sida acuta R. tuberosa (Plant)

ZnO Ag CuO nanocrystals Ag Ag ZnO Au Ag ZnO Cu2O/CuO mixture CuO CuO

Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial Antibacterial

[37] [33] [38] [18] [39] [40] [41] [42] [27] [43] [5] Present study

activity activity activity activity activity activity activity activity activity activity activity activity

Fig. 8. FE-SEM analysis of (a) plain cotton fabric (b) cotton fabric impregnated with CuONPs.

3.6. FESEM Analysis of Phytosynthesized CuONPs Treated Cotton Fabrics The CuONPs coated, and uncoated cotton fabrics were morphologically analyzed using FESEM. The FESEM results revealed the clear and uniform distribution of CuONPs in and over the thin fabrics of cotton (Fig. 8b). Uncoated cotton fabrics were used as control showing the absence of CuONPs (Fig. 8a). Likewise, Hebeisha et al. and Duran et al. also performed SEM analysis to verify the existence of AgNPs on cotton fabrics [33,34]. Very recently, Sathiyavimal et al. characterized CuONPs incorporated cotton fabrics by SEM analysis [5]. Hence, the present study also performed FESEM analysis of cotton fabrics after incorporating them with CuONPs. Based on the FESEM analysis results, the cotton fabrics were subjected to determination of antibacterial activities. 3.7. Photocatalytic Activity The photocatalytic activity of CuONPs was analyzed using crystal violet as a model system for dye degradation. The efficiency of CuONPs for the degradation of CV at 585–590 nm and at different time intervals was assessed. Initially, after 60 min of incubation, a strong indication of Cu+ ion generation was detected by the change of light blue colour in the solution but after 120 min of incubation, a complete disappearance of colour in the reaction mixture was observed. In the presence of CuONPs, the primary absorption peak at 586 nm decreased slowly with the increasing sunlight exposure time. This indicated the photocatalytic degradation of CV dye in the presence of CuONPs (Fig. 9). While in the absence of CuONPs (control), the solution did not show any progress [35]. Previous reports on photocatalytic research revealed that the photocatalytic activity of the metallic nanoparticles would depend on the crystallographic structure, morphology, and size of the particles [36]. Roy et al. used CuONPS synthesized using Impatiens balsamina leaf

Fig. 9. The photocatalytic efficiency of CuONPs on the degradation of Crystal violet dye as a model system. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

bacteria. The particle seems consistent against the bacteria for 24 h till now. In our report we have embedded the CuONPs in the cotton fabrics, likewise Nam et al. [32] has reported that silver cotton nanocomposite fiber retained 93% of antimicrobial activity even after 50 home laundering cycles. This was due to the smaller size of the nanoparticles, increasing their ability to trap inside the cotton fabrics. Therefore considering the smaller size of CuONPs synthesized in our study, the consistency of CuONPs may be for a longer period of time course. 148

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extract for the photodegradation of methylene blue and congo red in 72 h but the present study showed complete degradation of CV at the end of just 2 h [23]. Therefore, this study clearly proved the efficient photodegrading potential of CuONPs synthesized using R. tuberosa under direct sunlight.

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4. Conclusion The implementation of phytonanotechnology for the synthesis of nanoparticles has proved as an ecofriendly and a non-toxic approach. The bioactive or phytochemical components of the plant extract are potential capping and reducing agents leading to the reduction of NP toxicity. The present report has used R. tuberosa for the first time to synthesize CuONPs. Characterization of CuONPs revealed the nanorod structure and coating of the stabilizing agent over the nanoparticles. CuONPs synthesized using R. tuberosa showed multiple activities as antibacterial agents, coating agents over cotton fabrics and photocatalytic degradation of CV dye under direct sunlight. Therefore, the versatile applicability of CuONPs could pave way for the future applications of R. tuberosa mediated CuONPs in textile industries for the prevention of microbial damage to fabrics and bioremediation of dye from industries. References [1] P.D. Shankar, S. Shobana, I. Karuppusamy, A. Pugazhendhi, V.S. Ramkumar, S. Arvindnarayan, G. Kumar, A review on the biosynthesis of metallic nanoparticles (gold and silver) using bio-components of microalgae: formation mechanism and applications, Enzym. Microb. Technol. 95 (2016) 28–44. [2] T. Pradeep, Noble metal nanoparticles for water purification: a critical review, Thin Solid Films 517 (2009) 6441–6478. [3] J.B. Fathima, A. Pugazhendhi, M. Oves, R. Venis, Synthesis of eco-friendly copper nanoparticles for augmentation of catalytic degradation of organic dyes, J. Mol. Liq. 260 (2018) 1–8. [4] R.B. Shafreen, S. Seema, A.P. Ahamed, N. Thajuddin, S.A. Alharbi, Inhibitory effect of biosynthesized silver nanoparticles from extract of Nitzschia palea against Curlimediated biofilm of Escherichia coli, Appl. Biochem. Biotechnol. 183 (2017) 1351–1361. [5] S. Sathiyavimal, S. Vasantharaj, D. Bharathi, S. Mythili, E. Manikandan, S.S. Kumar, A. Pugazhendhi, Biogenesis of copper oxide nanoparticles (CuONPs) using Sida acuta and their incorporation over cotton fabrics to prevent the pathogenicity of Gram negative and Gram positive bacteria, J. Photochem. Photobiol. B Biol. 188 (2018) 126–134. [6] N. Chari, L. Felix, M. Davoodbasha, A.S. Ali, T. Nooruddin, In vitro and in vivo antibiofilm effect of copper nanoparticles against aquaculture pathogens, Biocatal. Agric. Biotechnol. 10 (2017) 336–341. [7] A.S.H. Hameed, C. Karthikeyan, A.P. Ahamed, N. Thajuddin, N.S. Alharbi, S.A. Alharbi, G. Ravi, In vitro antibacterial activity of ZnO and Nd doped ZnO nanoparticles against ESBL producing Escherichia coli and Klebsiella pneumoniae, Sci. Rep. 6 (2016) 24312. [8] A.S. Mansano, J.P. Souza, J. Cancino-Bernardi, F.P. Venturini, V.S. Marangoni, V. Zucolotto, Toxicity of copper oxide nanoparticles to Neotropical species Ceriodaphnia silvestrii and Hyphessobrycon eques, Environ. Pollut. 243 (2018) 723–733. [9] A.A. Keller, A.S. Adeleye, J.R. Conway, K.L. Garner, L. Zhao, G.N. Cherr, J. Hong, J.L. Gardea-Torresdey, H.A. Godwin, S. Hanna, Comparative environmental fate and toxicity of copper nanomaterials, NanoImpact 7 (2017) 28–40. [10] K. Saravanakumar, S. Shanmugam, N.B. Varukattu, D. MubarakAli, K. Kathiresan, M.-H. Wang, Biosynthesis and characterization of copper oxide nanoparticles from indigenous fungi and its effect of photothermolysis on human lung carcinoma, J. Photochem. Photobiol. B Biol. 190 (2018) 103–109. [11] F. LewisOscar, D. MubarakAli, C. Nithya, R. Priyanka, V. Gopinath, N.S. Alharbi, N. Thajuddin, One pot synthesis and anti-biofilm potential of copper nanoparticles (CuNPs) against clinical strains of Pseudomonas aeruginosa, Biofouling 31 (2015) 379–391. [12] M.I. Nabila, K. Kannabiran, Biosynthesis, characterization and antibacterial activity of copper oxide nanoparticles (CuO NPs) from actinomycetes, Biocatal. Agric. Biotechnol. 15 (2018) 56–62. [13] D. Laha, A. Pramanik, A. Laskar, M. Jana, P. Pramanik, P. Karmakar, Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage, Mater. Res. Bull. 59 (2014) 185–191. [14] G. Ren, D. Hu, E.W. Cheng, M.A. Vargas-Reus, P. Reip, R.P. Allaker, Characterisation of copper oxide nanoparticles for antimicrobial applications, Int. J. Antimicrob. Agents 33 (2009) 587–590. [15] A.G. Nurioglu, A.C.C. Esteves, Non-toxic, non-biocide-release antifouling coatings based on molecular structure design for marine applications, J. Mater. Chem. B 3 (2015) 6547–6570.

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