Nanoparticles
The nanoparticle synthesis using bacterial extracts is a complex and time-consuming technique of green synthesis. It is vital to ensure vigilant monitoring of the culture media throughout the process to avoid contamination. Otherwise, synthesized NPs could be less optimized and ineffective [ 2 ]. A study reported that the synthesis of ZnO-NPs can be carried out using Rhodococcus pyridinivorans and zinc sulfate as the substrate. The synthesized NPs were spherically shaped with a 100–130 nm size range confirmed through FE-SEM and XRD analysis [ 181 ]. The synthesis of nanoflowers (40 nm width and 400 nm height) with potent photocatalytic potency was also performed with B. licheniformis using the green synthesis technique [ 182 ]. The excellent antioxidant activity of NPs synthesized using Pseudomonas aeruginosa was also revealed, indicating that enhanced NP stability was attained due to the rhamnolipid of bacteria used. Thus, it is significant to consider that bacteria can be used as a better capping agent with outstanding stability and potency [ 183 ]. Green synthesis using a bacterial strain is well illustrated in Table 2 .
Summary of the bacteria-mediated synthesis of zinc oxide nanoparticles.
Strain of Bacteria | Family | Size of Nanoparticles Synthesized (nm) | Morphology of Nanoparticles | References |
---|---|---|---|---|
| Nocardiaceae | FE-SEM: 100–120 XRD: 120–130 | Hexagonal phase and roughly spherical | [ ] |
| Pseudomonadaceae | TEM: 35–80 XRD: 27, DLS: 81 | Spherical | [ ] |
NMJ15 | Pseudomonadaceae | TEM: 6–21 XRD: 21 | Spherical | [ ] |
| Pseudomonadaceae | AFM: 57.72 XRD: 42–64 | Oval and spherical | [ ] |
Bacillaceae | TEM: 5–15 XRD: 11 | Hexagonal | [ ] | |
Bacillaceae | TEM: 200 (nanopetal 40 nm width and 400 nm length) | Nanoflower | [ ] | |
( HM475278) | Enterobacteriaceae | SEM: 170–250 (at 30 min), 300–600 (at 60 min), 185–365 (at 90 min) | Spherical and nanoflower | [ ] |
Microcoleaceae | TEM: 30–55 XRD: ≈45 | Spherical | [ ] | |
sp. EAZ03 | Desertifilaceae | TEM: 88 XRD: 60–80 | Rod | [ ] |
sp. 2C8 and sp. VLA (cell-free extract) | Alteromonadaceae Vibrionaceae | 2C8-TEM: 10.23 ± 2.48 VLA-TEM: 20.26 ± 4.44 | Hexagonal wurtzite | [ ] |
Due to the efficient and large-scale productivity, lower cost, and convenient processing, numerous fungal strains are being used for the green synthesis of ZnO-NPs over bacteria [ 2 ]. Fungi are more tolerable and have better metal bioaccumulative properties than bacterial strains, making them a stronger candidate for nanoparticle synthesis [ 191 ]. A study found that fungal strains such as Candida albicans could be employed to synthesize quasispherical-shaped ZnO-NPs [ 192 ]. Similarly, the mycelia of Aspergillus fumigatus were used to make spherical aggregate-shaped NPs, which agglomerate into a larger size after a few days, indicating the stability and potent capping activity of fungus as a substrate [ 193 ]. Some examples of fungal-mediated synthesis are included in Table 3 .
Summary of the fungal-mediated synthesis of zinc oxide nanoparticles.
Fungal Strain | Family | Size of Nanoparticles Synthesized (nm) | Morphology | References |
---|---|---|---|---|
Trichocomaceae | SEM: 61 ± 0.65 XRD: 41 | Spherical Crystalline wurtzite | [ ] | |
Saccharomycetaceae | XRD: 25, SEM: 15–25, TEM: ~20 | Hexagonal wurtzite, quasispherical | [ ] | |
Trichocomaceae | DLS: 1.2–6.8 | Oblate spherical and hexagonal | [ ] | |
Trichocomaceae | SEM: 50–120 | Spherical | [ ] | |
Xylariaceae | TEM: 30–50, average: 34 SEM: 40–55 DLS: 30–50 XRD: 35–45 | Rod and hexagonal | [ ] |
Algae are photosynthetic organisms that are made up of single or multiple cells and lack essential components such as roots, stems, and leaves. Algae are classified into two types, macroalgae, and microalgae, as well as three groups, Rhodophyta (red pigmented), Phaeophyta (brown pigmented), and Chlorophyta (green pigmented). Algae have a limited significance in the synthesis of ZnO-NPs and are better suited for the production of other metal nanoparticles such as silver and gold nanoparticles. Microalgae are commonly employed for the green synthesis of NPs because they have a greater potential to minimize metal toxicity through the biodegradation process [ 198 ]. ZnO-NPs are typically synthesized using algae from the Sargassaceae family. Sargassum muticum was employed to make hexagonal wurtzite-shaped ZnO-NPs [ 199 ]. Similarly, nanoparticles of spherical, radial, triangular, hexagonal, and rod shapes were synthesized from S. myriocystum [ 200 ]. Furthermore, Chlamydomonas reinhardtii , a species of the Chlamydomonaceae family, was used to synthesize various-shaped NPs, such as nanorods, nanoflowers, and porous nanosheets [ 201 ]. Table 4 summarizes the ZnO-NPs synthesized by some of the algae.
Summary of the algal-mediated synthesis of zinc oxide nanoparticles.
Algae Strain | Family | Size of As-Synthesized Nanoparticles (nm) | Morphology of the Nanoparticles | Surface Functional Groups | References |
---|---|---|---|---|---|
| Sargassaceae | FE-SEM: 30–57 XRD: 42 | Hexagonal wurtzite | Sulfate group asymmetric with stretching band, asymmetric C–O band coupled with C-O-SO and -OH group, sulfated polysaccharides | [ ] |
Sargassaceae | SEM: 50 DLS: 25–50 XRD: 15–50 | Spherical | 3432 and 1609 cm presence of O–H stretching, 500 cm below suggests a Zn–O stretching vibration | [ ] | |
| Chlamydomonaceae | HR-SEM: 55–80 XRD: 21 | Rod | N–H bending band of amide I and amide II, C=O stretching of zinc acetate C=O, and C–O–C stretch of polysaccharide | [ ] |
Sargassaceae | DLS: 46.6 AFM: 20–36 TEM: 76–186 | Rectangular, triangle, radial hexagonal, rod, and spherical shape | Carboxylic acid, with O–H and C=O stretching bands | [ ] | |
Ulvaceae | TEM: 10–50, av.: 15 XRD: 5–15 | Triangle, hexagon, rod | 420 cm suggests ZnO, peaks at 1634.00, and 620.93 cm suggests ZnO stretching and deformation vibration | [ ] |
A plethora of studies suggests that the morphology and surface chemistry of nanoparticles influence their biodistribution, safety, and effectiveness in biological systems ( Figure 8 ). Characterization is the core tool for successful applications and the understanding of nanoparticles. Nanoparticle size characterization is complicated by the polydispersity of materials, yet it is important to determine the morphology since the nanoparticle size’s resemblance to biological moieties is assumed to impart many of their distinct nanomedicine capabilities. Optical microscopy cannot resolve nanostructures; therefore, electron microscopy is used to characterize the nanoparticles. SEM and TEM are used to characterize the shapes and sizes, but TEM is used more often because it uses more powerful electrons and presents high resolution and informative image details regarding the atomic scale-like morphology, aggregation state, and distribution, and observes the functionality of capping agents/phytochemicals in enclosing NPs. Some biological molecules such as liposomes and proteins do not deflect the electron beam sufficiently and are invisible to electromagnetic radiation; therefore, dynamic light scattering (DLS), a nondestructive approach that uses a monochromatic laser and is also known as photon correlation spectroscopy, is used to characterize these compounds in suspensions and solutions. Here, small changes in the intensity of scattered laser light in the nanoparticle solution are regulated with a photon detector to analyze the hydrodynamic diameter and morphology of NPs [ 204 ].
Morphology of ZnO nanostructures: ( A ) needles, rods, and wires; ( B ) helixes and springs; ( C ) nanopellets/nanocapsules; ( D ) flower, snowflake, and dandelion; ( E ) peanut-like; ( F ) interwoven particle hierarchy; ( G ) raspberry, nanosheet/nanoplate; ( H ) circular/round or sphere-shaped. (Reprinted from [ 209 ]; open access under CC BY).
The characterization of nanoparticles in animal tissue is accomplished by energy dispersion X-ray analysis (EDX), which assists in identifying the elemental composition and linkage of metabolites and also facilitates the interpretation of biodistribution of synthesized nanoparticles. Furthermore, atomic force microscopy (AFM) helps in determining the 3D geography (height and volume) of NPs; Fourier transform infrared spectroscopy (FTIR)-attenuated total reflectance (ATR) is an easy and nondestructive technique that contributes metabolites, chemicals, etc. through the synthesis and capping of NPs; UV–visible-diffuse reflectance spectroscopy (UV-DRS) is used to study the optical property of colored samples where the reflectance measurements are utilized to investigate the surface plasmon resonance of metals and hypersensitive biological analysis [ 205 ]; thermal gravimetric-differential thermal analysis (TG-DTA) provides information about the thermal stability, phase transition, and effect of the oxidative as well as reductive environment; photoluminescence (PL) analysis is utilized to determine the band gap, and crystalline purity and impurities; and x-ray photoelectron spectroscopy (XPS) can be used to characterize the morphology, and bioactive surface and material surface chemistry of NPs [ 206 , 207 , 208 ].
ZnO is one of the most significant II-VI compound semiconductor materials in scientific research and technological applications with noncentrosymmetric structures and multiple shape-induced functions. By adjusting the hydrothermal reaction parameters (such as precursor concentration, reaction duration, and pH), several morphologies of ZnO, including microrods, hexagonal pyramid-like rods, and flower-like rod aggregates, have been synthesized, respectively, on glass substrates. The production of ZnO microrods is significantly influenced by the precursor concentration. With longer reaction times, ZnO crystals can change from hexagonal pyramids to rod-like laths. ZnO rod aggregates that resemble flowers are produced at higher pH levels. The findings could provide a strategy for producing ZnO crystals in a certain desirable form [ 210 ]. Similarly, in a recent study, Doustkhah et al. hydrothermally transformed zinc-based metal-organic frameworks into ZnO nanostructures with temperature-dependent tunable structures and catalytic activity, which at an elevated temperature displayed high crystallinity and better dye degradation efficiency than at a lower temperature [ 211 ].
Most of the group II-VI binary compound semiconductors crystallize as hexagonal wurtzite or cubic zinc-blende, with each anion surrounded by four cations at the corners of a tetrahedron. The iconicity of the II-VI compound semiconductor ZnO lies at the interface between covalent and ionic semiconductors. Wurtzite, blende, and rocksalt are potential ZnO crystal formations. Wurtzite is the most thermodynamically stable of these crystal forms at room temperature, but blende is stable when developed on a cubic substrate and rocksalt is stable when synthesized at very high temperatures [ 212 ]. In contrast to the zinc-blende structure, which has two interpenetrating face-centered-cubic (fcc) sublattices that are displaced along the body diagonal by one-quarter of a body diagonal, the wurtzite structure is made up of two interpenetrating hexagonal-closed-packed (hcp) sublattices. Due to the decrease in lattice dimensions, which favors iconicity over a covalent nature, and the structure’s six-fold coordination, wurtzite can undergo the same transformation as other II-VI semiconductors to become rocksalt [ 212 ].
This review aimed to explore the synthesis, characterization, and biological activities of ZnO-NPs, illustrating their mechanism of action. Extensive discussion was centered on the green synthesis approach and its biomedical applications. The pathways of different bioactivity were explained, with special emphasis on ZnO-NPs’ biopotency with regard to antibacterial, antifungal, anticancer, anti-inflammatory, antidiabetic, antioxidant, antiviral, wound healing, orthopedic implants, bone healing, and cardioprotective activity, along with the concise interpretation of the green synthesis of nanoparticles using biological sources. The importance and significance of ZnO-NPs in pharmaceutical and biological sectors have attracted scientists to perform an extensive study of their applications in multiple ailments. Green synthesis is an eco-friendly approach that reduces costs, increases production, and improves biocompatibility in humans. Biofabrication with natural compounds helps to stabilize the nanoparticles with reduced toxicity and higher reduction potential. ZnO-NPs possess several compelling pharmacological activities. Special focus should be given to ZnO-NP generation through plant-mediated synthesis, bearing tremendous applications in the fields of pharmaceuticals, food, and cosmetics. The advancement of nanotechnology in the formulation of metal oxide nanoparticles can contribute to the reduction in the dosage used with optimum desired effects and low toxicity.
We are thankful to Arpita Roy, Sharda University, India, for her feedback on the manuscript.
ZnO-NPs: zinc oxide nanoparticles; ROS: reactive oxygen species; SOD: superoxide dismutase; GSTs: glutathione S-transferases; NPs: nanoparticles; SEM: scanning electron microscopy; TEM: transmission electron microscopy; XRD: X-ray diffractometer; DLS: dynamic light scattering; EM: electron microscopy; HRTEM: high-resolution transmission electron microscopy; HRSEM: high-resolution scanning electron microscopy; FE-SEM: filed emission scanning electron microscopy; AFM: atomic force microscopy; GSH: glutathione; GPx: glutathione peroxidase; MSG: monosodium glutamate; DPPH: 2,2-diphenyl-1-picrylhydrazyl; NEFA: nonesterified fatty acid; iNOS: inducible nitric oxide synthase; PGE2: prostaglandin E2; NF-κβ: nuclear factor-kappa b; COX 2: cyclooxygenases 2; IL-1: interleukin-1; TNF: tumor necrosis factor; IL-6: interleukin-6; IL-12: interleukin-12; IL-18: interleukin-18; ATR: attenuated total reflection; EDAX: energy dispersion analysis of X-ray; PL: photoluminescence; XPS: X-ray photoelectron microscopy; TG-DTA: thermal gravimetric-differential thermal analysis; UV-DRS: UV–visible reflectance spectroscopy; BMs: biodegradable metals; ALP: alkaline phosphatase; hBMSCs: human bone marrow-derived mesenchymal stem cells; hDPSCs: human dental pulp stem cells; MDR: multidrug-resistant; HPMC: hydroxypropyl methylcellulose; FBS: fasting blood sugar; CAT: catalase.
Tettey and Bhattarai acknowledge funding support in part from National Science Foundation (EiR-2100861) for their contribution to this review work.
Conceptualization, N.P. and N.B.; methodology, A.K.M.; writing—original draft preparation, A.K.M., S.B., A.G., F.T., N.B., A.K.S. and N.P.; writing—review and editing, S.K., S.J. and D.P.B.; editing images, S.B. and F.T.; supervision and project administration, N.P. and N.B. All authors have read and agreed to the published version of the manuscript.
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In this study, ZnO nanoparticles were fabricated by co-precipitation method. The synthesized nanoparticles possessed monodispersity with the average size 20–30 nm. Since the industrial effluents may not be at neutral pH, the effect of pH on the rate of degradation is important and need to be considered. In order to investigate the effect of pH on ZnO nanoparticles photocatalytic activity, the photocatalytic degradation of Rose Bengal, Methylene blue, and Bromocresol green dyes, was studied with different pH values. It was observed that the adsorption of the dyes onto ZnO nanoparticles surface is strongly dependent on the pH of the solution which plays an important role in photocatalytic degradation.
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Photocatalytic degradation of methylene blue dye by zinc oxide nanoparticles obtained from precipitation and sol-gel methods.
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Kazeminezhad, I., Sadollahkhani, A. Influence of pH on the photocatalytic activity of ZnO nanoparticles. J Mater Sci: Mater Electron 27 , 4206–4215 (2016). https://doi.org/10.1007/s10854-016-4284-0
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Published : 08 January 2016
Issue Date : May 2016
DOI : https://doi.org/10.1007/s10854-016-4284-0
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Title: | Investigations on certain metal oxide based semiconductor nanomaterials for photocatalytic activities |
Researcher: | Rajeswari, R |
Guide(s): | |
Keywords: | Engineering and Technology Engineering Engineering Chemical Semiconductor nanomaterials Metal oxide |
University: | Anna University |
Completed Date: | 2020 |
Abstract: | Photocatalysis is an acceleration of a photoreaction using semiconductor catalyst by the activation of a light energy. It can be referred to the combination of both photochemistry and catalysis. As compared to metal, semiconductors are the best photocatalysts due to their distinctive bandgap structure which makes the photoexcitation. They also act as sensitizers due to their filled valence band and empty conduction band in the light induced redox reaction. Indeed, most of the semiconductor nanomaterials have some intriguing properties such as less toxic, cost efficient, reusable, stable, insoluble and easy to fabrication. Among them, the semiconductor metal oxides (ZnO, MoO3 and Nb2O5), metal sulfide (MoS2) and their heterostructure (ZnO-MoS2) are greatly attracted in the field of heterogeneous photocatalyst for the toxic dye removal applications due to their unique band gap energy and tunable physico-chemical properties. Thus, our focuses on the synthesis of different semiconductor nanomaterials by simple and ecofriendly method for waste water treatment applications. The preparation of zinc oxide (ZnO) nanoparticles (NPs) by green synthesis route using carica papaya leaf extract for photocatalytic application has been demonstrated. In this work, the phase pure ZnO NPs were synthesized via facile green synthesis method, where zinc acetate dihydrate was used as precursor and papaya leaf extract as reducing agent. The structure and phase formation of the synthesized material was confirmed by X-Ray diffraction and FT-IR analysis. The bandgap energy for the prepared ZnO NPs was calculated from the DRS spectra and it is found to be 3.32 eV. The surface morphology and phase purity of ZnO NPs was characterized by FE-SEM and EDX analysis, respectively. Electron microscopic analysis indicates that ZnO NPs are spherical in shape with particle size of ~50 nm. Importantly, the as synthesized ZnO NPs were used as efficient photocatalyst for Methylene Blue (MB) dye degradation. It is persistent to note that the prepared ZnO NPs almost completely degraded the MB dye under UV light condition after 180 min illumination tim newline |
Pagination: | xxiii,121 p. |
URI: | |
Appears in Departments: | |
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Scientific Reports volume 13 , Article number: 20809 ( 2023 ) Cite this article
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The design of a green photocatalytic system that harnesses renewable and eco-friendly constituents holds the potential to offer valuable insights into alternative strategies for treating toxic multi-components in refinery water effluents. A significant challenge in implementing a practical and viable approach is the utilization of solar energy—an abundant, natural, and cost-effective resource—for photochemical processes within advanced oxidation processes. In this study, we explored the use of zinc oxide nanoparticles (ZnO NPs) as photocatalyst prepared via an environmentally friendly synthesis approach, resulting in the formation of crystalline wurtzite nanoparticles, with an average size of about 14 nm relatively spherical in shape. Notably, the extract derived from Moringa oleifera was employed in this investigation. These nanoparticles were characterized and validated using various characterization techniques, including X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy. For comparison, conventionally synthesized ZnO NPs were also included in the evaluations. The findings reveal that, under illumination, biosynthesized ZnO nanoparticles (NPs) exhibit photocatalytic performance in effectively breaking down the organic compounds present in synthetic petroleum wastewater. Photochemical analysis further illustrates the degradation efficiency of Green-ZnO, which, within 180 min of irradiation resulted in 51%, 52%, 88%, and 93% of removal for Phenol, O-Cresol. Under optimal loading conditions, NPs produced via the green synthesis approach perform better when compared to chemically synthesized ZnO. This significant improvement in photocatalytic activity underscores the potential of eco-friendly synthesis methods in achieving enhanced water treatment efficiency.
Introduction.
Water is an indispensable valuable resource used in a variety of industrial operations and is essential to all kinds of life. Environmental pollution caused by dangerous chemicals has recently become one of the biggest issues facing industrialized countries. One of the industries that produce a lot of wastewater is the petroleum refining industry. Wastewater produced by the petroleum industries contains a variety of substances, mostly organic molecules (primarily aromatic and aliphatic hydrocarbons) and total solids dissolved (such as salts, barium, and strontium).
Crude oil includes considerable quantities of monoaromatic hydrocarbons including toluene, benzene, ethylbenzene, and xylene (BTEX), which are categorized under volatile organic compounds (VOCs), and trace levels of polycyclic aromatic hydrocarbons (PAHs) 1 . These toxic compounds find their way into the delicate ecological balance via the discharge of wastewater from petroleum industrial facilities, permeating the air, soil, and water, thereby exacerbating environmental pollution 2 . The ecosystem and living species are seriously threatened by a rise in toxins in the water bodies, which can have severe and long-lasting effects Indeed, this can harm aquatic life, disrupt the food chain, and potentially affect human health if contaminated water is used for drinking, irrigation, or other purposes 3 .
Refinery effluents are subject to strict regulations and monitoring to ensure that these potentially harmful compounds are controlled and reduced to safe levels before discharge into the environment. To combat the environmental challenges posed by the release of toxic compounds from petroleum industrial plants, it is essential to promote the adoption of recycling and sustainable practices in the industry. These efforts not only contribute to environmental protection but also offer economic benefits and support long-term water resource preservation 4 .
This urgent concern has prompted a concerted effort to discover renewable technologies for water remediation with the following key tenets: increased efficiency and self-sufficiency. Petroleum refineries commonly employ primary and secondary wastewater treatment techniques. In the primary treatment phase, oil–water separation is achieved through physical methods like sedimentation or dissolved air flotation. To tackle impurities, coagulation with chemicals like aluminum hydroxide or ferric hydroxide is utilized, forming sludge. Nevertheless, these technologies come with inherent drawbacks and constraints. Notably, they generate concentrated sludges necessitating further processing and discharge, which can impose financial constraints due to the substantial initial investments demanded 5 . In lieu of conventional treatment methods, Advanced Oxidation Processes (AOPs) offer a promising alternative for swiftly breaking down contaminants in aquatic environments. These innovative techniques involve the generation of hydroxyl radicals (OH.), among other reactive species, which can effectively interact with organic compounds and facilitate their complete mineralization 6 . Such processes include UV 7 ; O 3 /H 2 O 2 8 ; O 3 /UV 7 , 8 ; photo-Fenton and Fenton processes 4 , 9 and photo-catalysis 4 .
Among these techniques, solar photocatalysis is attracting considerable interest as a sustainable and environmentally friendly technology for petroleum refineries wastewater treatment owing to its ability to oxidize a wide range of organic pollutants.
Presently, a variety of semiconductor-based nanophotocatalysts have been applied in water pollution remediation, with a significant emphasis on metal oxide nanoparticles 10 , 11 , 12 . Notably, zinc oxide (ZnO) has garnered considerable attention in this regard. ZnO stands out due to its outstanding charge transport properties, characterized by a 3.3 eV bandgap and a high excitation binding energy of 60 meV. Moreover, it exhibits excellent chemical stability, non-toxic nature and long-term photo-stability. These distinctive properties together produce an impressive photocatalytic behavior 13 .
Fundamentally, when a semiconductor boasting a suitably wide band gap absorbs light energy surpassing its own, it prompts the migration of valence band electrons (e − ) to the conduction band (CB), creating vacancies, or holes (h + ), in the valence band (VB). These photo-excited electrons and holes subsequently initiate redox reactions with species whose redox potentials align appropriately. This interplay indeed induces reduction and oxidation reactions, giving rise to the production of superoxide (O 2 . ) and hydroxyl (OH . ) radicals, which play a pivotal role in breaking down the organic pollutant 14 , 15 .
Indeed, the generated hydroxyl radicals, known for their strong oxidation properties, will initiate the breakdown of the contaminants adhered to the photocatalyst’s surface, leading to the prompt formation of intermediate substances. These intermediates will ultimately transform into environmentally friendly compounds like carbon dioxide (CO 2 ) and water (H 2 O), as indicated in (Eq. 10 ).
Thus, the process of solar-induced photodegradation of toxic organic substances through redox reactions can be outlined in the following manner 16 , 17 :
Four aromatic and aliphatic hydrocarbons often discovered in refinery effluent were designated as target pollutants to evaluate their removal effectiveness by solar-assisted photocatalysis, specifically, Phenol, O-Cresol, Toluene, and Xylene. Figure 1 illustrates the redox reaction occurring during photocatalysis over ZnO NPs.
Scheme of PC mechanism occurring over ZnO.
Several methods for NPs synthesis are under consideration. They include both physical and chemical approaches, which, while effective, often entail high costs, time consuming, and environmentally toxic. The environmental compatibility is a significant advantage when it comes to applications involving water treatment, as it ensures that no harmful byproducts or residual toxicity are introduced during the remediation process. Indeed, in conventional processes, common reducing agents, such as sodium citrate, sodium borohydride, and various alcohols are widely known for their hazardous properties, their toxicity, flammability, explosiveness, and resistance to decomposition. Therefore, nowadays different researchers attempted to provide safer, non-toxic, and ecofriendly approaches for NPs fabrication. One such innovative approach is the biological synthesis of NPs. In the process of green synthesis, a natural extract such as microorganisms and/or plant extracts is harnessed as an environmentally sustainable alternative reducing and capping agent. Consequently, the resulting NPs are devoid of any remnants of organic solvents or toxic chemicals, rendering them inherently eco-friendly when introduced into the environment. This approach offers a distinct advantage over conventional methods, due to its simplicity, cost-effectiveness, environmental friendliness, and relative reproducibility 18 , 19 , 20 , 21 , 22 .
Based on several studies, green synthesis presents an alternative and promising approach to produce NPs that are safer, with reduced chemical toxicity, benefiting both human health and the environment 23 , 24 , 25 , 26 . Jayarambabu et al. aimed to synthesize ZnO NPs using Lawsonia inermis leaf extract and explore their potential toxicological impacts. The histopathological assessment revealed the safe use of biosynthesized ZnO NPs, confirming their non-toxicity and compatibility with biological systems, thus indicating their promise in the treatment of various diseases. This study conclusively establishes the harmlessness of the biogenic production of ZnO NPs on all vital organs 27 . Moreover, early literature has shown that, compared to conventionally produced NPs, biosynthesized ZnO NPs significantly suppress both bacterial and fungal diseases 28 . Furthermore, a recent review lends support to the utilization of environmentally-friendly produced ZnO NPs as feed additives, highlighting their potential to enhance immunity against viral infections 24 . ZnO NPs derived from natural resources have received approval from the United States Food and Drug Administration (FDA). They are classified as “GRAS,” which stands for “Generally Recognized As Safe.” 29 . Rashidian et al. 23 conducted a study to assess the toxicological effects of green synthesized versus commercial ZnO NPs on the immune responses within the skin mucus of carp. The results of this investigation revealed that green ZnO NPs exhibited significantly reduced immunosuppressive effects on important components of fish skin mucus. These green NPs hold immense promise for a wide range of applications in the realms of biology, agriculture, and environmental monitoring. In the future, they have the potential to significantly enhance ecological protection and conservation efforts 30 , 31 .
This study presents a green synthesis approach for the production of ZnO photocatalysts, designed to support sustainable and environmentally friendly water remediation processes. This method involves the use of safer precursors, the elimination of hazardous compounds, the reduction of energy consumption and the utilization of renewable natural resources.
The added value of our strategy toward water remediation achievements is articulated in 3 aspects:
Eco-friendly photocatalyst fabrication process, with the addition of few or no chemical compounds during the synthesis, which imposes the respectful aspect to the environment when released into the ecosystem.
Sustainable and cost-effective nanotechnology. On the one hand it employs a green synthesis using readily accessible and cost-effective plant extracts. On the other hand, it utilizes photocatalysis through natural sunlight instead of artificial lighting, which not only has a shorter operational life but also demands a high energy input. This dual-pronged approach simplifies the process, reduces costs, and enhances scalability for widespread application.
Simultaneous degradation of organic compounds, present in refinery effluents (Phenol, O-Cresol, Toluene, Xylene).
Therefore, in the present work, we highlight the utilization of M. Oleifera leaf, a natural substance as a reducing and capping agent to generate crystalline ZnO NPs. This study illustrates the initial efforts to optimize multicomponent synthetic refinery wastewater’s oxidation processes using solar light, coupled with biosynthesized photocatalyst. The prepared materials were investigated by means of X-ray diffraction (XRD), Transmission electron microscope (TEM), field emission scanning electron microscope (FESEM), and energy-dispersive X-Ray spectroscopy analysis (EDXS). Photocatalytic degradation of synthetic refinery wastewater (SRW) with the prepared catalysts is also reported.
Biosynthesis of zno nps using moringa oleifera leaves extract (green-zno), declaration statement.
We declare that the collection of plant material is in accordance with relevant institutional, national and international guidelines and legislation.
Moringa oleifera leaves have served as an eco-friendly alternative natural reducing and capping agent. The “drumstick tree,” also known as Moringa oleifera Lam ., is acknowledged as a plentiful and reasonably priced plant. The phytochemical profile of its leaves showed the presence of essential bioactive compounds; vitamins, phenolic acids, flavonoids, and glucosides 32 , 33 .
Moringa oleifera plant has been cultivated and collected from the Higher Agronomic Institute of Chott Mariem (ISA CM), Tunisia. 10 g of cleaned and dried M. Oleifera leaves were boiled for 30 min in 100 mL of double distilled water at 60 °C under magnetic stirrer. The mixture was brought down to room temperature (for 1h45), then filtered through filter paper and a light-yellow solution. The filtered plant extract was kept in a refrigerator at 4 degrees Celsius for future use 34 .
A magnetic stirrer was used to heat 60 mL of M. Oleifera leaf aqueous extract to 80 °C before adding 6 g of zinc nitrate hexahydrate (Zn(NO 3 ) 2 .6H 2 O). The mixture was boiled until a yellow-tinted paste formed. After that, it was transferred to a ceramic crucible, then calcined for 2 h in a furnace at 500 °C. Ultimately, a light yellow powder was collected 34 .
With certain adjustments, the chemical synthesis was created in accordance with the earlier work 35 . After vigorously swirling 6 g of zinc nitrate hexahydrate (Zn(NO 3 ) 2 .6H 2 O) into 60 ml of distilled water for 10 min, 2.0 M of ammonium hydroxide was added dropwise until the pH reached 10. The resulting white precipitate was passed through a filter before being calcined for two hours at 500 °C in a furnace.
Several analytical techniques were used to characterize the ZnO synthesized samples that were shown in the preceding sections. The UV–VIS absorbance spectra were acquired in an integrating sphere using a LAMBDA 365 UV/Vis Spectrophotometer in the range 300–600 nm. An X-Ray Diffractometer was used to characterize the structural properties (Siemens D5000). The angular 2 diffraction ranged from 5 to 70. As a sample holder, a low background Si wafer was employed. A copper X-ray tube provided CuKα radiation (0.15414 nm). The particles morphologies were studied by a FESEM (Thermo Scientific Fisher operated by EDS-Software-pathfinder) associated with EDXS (Oxford INCA PentaFET- × 3). TEM-SAED was used to assess shape, size, and crystallinity. TEM figures were collected using a Transmission Electron Microscope (JEOL model 1011). The solid samples were dispersed in ethanol by sonication, and droplets of zinc oxide NPs suspensions were poured onto a carbon coated-copper grid. Further the material was dried at room temperature and transferred to electron microscope for analysis 36 .
The pH drift technique was used to find the point of zero charge (pHpzc) of the biosynthesized ZnO. A series of 0.01 M NaCl solutions (10 mL each) were formed, and their pH values (pH 0 ) were adjusted between 5.0 and 10.0 by adding 0.1 M HCl and 0.1 M NaOH. The suspensions were stirred at 25 °C with 0.02 g of ZnO added to each solution. The solutions’ ultimate pH readings were obtained (pH f ) after 24 h 37 . The variance between the initial (pH 0 ) and final (pH f ) readings was plotted against the starting pH0 (Y-axis) (X axis). The resultant curve’s intersection generated the pHpzc where pH = 0 38 .
Four aromatic and aliphatic hydrocarbons often discovered in refinery effluent were designated as target pollutants to evaluate their removal effectiveness by solar-assisted photocatalysis. Table 1 shows the composition of the synthetic water based on earlier studies with Real Refinery Wastewaters (RRWs) 7 , 39 , 40 , 41 , 42 . To prepare the SRW, 900 mL of distilled water was first mixed with 5 mg of Triton-X, the necessary salt quantities, and non-soluble compounds. A homogenizer was then used to emulsify the mixture for 30 min. The mixture was then supplemented with the required amounts of soluble organic materials while being vigorously agitated. Prior to use in the tests, the solution was then adjusted into 1000 mL in distilled and agitated for an additional 30 min to guarantee stable wastewater before use in the studies.
HPLC was used to determine the concentrations of the contaminants (Phenol, O-Cresol, Toluene, and Xylene) in the synthetic modeling water (Shimadzu LC-20AT). The separation was obtained through a C18 TeknoKroma column (4.6 × 250 mm, 5 micron) and detected at wavelength of 254 nm. The concentrations of each component were evaluated based on their respective calibration curves using standards.
The set of experiments was carried out in a borosilicate reactor with 550 mL of synthetic wastewater as a photoreactor. For 30 min, the liquid was mixed in the dark in order to assure the adsorption of compounds on the solid surface. An air-cooled 1500-W Xenon lamp in a solar box that simulates sunlight and emits light in the 300–800 nm range was used to irradiate the reactor (ATLAS, SUNTEST CPS +). The illumination was adjusted at 250 W/m 2 . The pH of solution was adjusted using dilute sodium hydroxide and hydrochloric acid solutions. The samples collected at fixed time intervals were centrifuged for15 minutes at 8000 rpm in advance of the data analysis.
Characterization of the synthesized nps, uv visible absorption.
The UV–vis absorption spectra of ZnO materials are depicted in Fig. 2 (a). Both samples exhibited UV–vis absorption spectra, with a wide intense absorption from about 350 nm, which may be linked to the intrinsic absorption of the BG of ZnO NPs caused by electron (e−) transfer out from VB towards the CB 34 , 43 , 44 , 45 , 46 .
( a ) UV–Visible absorption spectrum ( b ) Inset. Plot of (αhυ) 2 versus photon energy of Green-ZnO and Chem-ZnO.
Since ZnO is a direct band gap Semicond., its ABS coefficient (α) is correlated to the excitation energy by the formula:
where A is a proportionality constant, h is the Planck constant, v is the frequency of vibration, and n is an exponent, 1/2, that characterizes direct allowed optical transitions.
E g is calculated by plotting (αhυ) 1/n vs. (hυ) and extrapolating to (αhυ) 1/n = 0 (Fig. 2 b). The extrapolation of the linear part until its intersection with the photon axis was employed to approximate the optical BG. From Fig. 2 (b), E g values are 3.16, and 3.07 eV for Green-ZnO, and ZnO-Chem respectively 47 , 48 , 49 . It denotes a widening of the optical BG for the Green-ZnO compared to Chem-ZnO. It is thought that a significant contributing element to this blueshift is the quantum size effect. As the grain size decreases, the continuous energy bands split off into discrete levels, causing the effective expand of the BG. Similar earlier reports also noted these results 44 , 50 , 51 .
The XRD patterns of green produced ZnO NPs derived from zinc nitrate hexahydrate and Moringa leaf extract, as well as conventionally generated ZnO NPs formed from zinc nitrate hexahydrate and ammonium hydroxide are illustrated in Fig. 3 .
XRD patterns of green and chemically synthesized ZnO NPs.
In both cases, the XRD graph demonstrated that the synthesized product was in crystal and that no further impurities could be found once compared to the structure known (ZnO, 04-016-6648). The reference pattern’s hexagonal structure and each of the prominent peaks in the samples were perfectly correlated.
The ZnO NPs' acquired XRD pattern reveals the positions of 2 degree diffraction peaks at 31.75, 34.43, 36.23, 47.55, 56.58, 62.89, 66.42, 68.17, and 69.11 with matching Miller indexes (hkl) of (100), (002), (101), (102), (110), (103), (200), (112), (201) respectively. This demonstrates ZnO’s hexagonal wurtzite phase (JCPDS: 36-1451).
Scherrer’s formula was applied to the high intensity peak (101) to estimate the crystallite size : D = Kλ/β cos θ Where K is a constant (0.9), λ is the X-ray wavelength, and β is full width at half maximum (FWHM) 52 . ZnO NPs have an average crystallite size of 12.51 nm for Green-ZnO and 11 nm for Chem-ZnO. Based on the Debye–Scherrer equation, Both NPs showed almost the same crystallite size. Indeed, in XRD analysis, it should be noted that the crystallite size is assumed to be the size of a coherently diffracting domain and is not necessarily to be the same as the particle size. Furthermore, according to literature, it has been found that the XRD peak can be widened by defects and internal stress 53 , 54 .
The surface morphology of chemically produced and green ZnO NPs is examined using a FE-SEM.
The SEM image Fig. 4 (a) of chemically formed ZnO reveals a range of irregularly shaped NPs clustered. We can observe that the chemically obtained ZnO have no defined geometry. On the other hand, the image of biosynthesized ZnO (Fig. 4 b) reveals NPs with well-defined structures at the nanoscale relatively spherical in shape with clear separation 49 . These NPs are surrounded with biomolecules found in the extract, which maintain them apart and avoid agglomeration. This demonstrates that the addition of the plant extract throughout the reaction had a significant influence on the formation mechanism, ending a more defined pattern with less agglomeration 35 , 55 .
FE-SEM: ( a ) chemically synthesized and ( b ) biosynthesized ZnO NPs.
Furthermore, the green method's obtained shape consolidates the physical properties of the NPs, enhancing their qualities and efficiency in many applications. Figure S1 allows us to determine an average size for the biosynthesized ZnO NPs of 13.95 nm. With obvious signals from the atoms of zinc and oxygen and the very low intensity of the carbon atom, the EDX spectrum (Figs. S2 and S3 ) of produced ZnO NPs reveals their chemical content and validates their purity 49 . The spectrum of Fig. S3 revealed additional peaks corresponding to Magnesium (Mg), Sulfur (S), Chlorine (Cl), Potassium (K) and Calcium (Ca) in very small quantities. Generally, these compounds are contained in the leaf extract of Moringa oleifera 55 , 56 , 57 .
TEM images were used to investigate the in-depth properties of chemically synthesized and biosynthesized ZnO NPs. The TEM micrograph of chemically synthesized ZnO in Fig. S4 (a) depicts the clustering and irregularity of chemically synthesized ZnO structures. On the other hand, Fig. S4 (b) reveals TEM micrograph of the biosynthesized ZnO NPs, giving rise to isolated NPs relatively spherical in shape. This figure (Fig. S4 b) is taken at high resolution and confirms the presence of spheroid-like and hexagonal shapes. The histogram in Fig. 5 shows the particle sizes of Green-ZnO NPs ranging from 9 to 18 nm in diameter, with an average size of about 14 nm and a standard deviation of 2.1. These outcomes validate the SEM analysis.
Particle size distribution histogram of Green-ZnO NPs.
The particles are distributed uniformly which is owing to the existence of organic compounds that encase the particles and act as a capping agent, blocking their aggregation. As a result, it is clear that biosynthesized ZnO has lower particle size and better morphological control than chemically produced ZnO 35 .
The SAED pattern (Fig. S4 c–d) was displaying distinct bright dotty rings, demonstrating the particles' crystalline structure, which is consistent with the XRD pattern shown in Fig. 3 .The corresponding SAED pattern of the chemically synthesized ZnO displays more discrete spots, indicating the single crystalline nature compared to the biosynthesized, which could be because of the residual organic compounds used during the green fabrication process.
Nitrogen adsorption–desorption profiles using BJH and BET techniques were employed to assess the surface properties and the type of porosity of green and chemically produced ZnO NPs. The pore size distribution and porosities were obtained from the desorption isotherm branch by using BJH approach, and the specific surface area was acquired using the BET method.
The specific surface area of the biosynthesized and chemically produced ZnO NPs is 19.789 m 2 /g and 4.923 m 2 /g respectively. The creation of smaller particle sizes may be responsible for the increase in the surface area of green ZnO. Moreover, the pore volumes of Green ZnO and chemically synthesized ZnO are 0.149 cc/g and 0.020 cc/g, respectively. The quantity of ZnO active sites and surface area increase with increasing pore volume 58 , 59 , so increases the adsorption capacity, which therefore boosts the photocatalytic effectiveness. (Fig. S5 a–d).
Catalyst loading.
Heterogeneous photocatalysis assays were conducted initially at free pH for 180 min with ZnO catalyst loads of 0.1, 0.25, and 0.5 g/L. All studies proceeded with a previous 30-min adsorption stage in the dark. This period of time was determined based on the results of the catalyst’s 60-min adsorption testing. Before the analytical processes, the samples collected were centrifuged for 10 min at 10,000 rpm.
It can be assumed that 0.1 and 0.25 g/L concentrations show an initial superior adsorption; however, 0.5 g/L concentration exhibits lower adsorption. Considering that the adsorption capacity typically rises with surface area, additional pollutant molecules are adsorbed on the surface given by a high catalyst loading 60 . However, a common tendency of a decline in the removal was seen.
As can be observed, 0.25 and 0.5 g/L achieve nearly identical final results at the end of the 180-min experiment. Analyzing the degradation response reveals that raising the concentration has no discernible effect on photocatalytic performance, which makes 0.25 g/L an optimum catalyst concentration.
The surface charge of the semiconductor photocatalyst, the mechanism, and the rate of reactive oxygen species (ROS) formation are all significantly influenced by the solution's pH value 61 . This, in turn, affects the rate of photocatalytic degradation of contaminants 62 , 63 .
The point of Zero charge pH (pHpzc) of ZnO is 8 according to Fig. 6 and in agreement with previous references 64 , 65 .
Point of zero charge (pHpzc) of biosynthesized ZnO nanoparticles.
In this regard, the elimination of each pollutant on ZnO at four distinct pH conditions viz. 5, 7, 8, and 9 have been studied at a constant concentration of catalyst 0.25 g/L. (Fig. 6 ). The C/Ci vs. time graph (where C denotes the concentration at various time intervals and Ci denotes the compound’s starting concentration) using the biosynthesized ZnO NPs (Green-ZnO) under simulated solar irradiation is shown in Fig. 7 (a–d).
Effect of initial pH on the photocatalytic activity of biosynthesized ZnO photocatalyst toward ( a ) Phenol, ( b ) O-Cresol, ( c ) Toluene, ( d ) Xylene after 30 min dark and 180 min of irradiation.
The percentage of phenol destroyed is found to be very low in an acidic media. These observations can be related to the phenomenon having positively charged NPs surfaces, which causes protonation of active sites and hence alters phenol adsorption, thereby affecting its removal 66 . Adsorption on ZnO will be less in the basic pH range, where phenol is predicted to be in the ionized state. As a result, surface-mediated degradation will be reduced 67 . Therefore, the neutral pH was the best suited for the phenol degradation.
Giving the basic nature of o-cresol (pKa = 10.316), under acid media, it tends to be positively charged 14 , 68 . As it is shown, the photodegradation % rose marginally as the pH climbed from 5 to 7. Nevertheless, above the optimum pH 7, there was a decrement in photodegradation%.
The maximum degradation efficiency of Toluene and Xylene (88.30% and 93.13% respectively) was reached with pH 7 following 180 min in the simulated sunlight/ZnO system. Remarkably, the results were comparable at pH values 7 and 9.
The increased removal effectiveness at basic pH can indeed be attributed to the fact that, in alkaline pH, OH . are more readily formed via oxidation of more hydroxyl radicals, that are present on the ZnO surface, thereby boosting the process performance 69 , 70 .
In all the 4 compounds, at pH8, which is the pH pzc the results are the worse ones. This behavior could be related to a possible aggregation of catalyst particles. Indeed, the zero surface charge creates zero electrostatic surface potential for pH levels near to pH zpc , which cannot generate the interaction rejection required to isolate the particles inside the solution. Aggregation occurs as a result, and photocatalyst clusters get bigger 71 .
Figure 8 (a–d) illustrates a comparison of time-dependent photocatalytic activity of both the Green-ZnO and the Chem-ZnO NPs towards each pollutant degradation. The photo-chemical analysis revealed that the degradation process with Green-ZnO within 180 min of irradiation resulted in 51%, 52%, 88%, and 93% of removal for Phenol, O-Cresol, Toluene, and Xylene respectively. However, in the case of Chem-ZnO, the percentage of degradation was 33%, 34%, 74%, and 89% of removal for Phenol, O-Cresol, Toluene, and Xylene respectively. The biosynthesis of ZnO clearly demonstrated a higher or quite equivalent degradation effectiveness in comparison to ZnO synthesized with conventional chemical route.
Photocatalytic activity of biosynthesized and chemically synthesized ZnO at optimum conditions toward ( a ) Phenol, ( b ) O-Cresol, ( c ) Toluene, ( d ) Xylene after 30 min dark and 180 min of irradiation.
A similar trend has been documented in prior studies that investigated dye degradation, whether using environmentally friendly or chemical synthesis methods 72 , 73 . It is widely assumed that the morphology, surface, and crystallinity of material are mainly responsible for its photocatalytic activity 74 . Indeed, the plant extract's bioactive substances aid in the development of ZnO nuclei through capping but also stabilizing them. As a result, the green method produces NPs that have greater distribution, structure-tunable, and are size-controlled 75 , 76 , 77 compared to the chemically synthesized sample, which could provide stability, a larger specific surface area, and reduced particle sizes, thus, high photogenerated charge carrier separation capabilities, enhanced light absorption and finally better degradation of pollutant molecules.
Tables S1 , S2 , and S3 in the Supplementary Information section offer a comparative analysis of our research findings with those from previous studies focusing on ZnO synthesized through various methods for the PC degradation of petroleum hydrocarbon contaminants. This comparison underscores the competitiveness of the results we have obtained in this study when compared to existing efficiency standards.
The primary objective of this research is to explore an environmentally sustainable, uncomplicated, and cost-effective solution that can either reduce the volume of waste discharged in effluents or promote the reuse of purified water, thus reducing the consumption of freshwater. The novel approach for photocatalyst synthesis employed in this study represents an initial step towards optimizing a more sustainable process, especially, when paired with sun energy, this allows an economically feasible route in the application of solar photocatalysis. Importantly, According to a previous study, the economical evaluation points out that the highest loads for the cost composition are due to catalyst synthesis, corresponding to 95% in a solar photocatalysis system 34 .
Ultimately, working with photocatalysts in form of powder needs a post-processing removal of the NPs from the liquid solution which could be an inefficient additional process step especially from an industrial perspective. For this reason, the development of photocatalysts immobilized as coatings is thus an improvement. That will require modifying the substrate, using a different thickener, or introducing a linker between ZnO and the substrate. In this case, the stability parameter and a study of reusability would be significant. We consider that an interesting topic for our ongoing and future research.
We reported on the photocatalytic activity of ZnO nanoparticles biosynthesized through a sustainable, cost-effective, easily scalable, and eco-friendly approach. Moringa oleifera leaves extract was used as reducing and stabilizer agent, hence playing a significant role towards structural evolution. The reported results reveal that Green-ZnO can be fruitfully exploited for the removal of toxic compounds present in refinery effluents particularly; Phenol, O-Cresol, Toluene, and Xylene with 51%, 52%, 88%, and 93% in sequence. Indeed, the PC efficiency of green-synthesized ZnO NPs is almost equivalent to that of ZnO via a conventional chemical synthesis. The ability of the proposed approach to use sunlight as the only energy input and photocatalysts with low cost and minimal environmental impact underline its significance in the ongoing efforts towards wastewater remediation.
Data are available from the corresponding author Prof. Chérif Dridi, upon reasonable request.
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The authors would like to thank the Tunisian MHESR for supporting this work and the University of Sousse for the “Bourse d’alternance” fellowship awarded to Mrs. Asma El Golli. The authors also acknowledge Dr Raoudha Khenfir Ben Jenana from the Higher Agronomic Institute of Chott Mariem (ISA CM), Tunisia, for providing the Moringa oleifera plant.
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A. El Golli & C. Dridi
Departament d’Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans, 26, 43007, Tarragona, Spain
S. Contreras
High School of Sciences and Technology of Hammam Sousse, University of Sousse, Sousse, Tunisia
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A.E.G.: Conceptualization, Investigation, Methodology, Writing– original draft. S.C.: Conceptualization, Methodology, Validation, Writing – review & editing, Funding acquisition. C.D.: Conceptualization, Methodology, Validation, Writing – review & editing, Supervision, Funding acquisition. All authors reviewed and approved the submission of the manuscript.
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El Golli, A., Contreras, S. & Dridi, C. Bio-synthesized ZnO nanoparticles and sunlight-driven photocatalysis for environmentally-friendly and sustainable route of synthetic petroleum refinery wastewater treatment. Sci Rep 13 , 20809 (2023). https://doi.org/10.1038/s41598-023-47554-2
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In this research, the nonlinear optical properties of specific nonconjugated conductive polymers and gold nanoparticles in transparent dielectric media have been investigated. Photovoltaic devices utilizing nonconjugated conductive polymers have also been studied. Nonconjugated conductive polymers are polymers with at least one double bond in the repeat. 1,4-polyisoprene (cis and trans), styrene butadiene rubber, and poly(β-pinene) are readily available examples of nonconjugated conductive polymers that have been investigated. Nonconjugated conductive polymers exhibit increases of many orders of magnitude in electrical conductivity upon doping with electron acceptors such as iodine. This change in conductivity results from charge-transfer from isolated double bonds in the polymer to the dopant. Exceptionally large optical nonlinearities have been reported for nonconjugated conductive polymers since they form sub-nanometer size metallic domains (quantum dots) upon doping. Nonconjugated conductive polymers have been shown to have many potential applications in nonlinear optics, electro-optics, and photovoltaics. The quadratic electro-optic effect and electroabsorption have been investigated in several nonconjugated conductive polymers including cis-1,4-polyisoprene, trans-polyisoprene, styrene butadiene rubber, and polyethylene terephthalate. The effects of iodine doping on polyethylene terephthalate have also been investigated using spectroscopy. Metallic nanoparticles in a dielectric medium have also been shown to have high magnitude nonlinear optical susceptibilities. Large nonlinear susceptibilities have been reported near the surface plasmon resonance frequencies in the materials. These effects have been attributed to dielectric confinement of charges within the metal nanoparticles and were predicted theoretically to be related to the size of the related charge-system. The nonlinear optical properties of gold nanoparticles in a dielectric medium (glass) and Iodine-doped nonconjugated conductive polymers have been investigated. These studies used the field-induced birefringence method to measure the Kerr effect in these materials. Measurements of Kerr coefficients for the materials investigated have been performed. The magnitudes of the Kerr coefficients for the gold nanoparticle samples have been compared and used to verify theoretical models on the relationship between particle diameter and third-order optical susceptibility. Nonlinear absorption (electroabsorption) has also been measured in these materials. These measurements were made using applied electric fields to change the absorption of the material. The results have been used to gain theoretical understanding of optical nonlinearities of metallic nanoparticles down to the sub-nanometer dimensions. The nonlinearity has been shown to increase as 1/𝑑^3 where d is the diameter of the nanoparticle (quantum dot). Newer nonconjugated conductive polymers such as polyethylene terephthalate have also been studied. Photovoltaic devices utilizing Iodine doped nonconjugated conductive polymers have been constructed and evaluated. These devices were fabricated in a similar way to dye-sensitized solar cells with the polymer used as the absorbing layer. Incident light on the cell excites electrons in the nonconjugated polymer which are then transferred through an electrolyte to a thin layer of titanium dioxide. The created devices were exposed to light and their open-circuit voltages and short-circuit currents were measured. These results have been compared for the various nonconjugated polymers. The stability of the devices has also been investigated. The cells typically show degradation in the photocurrent output over time. Attempts were made to determine the cause of the rapid reduction in output and to find a method of extending the lifetime of the fabricated cells. These studies showed that sealing cells in order to reduce the loss of the liquid electrolyte can extend the lifetime of the cells.
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Ph.D. Candidate: Ziwei Han University of California, Irvine, 2024 Professor Adeyemi Adeleye
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Abstract: Heavy metal contamination in agricultural systems - soil and irrigation water - is a challenging problem with serious consequences on food safety and human health. Unlike most traditional treatment methods, engineered nanomaterials provide a unique opportunity to prevent and remediate heavy metal contamination in water and farm soils. However, there is a wide knowledge gap on the fundamentals of interactions between nanoparticles and dissolved toxic metallic ions in complex agricultural matrices. This dissertation focuses on understanding the unique chemistry of interactions between nanoscale zerovalent iron (NZVI) and metallic contaminants in water and farm soils and demystifies NZVI-based treatment.
BMC Oral Health volume 24 , Article number: 752 ( 2024 ) Cite this article
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Tissue conditioners are used for treating and improving the tissues supporting complete dentures. On the other hand, recent advances in nanotechnology have revolutionized various fields of science, including dentistry. The present study aimed to investigate novel antimicrobial applications of copper oxide nanoparticle-based tissue conditioner used in complete prostheses.
The present experimental study included 126 tissue conditioner samples with different concentrations of copper oxide nanoparticles (20%, 10%, 5%, 2.5%, 1.25%, 0.625%, and 0% w/w). The samples were incubated with Enterococcus faecalis , Pseudomonas aeruginosa , and Candida albicans in 24-well plates for 24 h. Then, samples from the wells were re-incubated for 24 h, and the microorganisms were counted.
The culture media containing E. faecalis and P. aeruginosa showed significantly different growth between different nanoparticle concentrations following 24 h ( P < 0.001), showing a reduction in bacterial growth with increased nanoparticle concentration. Both bacteria did not show any growth at the 20% concentration. However, C. albicans showed significant differences in growth between different nanoparticle concentrations following 48 h ( P < 0.001), showing a reduction in growth with increased nanoparticle concentration. Also, the least growth was observed at the 20% concentration.
In conclusion, the CuO nanoparticles were prepared using a green synthesis methon in the suitable sizes. Moreover, the tissue conditioners containing CuO nanoparticles showed acceptable antimicrobial properties against E. faecalis , P. aeruginosa , and C. albicans .
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Replacement of lost teeth is essential for health and high quality of life since edentulism can negatively affect facial aesthetics, speaking, and mastication [ 1 ]. There are different methods for replacing lost teeth, including implant-supported prostheses, implant-supported dental bridges, and removable prostheses [ 2 , 3 ]. However, some of these options, such as dental implants, are less frequently used compared to other options due to limitations of the oral cavity and cost-ineffectiveness [ 4 ]. Considering the increased life expectancy of the middle-aged and the elderly, as well as the high prevalence of edentulism in this population, dental prostheses have become extensively popular in this age group. The prostheses used for tooth restoration should show enough biocompatibility in the oral cavity while improving facial aesthetics [ 5 ]. Moreover, prostheses should be properly designed in order to meet the physiological needs of the oral cavity, support the related soft and hard tissues without causing injuries, and have prolonged durability, thereby making the edentulous patients needless to new prostheses for several years [ 6 ].However, various bacterial and fungal species living in the oral cavity as the natural flora can turn into pathogens under certain conditions, such as prolonged use of dental prostheses. Thus, long-term use of these prostheses may result in stomatitis. Moreover, several factors, such as mucosal trauma, tobacco use, malignancies, endocrinopathic disorders, and the use of antibiotics, which can change the natural flora of the oral cavity, can predispose patients to prosthesis-induced stomatitis [ 7 ].On the other hand, tissue conditioners can be used for treating and improving the tissues supporting complete dentures. Lining the poor-fitting dentures helps in tissue healing and regeneration before molding for a new denture. Moreover, tissue conditioners can be used for temporary reasons, whether accessory or diagnostic, such as restoring the occlusal vertical dimensions and occlusal correction of old prostheses. Also, they can be used for evaluating the need for a permanent soft liner for patients with chronic or denture-induced pain [ 8 ].
Numerous efforts have been made to incorporate antimicrobial additives into the structures of tissue conditioners. These additives include antibiotics, essential oils, herbal oils, and notably, nanoparticles with antimicrobial properties [ 9 ]. Although some of these tissue conditioners show promising results against microorganisms, several deficiencies have been reported for the investigated cases. Among these defects, the lack of stability of the materials added to the tissue conditioner and the harmful effect on the mechanical properties of the tissue conditioner can be mentioned. Despite the positive effect of antimicrobial agents on tissue conditioners, there are no commercial antimicrobial tissue conditioners yet [ 9 , 10 , 11 , 12 , 13 ].
Nanotechnology has made significant advancements in various scientific domains, including dentistry, offering remarkable possibilities. One of the key attributes of nanoparticles is their high surface-to-volume ratio, which contributes to their exceptional properties [ 10 ]. Additionally, nanoparticles possess considerable strength and mechanical characteristics due to the formation of robust cross-links within polymer structures. Fragmenting materials into nanoparticles can be a potent method for creating structures with exceptionally high strength and excellent mechanical properties [ 11 ]. Furthermore, certain nanoparticles, such as silver, gold, copper, or zinc nanoparticles, exhibit antimicrobial properties [ 12 , 13 ].
Despite their considerable optical, catalytic, electrical, and antifungal/antimicrobial properties, copper nanoparticles are less known in the field of nanotechnology compared to other nanoparticles [ 14 ]. However, multiple studies have shown their antimicrobial effects on human pathogens [ 15 , 16 ]. Previous studies have introduced silver, zinc, or chitosan nanoparticles into the tissue conditioners’ structures to investigate their antimicrobial effects. However, despite their beneficial properties, copper nanoparticles are dramatically cost-effective, which justifies their use instead of other metal nanoparticles [ 17 ]. Considering the numerous shortcomings mentioned in relation to various substances added to tissue conditioners, the importance of the present study is to investigate the use of antimicrobial properties of copper nanoparticles in combination with tissue conditioners.
A study by Homsiang et al. used added zinc oxide nanoparticles to tissue conditioners, reporting their antifungal activity [ 18 ]. Moreover, Mousavi et al. have investigated the antimicrobial properties of silver, zinc, and chitosan nanoparticles [ 19 , 20 ].
In dentistry, Pseudomonas aeruginosa infections often develop in patients with apical periodontitis and pulp necrosis [ 21 , 22 ]. Moreover, Enterococcus faecalis , the predominant species of enterococcus genus in humans, is associated with several oral diseases, such as dental caries, root canal infections, periodontitis, and peri-implantitis [ 23 , 24 ]. Also, immunocompromised individuals have increased colonization of Candida albicans in their oral cavity, leading to potential oral candidiasis [ 25 , 26 , 27 ].
To the best of our knowledge, no study has ever investigated the effect of adding copper oxide nanoparticles into the tissue conditioners’ structures on their antimicrobial properties. Thus, the present study aimed to investigate the antibacterial and antifungal properties of tissue conditioners used in complete prostheses following adding different ratios of copper oxide nanoparticles. The antimicrobial effects have been evaluated against P. aeruginosa , E. faecalis , and C. albicans .
Sample size.
In the present experimental study, the sample size was calculated at a minimum of 6 for each group using a confidence level of 95%, a statistical power of 80%, and the findings of previous studies [ 28 , 29 ]. Thus, we used a total sample size of 126, considering 21 subgroups.
The hydroalcoholic extract was prepared by grinding 20 g of propolis into a powder, which was then added to 100 mL of a hydroalcoholic solution (3:7 v/v) and kept at room temperature for one week. The hydroalcoholic solution, primarily composed of absolute ethanol, facilitated the extraction of polyphenolic compounds from the propolis, resulting in a higher extraction rate. After one week, the solution was filtered using a Whatman ® filter paper to remove any remaining propolis particles. The filtrate was then subjected to centrifugation at 4000 rpm to separate any solid particles. The resulting supernatant, free from solid particles, was preserved at 4 °C for future experiments. For the preparation of copper oxide nanoparticles, a solution containing 10 ppm of copper chloride was dissolved in deionized water. The copper chloride solution was mixed with the propolis extract solution at a temperature of 80 °C and stirred for 2 h at a uniform speed. The solution was filtered using a Whatman ® filter paper to eliminate impurities, followed by centrifugation at 4000 rpm. The precipitate obtained was isolated and purified. The supernatant from the previous centrifugation step was subjected to further centrifugation at 8000 rpm. The resulting precipitate was rinsed several times and utilized for the identification and characterization of the copper oxide nanoparticles [ 30 , 31 ].
The present study used the TDV Soft Provisional tissue conditioner (TDV Dental Ltda, Brasil) to prepare samples with 20%, 10%, 5%, 2.5%, 1.25%, 0.625%, and 0% (w/w) copper oxide nanoparticle. The copper oxide nanoparticles were added to the tissue conditioner powder with a certain powder-to-solution ratio and were mixed for 30 s to become homogenized based on the manufacturer’s instructions. Then, the solution was poured into molds of equal sizes (diameter: 12 mm, depth: 2 mm). The mixed paste was placed between glass slides until it hardened [ 27 ]. Moreover, the samples with undesirable shapes, uneven surfaces, wrong powder-to-liquid ratios, and bubbles were excluded from the study.
The present study evaluated the standard human pathogens, including E. faecalis ( ATCC 29,212 ) , P. aeruginosa (ATCC 27,853), and C. albicans ( ATCC 10,261 ) , which were obtained from the Microbial Bank of the Microbiology and Mycology Laboratory, School of Medicine, Hamedan University of Medical Sciences. The bacteria were cultured in blood agar media, while C. albicans was cultured in sabouraud dextrose agar media under laboratory conditions. A suspension with the concentration of 0.5 McFarland (1.5 × 10 8 bacteria/mL) measured using a spectrophotometer (Spectrophotometer Single Beam AE-S60-4 V, A & E Lab co, UK) was prepared from the grown colonies and then was diluted to obtain a suspension in Mueller Hinton broth media with the concentration of 1.5 × 10 5 bacteria/mL. Then, 200 µL of the suspension was added to tissue conditioner samples using a sampler (BRAND, Transferpette S, Germany). Afterward, the samples were incubated at a temperature of 37° C for 24 h, except for the media containing C. albicans that were incubated for 48 h.
The broth media containing the microbes on the tissue conditioners was sampled using a sterile swab, and the bacteria or fungi were cultured on blood agar or sabouraud dextrose agar media, respectively, using the lawn culture method. Following incubation for 24 h, the colonies were counted and reported using the CFU/mL.
The following methods were used for the characterization of nanoparticles:
X-Ray Diffraction (XRD): This method used the X-ray diffractometer (Xpert Pro MPD, Panalytical, Netherlands) at the wavelength of 1.5405 Å and the power of 40 KV/30 mA to evaluate the crystal structure of nanoparticles.
Fourier-Transform Infrared spectroscopy (FTIR): This method used the FTIR spectrometer (Spectrum400, PerkinElmer, USA) and also was conducted by KBR pellet technique under identical situations in the 500–4000 cm − 1 region.
Transmittance Electron Microscope (TEM): This device was used to examine the surface morphology and size of the nanoparticles. A transmittance electron microscope (TEM, Zeiss; EM10C model, Germany) at an accelerating voltage of 100 kv was used.
Data analysis was performed using the SPSS software version 27 (SPSS Inc., Chicago, Illinois, United States). The mean and Standard Deviation (SD) of growth was calculated in each group. Then, the intergroup comparisons of the 24-hour growth of bacteria between different concentrations of copper oxide nanoparticles were performed using the one-way Analysis Of Variance (ANOVA). In case of significant differences, Turkey’s post hoc test was used to find certain concentrations with significantly different growth of the microorganism. Moreover, the intragroup comparison of C. albicans growth between 24-hour and 48-hour assessments was performed using the Mann-Whitney test. Also, the significance level was set at 0.05 for all tests, except for the post hoc tests, which had a significance level of 0.002.
Figure 1 presents the X-ray diffraction pattern of the copper oxide nanoparticles, showing monophasic nanoparticles with monoclinic structures. The peaks’ intensity and position in the obtained pattern completely correspond to the previously reported patterns. Figure 2 presents the TEM image taken from the copper oxide nanoparticles, showing crystalline copper oxide nanoparticles with a diameter of 30–70 nm.
X-ray diffraction pattern of copper oxide nanoparticles
TEM image of copper oxide nanoparticles
According to the FTIR of copper oxide nanoparticles in Fig. 3 , the half-broad band at about 3401 cm − 1 shows the stretching frequency of the hydroxyl group, an indicator of the surface morphology of the synthesized nanoparticles. Moreover, a peak in the 1047 cm − 1 corresponds to the bonds between copper and hydroxyl groups.
FTIR of copper oxide nanoparticles
Table 1 presents the intergroup comparison of bacterial growth in different concentrations of copper oxide nanoparticles following 24 h, while Fig. 4 shows the mean bacterial growth in logarithm in different nanoparticle concentrations. According to Table 1 , the culture media containing E. faecalis and P. aeruginosa showed significantly different growth between different nanoparticle concentrations ( P < 0.001), showing a reduction in bacterial growth with increased nanoparticle concentration. Interestingly, both bacteria did not show any growth at the 20% concentration.
The mean bacterial growth in logarithm in different concentrations of copper oxide nanoparticles following 24 h
Table 2 presents the intergroup and intragroup comparison of C. albicans growth in different concentrations of copper oxide nanoparticles following 24 and 48 h, while Fig. 5 shows the mean growth in different nanoparticle concentrations following 48 h. According to Table 2 , C. albicans showed equal growth in all nanoparticle concentrations following 24 h, showing no significant difference ( P > 0.05). However, the growth significantly reduced following 48 h of culture compared to the 24-hour assessment ( P = 0.002), with the mean 24-hour growth being 9.9 × 10 4 folds higher than the 48-hour growth. Moreover, the 48-hour growth was significantly different between different nanoparticle concentrations ( P < 0.001), showing a reduction in growth with increased nanoparticle concentration. Thus, the least growth was observed at the 20% concentration.
The mean growth of C. albicans in different concentrations of copper oxide nanoparticles following 48 h
Considering the significant intergroup differences in all studied pathogens calculated using the one-way ANOVA, pairwise comparisons were performed for each pathogen between different concentrations. Table 3 presents the pairwise intergroup comparisons using Tukey’s post hoc test. According to Table 3 , culture media containing E. faecalis showed significant differences in 0-1.25%, 0-2.5%, 0-5%, 0-10%, 0-20%, 0.625-1.25%, 0.625-2.5%, 0.625-5%, 0.625-10%, and 0.625-20% pairwise comparisons following 24 h of culture ( P < 0.001). Moreover, P. aeruginosa showed significantly different 24-hour growth in 0-0.625%, 0-1.25%, 0-2.5%, 0-5%, 0-10%, and 0-20% pairwise comparisons ( P < 0.001). Also, C. albicans showed significantly different growth between the 0% and 20% concentrations ( P < 0.001), as well as the 0.625% and 20% concentrations ( P = 0.002). Thus, the growth was reduced in all pathogens with increased concentrations of copper oxide nanoparticles.
The present study was the first to investigate the effect of tissue conditioners containing copper oxide nanoparticles on the growth of E. faecalis and P. aeruginosa .
The green biosynthesis of CuO nanoparticles was successfully conducted using a non-toxic, cost-effective, easy, and eco-friendly approach. These copper nanoparticles will probably be used in pharmaceutical formulations, drug delivery systems, and biomedical applications in the future since they can be prepared from natural products using a green biosynthesis method [ 32 ]. According to the findings from XRD, FTIR, and TEM investigations, the CuO nanoparticles made in the present study had monoclinic crystalline structures. Moreover, they had a suitable diameter in the nm range while maintaining their desirable properties and bonds.
Infection with P. aeruginosa is often reported in patients with apical periodontitis and pulp necrosis. Almost all patients with such infections are of lower socio-economic status and have poor oral and dental hygiene, gingivitis, and decayed teeth. The considerable resistance of P. aeruginosa to most antibiotics often makes its treatment extremely difficult, whether systematic or focal. In the present study, P. aeruginosa was used as a representative of gram-negative, antibiotic-resistant bacteria [ 22 ].
On the other hand, Enterococci are the causative agent of various infections, including endocarditis, meningitis, urinary tract, neonatal, and wound infections. Some of these infections are potentially fatal. Moreover, they are globally known as significant nosocomial pathogens, considering the growing emergence of antimicrobial-resistant phenotypes in the last few decades. Enterococci are resistant to vancomycin, tetracyclines, penicillins, cephalosporins, and aminoglycosides. Also, E. faecalis is often the cause of root canal treatment failure due to its high antibiotic resistance. In the present study, E. faecalis is the representative of gram-positive, antibiotic-resistant bacteria [ 23 , 24 ].
Considering the movement limitations of elderly patients using removable prostheses, [ 6 , 7 , 8 ] one of the clinical applications of tissue conditioners containing CuO nanoparticles is to help these patients prevent the growth of pathogenic microorganisms, which is facilitated the observance of hygiene by patients.
Previous research has reported the reactive oxygen species production and resultant oxidative stress as the potential cause of the antibacterial properties of copper nanoparticles. Moreover, these nanoparticles can show direct cytotoxicity by disrupting the membrane function, altering its permeability, and attacking different cellular structures and proteins containing phosphorus and sulfur [ 25 ]. It is worth mentioning that the present study did not use CuO concentrations higher than 20% since they exert cytotoxic effects. Moreover, we used the principles of the Minimal Inhibitory Concentration (MIC) technique to dilute the CuO nanoparticle concentration by half in each step [ 19 , 33 ]. Also, according to Chul Lee et al. the no-observed-adverse-effect levels of Cu nanoparticles and Cu micro particles were determined to be 100 and ≥ 400 mg/kg/day, respectively [ 33 ]. As nanoparticles are solid and in combination with tissue conditioner in our study, they are much harmless compared to the previous study that nanoparticles were used in solution form.
The present study used the colony counting method to assess the number of microorganisms, which is superior to the optical absorption density method since it does not count the non-viable microorganisms [ 34 ]. The reduced growth of E. faecalis and P. aeruginosa in different concentrations of CuO nanoparticles confirmed the benefit of this method. Moreover, the increasing concentration of CuO nanoparticles could directly reduce bacterial growth. Also, the 20% CuO nanoparticle concentration completely stopped the growth in both studied bacteria.
A study by Maqusood et al. evaluated the antimicrobial effect of CuO nanoparticles, reporting compatible results with the present study regarding the effect of these nanoparticles on E. faecalis and P. aeruginosa . Moreover, its effect on E. faecalis was comparable with streptomycin as the standard positive control [ 35 ]. Also, another study by Mardones et al. used CuO nanoparticles inside the root canal to suppress bacterial growth. Furthermore, they conducted an in vitro assessment of E. faecalis growth, reporting a dramatically reduced growth following 24 h compared to the negative control group, which was compatible with our findings. It seems that CuO nanoparticles have higher inhibitory effects on bacterial growth compared to Cu particles with conventional dimensions due to increased bacterial exposure to Cu and facilitated penetration into the cells of the microorganisms [ 36 ].
On the other hand, a study by Mousavi et al. used ZnO-Ag-based tissue conditioners to inhibit the growth of E. faecalis and P. aeruginosa , reporting complete growth arrest in 20% nanoparticle concentration. This study was compatible with the present study regarding the nanoparticle concentration and incubation duration. Thus, it can be concluded that ZnO-Ag and CuO nanoparticles have equal antimicrobial effects [ 27 ]. Moreover, another study investigated the antimicrobial effect of chitosan-based tissue conditioners, reporting complete growth arrest in 5% and 10% chitosan nanoparticle concentrations for P. aeruginosa and E. faecalis , respectively. Thus, it can be concluded that chitosan nanoparticles have a higher inhibitory effect on the growth of these two bacteria compared to CuO nanoparticles [ 20 ]. Also, a study by García Marin et al. compared the antimicrobial effect of Cu nanoparticles on C. albicans compared to common drugs used for treating C. albicans infections, including fluconazole, nystatin, and amphotericin B, reporting a higher antifungal effect for CuO nanoparticles compared to amphotericin B. Furthermore, the observed effect was highly concentration-dependent [ 37 ]. Thus, the mentioned study was compatible with our findings.
Geographically, propolis samples exhibit distinct chemical compositions that directly influence their antioxidant properties. For instance, ethanolic extracts of propolis from Russia and Italy demonstrate similar antioxidant effects due to the presence of shared polyphenols. In contrast, Brazilian propolis has a relatively lower antioxidant effect owing to its diminished polyphenol content [ 38 ]. However, the current understanding of the properties of Iranian propolis is limited and incomplete. Further research is required to comprehensively explore its therapeutic potential. The utilization of propolis is driven by its well-documented therapeutic properties, aiming to augment the economic value of raw propolis and facilitate the development of innovative pharmaceuticals [ 39 ].
According to Amiri et al. study, [ 40 ] copper nanoparticles have a preventive effect on infections caused by different species of Candida. Also, according to the study of Garcia-Marin et al. [ 37 ], copper oxide nanoparticles have a very high effect as a topical antifungal treatment against Candida albicans.
According to the findings of this study on the antimicrobial effects of CuO nanoparticles, it is recommended to do more research regarding the addition of these nanoparticles in heat-cured and 3D-printed denture base resins.
In the end, it is recommended to conduct further studies on the physical and mechanical properties of CuO nanoparticle-based tissue conditioners. Moreover, the antimicrobial effects of such tissue conditioners should be investigated on a more extensive range of microorganisms found in the oral cavity. More research regarding antibiotic resistance tests and biofilm formation is also recommended.
In the present study, the CuO nanoparticles were made properly in suitable sizes. Moreover, the tissue conditioners containing copper oxide nanoparticles showed acceptable antimicrobial effects against E. faecalis , P. aeruginosa , and C. albicans . Also, it is recommended to conduct further studies on this topic to find the optimal concentration of CuO nanoparticles in tissue conditioners, thereby introducing the application of nanoparticles to the field of dental material science to make commercial tissue conditioners containing copper oxide nanoparticles.
The datasets used and/or analysed during the current study available from the corresponding author on reasonable request.All data generated or analysed during this study are included in this published article [and its supplementary information files].
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This study is part of a PhD thesis at Hamadan University of Medical Sciences. The study was funded by Vice-chancellor for Research and Technology, Hamadan University of Medical Sciences (Code number: 140104212693).
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Department of Prosthodontics, School of Dentistry, Hamadan University of Medical Sciences, Hamadan, Iran
Saeed Nikanjam & Aria Yeganegi
Department of Microbiology, Faculty of Medicine, Hamadan University of Medical Sciences, Hamadan, Iran
Mohammad-Yousef Alikhani
Dental Implant Research Center, School of Dentistry, Hamadan University of Medical Sciences, Hamadan, Iran
Abbas Farmany
Department of Medical Parasitology and Mycology Department, School of Medicine, Hamadan University of Medical Sciences and Health Services, Hamadan, Iran
Seyed Amir Ghiasian
Department of Biostatistics, School of Public Health and Research Center for Health Sciences, Hamadan University of Medical Sciences, Hamadan, Iran
Roghayeh Hasanzade
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Saeed Nikanjam: A Aria Yeganegi2: B Mohammad-Yousef Alikhani: C Abbas Farmany: D Seyed Amir Ghiasian: ERoghayeh Hasanzade: Fconception: A, Bdesign of the work : A, Bthe acquisition, analysis: C, D, E, Finterpretation of data: A, B, F the creation of new software used in the work: D.
Correspondence to Saeed Nikanjam .
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This study was approved by an ethics committee of Hamadan University of Medical Sciences (Ethics No. IR.UMSHA.REC.1400.1004). Informed consent was obtained from the participants.
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Nikanjam, S., Yeganegi, A., Alikhani, MY. et al. Novel antimicrobial applications of copper oxide nanoparticles after combination with tissue conditioner used in complete prostheses. BMC Oral Health 24 , 752 (2024). https://doi.org/10.1186/s12903-024-04534-w
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DOI : https://doi.org/10.1186/s12903-024-04534-w
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ZnO nanoparticles were recommended by Bagabas et al. [106] for environmental applications. They synthesized ZnO nanoparticles from wet chemical route with cyclohexylamine in aqueous and enthanolic medium and detected the photodegradation of cyanide ions. ... (PhD Thesis) (2012) Google Scholar [3] H.N. Bose. Luminescence and allied phenomena ...
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