Article Cite This: ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX
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Carbon-Dot Initiated Synthesis of Polypyrrole and Polypyrrole@CuO Micro/Nanoparticles with Enhanced Antibacterial Activity Moorthy Maruthapandi,† Anjani P. Nagvenkar,† Ilana Perelshtein,† and Aharon Gedanken*,† †
Bar-Ilan Institute for Nanotechnology and Advanced Materials, Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
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S Supporting Information *
ABSTRACT: The carbon dot initiated polypyrrole (PPY) and CuO composite were synthesized into PPY@CuO using a simple one-step sonochemical approach. The synthesized PPY and the PPY@CuO were characterized using Fouriertransform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, 13C-solid-state nuclear magnetic resonance (NMR) spectroscopy, UV−visible spectroscopy, and scanning electron microscopy. A strong interaction was demonstrated between the PPY chains and CuO. This interaction led to changes in the backbone chain of the PPY@CuO composite when compared to the carbon dot initiated PPY. The antibacterial activity against Escherichia coli and Staphylococcus aureus of the carbon dot initiated synthesis of PPY and the sonochemically prepared PPY@CuO composite materials was revealed. The results indicate the biocidal efficacy of PPY@CuO on both Gram-positive and Gram-negative bacteria. The PPY@CuO composite exhibited an enhanced antibacterial performance in comparison with the carbon dot initiated PPY and CuO. This is a first report on the sonochemical synthesis of a polymer composite composed of PPY and CuO, demonstrating the efficacy of its antibacterial action at a concentration of 1 mg/mL of the composite involving 0.234 mg/mL of CuO. KEYWORDS: carbon dots, polypyrrole, CuO, polypyrrole@CuO, antibacterial activity, mechanism study
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Zn-doped CuO as an antibacterial agent.13,14 The current progress in the research on metal doped nanoparticles has resulted in the use of CuO for antibacterial, antioxidant, and sensing applications. To date, there is no report on the use of composites of CuO with polymers for biological applications. However, there are many reports on composites of conducting polymers that have been widely used for their antibacterial properties with metals and metal-oxide nanoparticles as the composite material, such as polypyrrole/zinc oxide/chitosan,15 polypyrrole Ag nanocomposite,16 PPY-nanotubes: Ag-NPs,17 polypyrrole/dextrin,18 polypyrrole/chitosan,19 polyaniline/ poly(vinyl alcohol)/Ag,20 TOCN/PVA−PPY film,21 PANI@ ZnO,22 polyaniline/Pt,Pd nanocomposite,23 polyaniline/Ag− Pt,24 PANI−Ag−Au nanocomposite, and gold polyanilinebased material.25−27 However, these polymer metal or metaloxide composites always exhibit drawbacks such as a complex synthesis method, toxicity, and the high cost of the precious metals (Au, Pt, Ag, and Pd) that are used to produce them. To avoid the problematic synthesis and economic concern in regard to the production of polymer composites, the sonochemical method was applied here to produce highly effective PPY@CuO.13,14
INTRODUCTION Conjugated polymers such as polyaniline (PANI), polypyrrole (PPY), and polythiophene (PT) are recognized as conducting polymers due to their electrochemical responsive properties rather than their structure. Such polymers are emerging as potentially useful materials in possessing magnetic, optical, and electronic properties associated with those of metals or semiconductors while retaining their polymeric structure and properties such as their ease of processing, flexibility, low toxicity, and adjustable electrical conductivity.1−4 However, general applications of PPY have been mostly limited to date owing to their poor mechanical properties. To improve these properties along with their physical and structural properties, various attempts have been made to prepare composite materials or complex forms containing PPY.5,6 The nanostructured conducting polymers can be synthesized both electrochemically and by means of the chemical oxidative method.7−10 Recently, our group has developed for the first time a new polymerization technique by which to synthesize these polymers. The conducting polymers, PANI and PPY, were synthesized using carbon dots (C-dots) as an initiator in the presence of UV-irradiation without the involvement of any other initiators.11,12 Fine metal-oxide nanoparticles of Zndoped CuO are of great interest due to their surprising sizedependent optical, biological, and electrical properties. Our research group has pioneered the synthesis and applications of © XXXX American Chemical Society
Received: March 1, 2019 Accepted: April 17, 2019 Published: April 17, 2019 A
DOI: 10.1021/acsapm.9b00194 ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX
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ACS Applied Polymer Materials
Synthesis of Polypyrrole. Pyrrole (1.0 g) was dissolved in 30 mL of 0.5 M nitric acid in a 100 mL beaker at room temperature. Three milliliters of aqueous solution of C-dots was added. The entire reaction mixture was activated by illumination with UV light for two days, resulting in a blackish-brown solid which was filtered, washed with distilled water, and dried at room temperature11 Synthesis of Polypyrrole@CuO. PPY (0.05 g) was added to 90 mL of ethanol in a 100 mL beaker. To this solution, the molar ratio of Cu acetate salt was dissolved in 10 mL of deionized water and added to this solution to reach a total concentration of 0.01 M in 100 mL of total solution (90 mL EtOH). The solution was sonicated until the temperature reached 60 °C. Ammonia was added until matching a pH of 8−9 (∼0.2 mL). The blue-tinted solution turned blackish-brown. A 30 min sonication was then carried out with the sonicated cell in an ice bath.13,14 Antibacterial Tests. To determine the composite’s antibacterial activity, both bacteria strains (E. coli and S. aureus) were incubated overnight in aerobic conditions at 37 °C in Luria−Bertani (LB) broth. Bacterial concentration was measured using optical density (OD595), and a final concentration of 107 bacteria was attained. For the antibacterial tests, 500 μL of the sample was added to the 500 μL of the bacterial suspension. The mixture was incubated at 37 °C with shaking at 200 rpm. One-hundred milliliter aliquots were removed after 3, 5, and 8 h, diluted 10-fold in 20% LB medium, and plated on the nutrient agar plates. The plates were dried and incubated for 16 h at 37 °C. The bacterial colonies at the appropriate dilutions were counted, and the number of viable bacteria was calculated using the colony-forming unit (CFU) method. Analytical Techniques. The synthesized PPY and PPY@CuO were analyzed by employing various techniques. Fourier-transform infrared (FTIR) spectra were measured using a Transon 27 spectrometer (Bruker Inc., Germany). The nature of the crystalline properties was assessed using an X-ray diffraction (XRD) technique measured by a Bruker Inc. (Germany) AXS D8 Advance diffractometer. Scanning electron microscopy (SEM) measurements for determining the morphology of the PPY and PPY@CuO were carried out using an FEI Magellan 400 L microscope. The sample for the SEM measurements was prepared by placing a small amount of dried powder of the synthesized material on a carbon tape attached to a copper strip, and the material was coated with gold to improve the conductivity. 13C Solid-state nuclear magnetic resonance (NMR) spectra were acquired using a Bruker 5000 Ultra Shield spectrometer (Bruker, Billerica, MA, United States). Thermogravimetric analysis (TGA) was performed using a PerkinElmer instrument (Norwalk,
In our previous work, the PPY was synthesized by the C-dot initiated polymerization method. The main goal of the present study was to prepare and evaluate the antibacterial behavior of the C-dot- initiated PPY micro/nanocomposite material incorporating CuO, which was achieved via the simple onestep sonochemical method. The effect of PPY or of CuO alone on the antibacterial activity of the micro/nanocomposite was also examined, and the composite was evaluated for its antibacterial behavior against the Escherichia coli and Staphylococcus aureus bacteria. Moreover, at a PPY:CuO ratio of 9:1 wt.; a distinct and very high synergetic effect of the polymer composite was detected, especially considering the low content of CuO. In addition, the mechanism behind the PPY@CuO micro/nanocomposite antibacterial effect was investigated by examining the reactive oxygen species (ROS) generation. A comparison of polypyrrole composites made with various materials, as reported in the literature, is provided in a Table1. Table 1. Comparison of Polypyrrole Composites Made with Various Materials PPY composite polypyrrole/ZnO/ chitosan PPY−Ag−NPs polypyrrole/dextrin polypyrrole/chitosan TOCN/PVA−PPY film this study
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concentration
time (h)
1−5 mg
24
19 wt % of PPy 1−5 mg
24
100 mg 100 mg
24 62
1 mg
8
24
solvent DPPH in EtOH AgNO3 in water DPPH in EtOH water
references 15 17 18 19 21
water
EXPERIMENTAL SECTION
Chemicals. Polyethylene glycol-400 (99.998%), copper acetate, pyrrole, and nitric acid were purchased from Sigma-Aldrich Israel. Preparation of C-Dots. Thirty milliliters of polyethylene glycol (PEG-400) was transferred into a 50 mL beaker which was placed in a hot water bath at 70 °C. The tip of an ultrasonic transducer was dipped into the PEG-400 and sonicated for 3 h at 65% amplitude.11
Figure 1. (a) TGA spectra of PPY and PPY@CuO; (b) XRD spectra for PPY, CuO, and PPY@CuO; and (c) the possible chemical structure of Cdot initiated PPY. B
DOI: 10.1021/acsapm.9b00194 ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX
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Figure 2. (a) UV−visible spectra for PPY and PPY@CuO and (b) FTIR spectra for PPY and PPY@CuO.
an FTIR spectrum with broad peaks around 1042−1704 cm−1; the band at 3390 cm−1 is assigned to N−H stretching, and the peaks at 1596 and 1518 cm−1 are attributed to CC stretching. The peaks at 2981 and 2905 cm−1 correspond to the C−H aromatic stretching; the peak at 1334 cm−1 is assigned to C−N stretching, and the peaks around 1105 and 1260 cm−1 are due to the C−H in-plane vibrations.11,28,29 The FTIR spectrum of the polymer composite reveals the sharp narrow peaks and displays the slighter shifts of the composite compared to those of the PPY. These slighter shifts result from the formation of the polymer composite of CuO with PPY. Morphology Studies. Morphology studies of the PPY polymer and PPY@CuO composite materials were conducted using SEM. Figure 3 (a,b) presents the SEM images of the PPY and the PPY@CuO composite. The SEM image of the PPY exhibits agglomerated spherical particles with a range of diameters between 1 and 4 μm. SEM images of the PPY@CuO micro/nanocomposite surface are depicted in Figure 3 (b). These images indicate that the PPY@CuO micro/nanocomposite particle shows
CT, United States) at a temperature range of 25−900 °C at a heating rate of 10 °C/min.
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RESULTS AND DISCUSSION The thermal stability of the PPY and PPY@CuO materials was examined by thermogravimetric analysis. Figure 1 (a) compares the TGA curve of the PPY with that of the PPY@ CuO: a better thermal stability of the PPY@CuO composite was revealed and compared to the PPY polymer. The TGA curves reveal the three stages of weight loss for the PPY and PPY@CuO. (1) Minor weight loss (5%) at 65−79 °C is due to the evaporation of moisture in both cases. (2) Major weight loss (27%) between 160 and 383 °C is due to the removal of oligomers from the PPY. For PPY@CuO, the composite material remained thermally stable until 480 °C and demonstrated a smaller weight loss (9%). The final stage of both materials was the decomposition at 480−600 °C with weight loss (37%). The 40% remaining weight was that of the composite residue of the CuO. The possible chemical structure of C-dot initiated PPY is depicted in Figure 1 (c). In addition, we performed an XRD analysis to further confirm the production of the PPY@CuO composite. The XRD diffraction patterns of the PPY and PPY@CuO are presented in Figure 1 (b). Each contains a broad diffraction peak around 2θ = 12−36.6° due to the periodicity in the polymer structure parallel to the polymer chains. The broad peak of PPY@CuO shows an extreme shift compared to the PPY, which could be due to the CuO7 resulting from the formation of a stable composite with polymer chains. The PPY@CuO also contains many additional minor sharp peaks around 2θ = 35.1, 29.6, 57.6, and 65.9°, which are due to the CuO, confirming its nature as a composite material. These extremely broad diffraction peaks indicate that the PPY and its associated PPY@CuO composite material are partially crystalline in nature. The materials were well-dispersed in double-distilled water to measure the UV−visible spectra. Further confirmation of the successful polymer composite preparation was attained through the UV−visible spectral analysis. Figure 2 (a) displays the UV−visible spectra of the PPY and PPY@CuO. The absorption peaks around 250−365 nm are ascribed to the π−π* transitions of the aromatic rings. Two changes can be observed in the PPY@CuO: the intensity of the peak gradually reduces, and the peak shifts around 271−310 nm, which are indicative of the well-defined features of the composite formation with the PPY. The FTIR spectra of the PPY and PPY@CuO materials are shown in Figure 2 (b). The PPY has
Figure 3. (a) SEM images of PPY; (b) SEM of PPY@CuO; and (c) DLS analysis of PPY, PPY@CuO, and CuO. C
DOI: 10.1021/acsapm.9b00194 ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX
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ACS Applied Polymer Materials broad size distribution. The CuO nanoparticles ranging from 50 to 200 nm appeared in aggregates on the surface of the PPY spheres, imparting a coarse surface. Particle Size Measurement by Dynamic Light Scattering (DLS). The particle sizes of the PPY, PPY@CuO, and CuO materials were analyzed by DLS measurements performed in aqueous dispersion medium and used to determine the average particle size and the polydispersity indices. The particle sizes are depicted in Figure 3 (c). The pristine PPY and PPY@CuO particle size varies from 3 to 6 μm and 2 to 4 μm, respectively. In the case of CuO, a wide size distribution is observed, indicated by the three peaks resembling three different populations of particle sizes. Twenty percent of the particles have size diameters between 200 and 700 nm; 30% of the particles are micrometer-sized ∼5 μm, and 50% are micro/nano-sized from 0.8 to 2 μm. The polydispersity indices of all three materials are below 1.0, demonstrating the particle nature of the polymers and strongly suggesting a good processability of polymer composite dispersions. Solid-State NMR Analysis. The polymeric composite materials were also analyzed using solid-state 13C NMR spectroscopy with the resultant spectra displayed in Figure 4.
Figure 5. (a and b) E. coli and S. aureus effects on PPY@CuO and its control.
both E. coli and S. aureus presented complete mortality after 8 h of exposure to the PPY@CuO composite. This is a clear indication of the synergetic effect observed for this composite, in contrast to such enhanced biocidal property of PPY alone or that of CuO alone. PPY has already been reported as an active biocidal agent.16,18,19,27,30−32 Because a known amount of PPY was used to synthesize the composite, the concentration of CuO in the composite was determined by ICP measurements, and thus, the control solution was prepared with the calculated quantity of CuO present in the composite. The antibacterial tests were performed at a concentration of 1 mg/mL of the composite which included 0.234 mg/mL of CuO. This is a substantially lower amount of CuO compared to that appearing in the literature reports, where complete mortality required a minimum of 18 h at a concentration of CuO.13,14 The current work thus demonstrates the significant ability of PPY to reduce the cytotoxic effect of metal-oxide nanoparticles for their application as antibacterial agents by providing a feasible route to synthesize the nanocomposites with biocompatible polymers exhibiting minimal cytotoxicity. Mechanism Behind the Antibacterial Effect of the PPY@CuO Micro/Nanocomposite. The suggested mechanism behind the observed biocidal activity of the samples was determined using the EPR (Electron Paramagnetic Resonance) technique, which measures the ROS production using DMPO as a spin trap.33 DMPO captures hydroxyl (OH·) radicals and superoxide (O2−·) and forms DMPO−OH as a final adduct, which shows a distinct quartet signal with the typical 1:3:3:1 signal intensity ratio. Figure 6 clearly shows a 3.5-fold and 2-fold rise in the ROS production of PPY@CuO when compared to PPY and CuO
Figure 4. Solid state 13C NMR spectra of PPY and PPY@CuO.
The solid-state NMR spectra of PPY and PPY@CuO show both a broad and a sharp peak. The peak around 125 ppm is attributed to the protonated carbon (C-1, C-10, C-11, and C14) in the polymer chain. The shoulder peaks around 108 and 115 ppm correspond to the protonated carbons of C-2, C-3, C6, and C-7 in the aromatic rings, and the peak around 122 ppm corresponds to the nonprotonated carbons of C-12 and C-13. The sharp peaks around 59 and 71 ppm originate from the protonated C-9 and nonprotonated C-16 carbon of the quinoid part of the polypyrrole structure. The solid-state 13C NMR spectra of PPY and PPY@CuO are almost similar in shape with the spectrum of PPY@CuO slightly shifted upfield, and the intensity of the shoulder peaks is reduced. This is evident in the peaks around 63, 108, and 115 ppm, compared to those of the PPY. These variations confirm the formation of a metal-oxide composite with PPY. Antibacterial Activity. The gram-negative (E. coli) and gram-positive (S. aureus) bacteria were used as test microorganisms for the evaluation of antibacterial activity of the composite material. Bacterial growth inhibition was assessed using the CFU per mL method. As can be seen in Figure 5,
Figure 6. EPR measurement for PPY, CuO, and PPY@CuO. D
DOI: 10.1021/acsapm.9b00194 ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX
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alone. The comparison is based on equal concentrations of CuO and PPY present in the PPY@CuO nanocomposite. The results indicate that ROS generation by the nanocomposite constitutes the crucial mechanism enabling efficient destruction of the bacteria. This synergistic effect between the PPY and CuO can be attributed to the fact that because PPY is a conductive polymer, its free electrons can combine with the O2 in the suspension to induce additional production of ROS.34 In addition, the presence of NH group and aromatic ring in polypyrrole increases its cationic behavior, inducing electrostatic/ionic interactions with bacteria. This interaction at the microorganism wall can lead to the leakage of intracellular electrolytes, causing cell death. Thus, the positive charge was supported, prominent to an enhanced antibacterial activity.32
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CONCLUSION In summary, the present work reports on a new polymer composite material: PPY@CuO. A simple one-step carbon dot initiated PPY was used as an antibacterial mediator, revealing its unique advantages over the conservative metal-oxide composites. The simple one-step sonochemical process of combining the polymer with metal-oxide to produce antibacterial properties was replaced by direct incorporation of metal-oxide nanoparticles and the action of PPY macroparticles to eradicate the bacteria. The novelty of this work lies in the development of a new polymer composite displaying highly effective antibacterial activity at a minimum concentration of CuO and achieving complete mortality within 8 h. This approach avoided the necessity for a large quantity of CuO replaced instead by the C-dots initiated polypyrrole.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsapm.9b00194. EDS result of PPY@CuO and the SEM images of bacteria treated by PPY@CuO and PPY (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail: gedanken@mail.biu.ac.il; Fax: +972-3-7384053; Tel: +972-3-5318315. ORCID
Aharon Gedanken: 0000-0002-1243-2957 Notes
The authors declare no competing financial interest.
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DOI: 10.1021/acsapm.9b00194 ACS Appl. Polym. Mater. XXXX, XXX, XXX−XXX