5.2
Impact Factor
Generic selectors
Exact matches only
Search in title
Search in content
Post Type Selectors
Search in posts
Search in pages
Filter by Categories
Corrigendum
Current Issue
Editorial
Erratum
Full Length Article
Full lenth article
Letter to Editor
Original Article
Research article
Retraction notice
Review
Review Article
SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY
5.3
Impact Factor
Generic selectors
Exact matches only
Search in title
Search in content
Post Type Selectors
Search in posts
Search in pages
Filter by Categories
Corrigendum
Current Issue
Editorial
Erratum
Full Length Article
Full lenth article
Letter to Editor
Original Article
Research article
Retraction notice
Review
Review Article
SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY
View/Download PDF

Translate this page into:

Original Article
2025
:18;
4632025
doi:
10.25259/AJC_463_2025

Au NPs immobilized over polydopamine-modified ZnO NPs: Catalysis over Sonogashira coupling and cytotoxic analysis against bladder cancer

, , ,
 Department of Urology, Shanxi Province Cancer Hospital, Shanxi Hospital Affiliated to Cancer Hospital, Chinese Academy of Medical Sciences, Cancer Hospital Affiliated to Shanxi Medical University, No. 3, Workers new street, Taiyuan, 030013, China

*Corresponding author: E-mail address: doctorzc1005@163.com (C. Zhang)

Received: , Accepted: ,
© 2025 Arabian Journal of Chemistry - Published by Scientific Scholar
Licence
This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-Share Alike 4.0 License, which allows others to remix, transform, and build upon the work non-commercially, as long as the author is credited and the new creations are licensed under the identical terms.

Abstract

In this study, a novel, simple, and ecologically safe way to design an Au/ZnO composite was achieved using a polydopamine (PDA) biopolymer as a reductant and encapsulating media. The anchored gold ions were reduced over the PDA-modified ZnO effectively without any harsh reagents. The abundant amino- and hydroxyl-groups over PDA functioned as green reducing agents to cap and reduce Au ions on the ZnO surface. The planned nanocomposites’ effective synthesis was confirmed by field emission-scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX), elemental mapping, transmission electron microscopy (TEM), inductively coupled plasma (ICP), and X-ray diffraction (XRD) analysis. Additionally, the ZnO@PDA/Au nanoparticles (NPs) demonstrated potent catalytic activity via Sonogashira coupling in the C-C bond formation mechanism. It is possible to recycle ZnO@PDA/Au after eight consecutive reaction cycles. The synthesis of many stilbene derivatives was accomplished by efficiently coupling phenyl acetylene with aryl halides. The bio-application of the ZnO@PDA/Au nanocomposite for anti-bladder cancer (BC) research against the related cell lines 5637 and TCCSUP was also investigated in vitro using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. In a dose-dependent fashion, the material decreased the cell survival of the malignant breast cell line. The cell lines’ respective IC50 values for the nanocomposite were found to be 208 and 195 μg/mL. ZnO@PDA/Au NPs were used in a 2,2-Diphenyl-1-picrylhydrazyl (DPPH) experiment to assess the antioxidant activity, and the findings revealed an IC50 value of 198 µg/mL. Soon, cancer treatment may appear quite promising given the impressive results demonstrated by the produced nanocomposite.

Keywords

Au NPs
Bladder cancer
C-C coupling
Polydopamine
ZnO

1. Introduction

Recent years have seen a surge in interest in metal nanoparticle (NP)-based catalysis derived from their exclusive catalytic properties due to exceptional surface-to-volume proportion, large number of surface active atoms, and other physicochemical features [1-2]. Shape and dimension of NPs are the two most crucial factors, which result in the formation of readily accessible chemical reactant binding sites on their surface. But after the reaction is finished, the NPs’ extremely tiny size makes it more difficult to separate and retrieve them [3-5]. Agglomeration is another issue with free and pure NPs, which significantly lowers their dispersion in solution and catalytic efficiency. Alumina, silica spheres, zeolites, Santa Barbara amorphous-15 (SBA-15), carbonaceous materials, and polymeric substrates are some of the supports used to stabilize the NPs and prevent their aggregation, thereby providing higher dispersion in polar and non-polar fluids [6-14]. However, a significant drop in reactivity occurred due to the adsorption of the NPs on the membrane surface, rendering the reactor system useless. One of the most practical solutions to all aforementioned issues is to immobilize the NPs on the support surface and within its pores through appropriate chemical modification, either by grafting polymer brushes or by employing various crosslinking or coupling agents.

In this study, we are motivated to offer a novel material in which Au NPs are produced on top of ZnO NPs functionalized with polydopamine (PDA). According to numerous reports, ZnO is a semiconductor belonging to groups II and VI that possesses a large and stable band gap (3.37 eV) at an ambient temperature. Characteristics of ZnO NPs, including shape, crystal size, band gap value, and enhanced catalytic capabilities, are influenced by element doping [15,16]. PDA coatings have garnered considerable attention recently as a universal surface-modifying agent and biomimetic polymer for various materials with a wide range of applications [17,18]. The bio-inspired synthesis of NPs is facilitated by the electron-rich environment created by the free hydroxyls and amines present [19,20]. PDA is expected to enable the entry of [AuCl4]_ ions to adsorb onto the ZnO NP support and then be reduced in situ to Au NPs. Adsorption of [AuCl4]_ anions to its hydroxyl and amine groups and in situ reduction of the adsorbed anions to Au NPS are thus the two functions that the PDA modified surface offers. As a result, this green synthesis does not require an external hazardous reducing agent.

The electron-rich functionalities of biomolecules provide bio-NPs with a notable degree of stability. Additionally, the biogenic synthesis approach provides new and structurally complicated entities linked to shape-controlled protocols. Hence, these protocols have been followed by numerous research groups [21-37]. Because of their many uses, Au NPs have attracted particular attention, as demonstrated by the recent articles on biogenic Au NPs [38-40]. Significant uses for Au NPs include colorimetric DNA detection, biological transmission electron microscopy (TEM), organo-pollutant degradation, disease diagnostics, nanomedicine, and catalysis [41-43]. Due to their distinct characteristics, Au NPs have significant catalytic activity when it comes to the production of fine organic compounds. The form, surface state, high surface-to-volume ratios, and evidently negative redox potential of Au NPs are all associated with their remarkable catalytic activity [44-46].

The potential of the synthesized ZnO@PDA/Au NPs in catalytic Sonogashira C-C coupling processes and in biological evaluation for bladder cancer (BC) proliferation suppression has been investigated. One of the strongest and most studied synthetic transformations is carbon-carbon bond formation, involving Heck, Hiyama, Negishi, Sonogashira, Stille, and Suzuki coupling catalyzed over transition metals, being very essential in the manufacture of diverse agents of everyday synthetic utility. [47-51]. Numerous research articles attest to the exceptional studies that have been carried out because of their noteworthy theoretical and practical significance [52,53]. However, we believe there are still numerous areas where the methodology can be improved, which is why we worked diligently to achieve the results. Over ZnO@PDA/Au NPs, a variety of C-C compounds (stilbenes) have been produced, providing exceptional yields in short reaction times.

Furthermore, the biological use of ZnO@PDA/Au NPs was extended to the prevention and treatment of human BC. Hematuria, recurrent and agonizing urination, and back pain are all possible indications. Imaging, urine cytology, and cystoscopy are used for diagnosis [54-57]. The reported recurrence rate for BC has been between 50-90% over the past five years, despite numerous attempts to reduce the recurrence and progression. This is due to inadequate diagnosis and treatment [58, 59]. Therefore, further techniques are urgently needed to improve BC treatments’ therapeutic and diagnostic performance. Recent uses of biogenic Au NPs include cancer diagnostics and the in vitro and in vivo administration of these particles as chemotherapeutic drugs. This has been crucial in treating human BC cells, such as 5637 and TCCSUP, with the ZnO@PDA/Au NPs nanocomposite, which has produced promising results.

2. Materials and Methods

2.1. Preparation of ZnO@PDA composite

Through ultrasonication, 20 mL of triethylene glycol (TEG), and 300 mg of zinc acetate were combined. The mixture was then heated for 5 h to cause reflux. The homogenous suspension was allowed to cool before ethyl acetate was added. After being collected by centrifugation and repeatedly cleaned with ethyl acetate, the pure ZnO NPs were vacuum-dried. Next, dopamine (0.05 g) was introduced to tris buffer (200 mL, 10 mM, pH = 8.5) after 0.5 g of ZnO NPs had been introduced. For 24 h at 25°C, the resultant mixture was vigorously churned. Following the reaction, the ZnONPs@PDA composite was separated by centrifugation, repeatedly cleaned using a 1:1 DI H2O-EtOH mixture, and then dried at 40°C.

2.2. Preparation of ZnO@PDA/Au NPs

The synthesized ZnO NPs@PDA (0.5 g) were sonicated in 100 mL of water. A 30 mL aqueous solution of 0.030 g of HAuCl4 was then added dropwise to it, and the mixture was triturated for 60 min at 80°C. After isolation, the ZnO@PDA/Au NPs were washed with distilled water, followed by 1:1 EtOH, before being dried for 24 h at 40°C. By using inductively coupled plasma-atomic emission spectroscopy (ICP-AES), the Au loading was found to be 0.036 mmol/g.

2.3. ZnONPs@PDA/Au catalyzed sonogashira coupling

In a standard reaction process, a reaction mixture including the ZnO@PDA/Au NPs catalyst (0.5 mol% %Au), phenylacetylene (1.1 mmol), haloarene (1 mmol), and Et₃N (2 mmol), in dimethyl formamide (DMF) (3 mL) was agitated at 100°C for the requisite time. Thin layer chromatography (TLC) was used to monitor the reaction’s progress, and after the catalyst was retrieved by centrifugation. After the reaction, the filtrate was extracted using EtOAc; the organic layer was dried and concentrated. Finally, acetone/petroleum ether (20%) was used as the eluent in column chromatography to purify the final products. All the products were authenticated by comparing them with data from the literature.

2.4. Antioxidant potential of ZnO NPs@PDA/Au nanocomposite

A biological specimen or a pharmaceutical drug’s antioxidant potential is usually determined through the 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assay. The ZnO@PDA/Au material suspension (5 mL) in different concentrations (1-1000 μg/mL) was mixed with ethanolic DPPH solution (0.2 mM, 1 mL), incubated, and after kept in the dark for a certain amount of time. It made the purple DPPH solution progressively vanish, and the UV-absorption spectra were recorded at 517 nm. The % inhibition or DPPH scavenging capacity was then calculated with the Eq. (1)

(1)
Inhibition   ratio   ( % ) = Abs   of   control − Abs   of   sample Abs   of   control × 100

2.5. Anti-BC potential of GO-CS/Au nanocomposite

The well-known 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric study was used to evaluate the cytotoxicity and anti-BC potential of the ZnO@PDA/Au NPs nanocomposite over the 5637 and TCCSUP cell lines. The related cells were initially cultured in appropriate media and preservatives (RPMI-1640 media, 10% FBS, 1% penicillin-streptomycin antibiotic) to enhance their efficiency and promote their proliferation in a humidified incubator with a CO2 environment at 37°C. The medium was taken out when they were cultured with around 85% confluency. The cells were then rinsed with FBS, treated with 0.5 mL of trypsin, and allowed to sit for 3 h. Following their removal from the incubator, the cells were monitored under an inverted microscope. 0.2 mL of RPMI-1640 growth medium per well was used to seed the cells in 96-well plates. The cells were treated with different concentrations of ZnO@PDA/Au NPs (5-1000 μg/mL) nanocomposite after a 24-h rest period. MTT solution was then employed in combination with Fetal bovine serum (FBS) media (10 μL). It enters the cell membrane and forms the purple formazan crystals after interacting with active cells. A microtiter plate reader set at 570 nm was used to measure the absorbance after the formazan was dissolved in DMF. The following formula was used to calculate the proportion of viable cells (Eq. 2).

(2)
Cell   viability   % = Total   cells − Dead   cells Total   cells ⋅ 100

3. Results and Discussion

3.1. Characterization of the synthesized ZnO@PDA/Au NPs nanocomposite

Several hydroxyl and amino organ functions in the PDA biomolecule, a biopolymer, were used as templates for the biogenic synthesis of ZnO@PDA/Au NPs. Mechanistically, the entering Au3+ ions were first encapsulated by these electron-rich organ functions by coordination, which was followed by the corresponding ions’ sustained reduction into NPs. Additionally, by coordinating with them, the Au NPs as synthesized guarantee stability. Scheme 1 shows the corresponding synthesis pathway. Additionally, the nanocomposite was physicochemically evaluated using advanced physicochemical techniques such as elemental mapping, X-ray diffraction (XRD), inductively coupled plasma (ICP), TEM, energy-dispersive X-ray (EDX), and field emission-scanning electron microscopy (FE-SEM).

Schematic synthesis of ZnO@PDA/Au NPs and its catalytic application in the Sonogashira coupling reactions.
Scheme 1.
Schematic synthesis of ZnO@PDA/Au NPs and its catalytic application in the Sonogashira coupling reactions.

The ZnO@PDA/Au NPs bio-nanomaterial’s shape, texture, and particle size were initially assessed by FE-SEM analysis, as shown in Figure 1. The particles have a fluffy cotton-like shape and fall within the nanometric range. It was discovered that the average particle size ranged from 30-40 nm. Nevertheless, the image did not allow for the independent identification of the ZnO@PDA composite or the Au NP deposition on its surface. Manual sample preparations indicated that the particles appeared clumped together.

FE-SEM image of ZnO@PDA/Au NPs
Figure 1.
FE-SEM image of ZnO@PDA/Au NPs

An elemental analysis using EDX was performed following FE-SEM study. Au, Zn, C, N, and O were confirmed to be constituents of the ZnO@PDA/Au NPs, as illustrated in Figure 2. The metals indicated the as-schemed structure, whereas the non-metals C, N, and O validated the PDA biocomposite. Additionally, elemental mapping analysis (Figure 3) was carried out to bolster the EDX results. The compositional species have been represented by colored dots that are scattered in a reasonably homomorphic fashion in an X-ray scan of a portion of an FE-SEM picture. The homogeneity of the components would surely have a significant impact on the chemical or biological properties of the material.

EDX spectrum of ZnO@PDA/Au NPs.
Figure 2.
EDX spectrum of ZnO@PDA/Au NPs.
Elemental mapping of ZnO@PDA/Au NPs
Figure 3.
Elemental mapping of ZnO@PDA/Au NPs

To further understand the inherent structure of the ZnO@PDA/Au bio-nanocomposite, TEM analyses were employed. The findings at various magnifications have been shown in Figure 4. The images accurately depict the grey-colored ZnO NP bulk and the faded PDA outer layer on top of it, as expected. Still, the most obvious sign of Au NPs were the black, spherical particles that were widely scattered. They are typically non-aggregated and between 10 and 15 nm in size.

TEM images of ZnO@PDA/Au NPs.
Figure 4.
TEM images of ZnO@PDA/Au NPs.

3.2. Catalytic application of ZnO@PDA/Au NPsnanocomposite

The catalytic activity of the synthesized material was assessed through Sonogashira coupling. To find the ultimate reaction conditions, optimization seemed crucial at first; therefore, iodobenzene and phenylacetylene were reacted as a probe. Table 1 documents the results of the search for the ideal conditions using variable parameters like base, catalyst load, solvent, and temperature. The catalyst and additional base are crucial to the reaction, and their absence could prevent the reaction from succeeding (entry 13, 18). A 60% yield was obtained in 12 h by first reacting the substrates with K2CO3 as the base and 0.5 mol% of Au-loaded catalyst in DMF medium at 100oC. Other conditions were maintained while experimenting with different solvents, such as acetonitrile, H2O, EtOH, and their mixes, as well as solvent-free circumstances, which resulted in mediocre yields and less than 60%. The best solvent for this reaction was determined to be DMF. The reaction was then screened using several additional bases, including Na2CO3, NaHCO3, K3PO4, and Et3N, the last of which produced the highest yield (entry 10, 98%) in just 5 h of reaction. Again, changing the temperature or the Au load did not yield better outcomes. Et3N as a base, DMF as a solvent, and 0.5 mol% catalyst at 100°C thus provided the optimal reaction conditions.

Table 1. Optimization of reaction between benzene iodide with phenylacetylene.a
Entry Solvent Base Au (mol%) T (°C) t (h) Yield (%)b
1 DMF K2CO3 0.5 100 12 60
2 H2O K2CO3 0.5 100 12 50
3 EtOH K2CO3 0.5 80 12 45
4 CH3CN K2CO3 0.5 80 12 50
5 H2O/EtOH (1:1) K2CO3 0.5 80 5 45
6 H2O/EtOH (1:2) K2CO3 0.5 80 5 50
7 H2O/EtOH (2:1) K2CO3 0.5 80 5 55
8 Solvent-free K2CO3 0.5 100 12 50
9 DMF Na2CO3 0.5 100 12 75
10 DMF Et3N 0.5 100 5 98
11 DMF NaHCO3 0.5 100 10 80
12 DMF K3PO4 0.5 100 7 65
13 DMF No base 0.5 100 12 0
14 DMF Et3N 0.5 50 10 75
15 DMF Et3N 0.5 120 5 98
16 DMF Et3N 0.4 100 8 75
17 DMF Et3N 0.6 100 5 98
18 DMF Et3N 0.0 100 24 0
aReaction conditions: Benzene iodide (1.0 mmol), phenylacetylene (1.1 mmol), base (2 mmol), catalyst, and solvent (3 mL).
bIsolated yields.

Subsequently, by examining the generalized conditions throughout a range of aryl halides, they were further confirmed. Aryl iodide and aryl bromide with variable functionality effectively interacted with phenylacetylene to afford the required products in very good to outstanding yields, as shown in Table 2. The same conditions were employed in parallel with chloroarenes; however, even after a 24-h reaction, none of them worked. Aryl halides have a reactivity order of I>Br>Cl, which was clearly determined by leaving capacity ground. Very good results were obtained from the calculation of the corresponding turnover number (TON) and turnover frequencies (TOF) for the successful reactions.

Table 2. ZnO@PDA/Au NPs catalyzed Sonogashira coupling.a
Entry R X Time (h) Yield (%)b TOF (h-1)c TON (h-1)d
1 H I 5 98 39.2 196
2 H Br 8 90 22.5 180
3 H Cl 24 0 0 0
4 4-CH3O I 5 98 39.2 196
5 4-CH3O Br 8 88 22 176
6 4-CH3O Cl 24 0 0 0
7 4-CH3 I 6 98 32.6 196
8 4-CH3 Br 7 92 26.2 184
9 4-CH3 Cl 24 0 0 0
10 4-Cl I 5 96 38.4 192
11 4-Cl Br 7 80 22.8 160
12 4-Cl Cl 24 0 0 0
aReaction conditions: Arylhalide (1 mmol), phenylacetylene (1.1 mmol), Et3N (2 mmol), DMF (3 mL), catalyst (0.5mol%Au) and 100°C; bIsolated yield.
cTOF, TOF = (yield/time)/amount of catalyst (mol).
dTON, TON = yield/amount of catalyst (mol).

3.3. Study of catalytic reusability

It is crucial to investigate reusability in heterogeneous catalysis. A centrifuge was used to isolate the nanocatalyst following the conclusion of a new set of probe reactions. After a thorough aqueous ethanol wash, it was dried. Later reaction batches utilized the regenerated active catalyst. It’s interesting to note that the catalyst was sufficiently resilient to be utilized for eight consecutive cycles with nearly unchanged reactivity (Figure 5). Due to the weak leaching of the catalytic material into the solution, a slight loss was seen following the seventh batch. The material’s durability was investigated through leaching studies. Results from the seventh run’s ICP-optical emission spectroscopy (OES) examination of the filtrate showed that a trace amount of Au leaching had occurred. The hot filtering test was followed by a second investigation to determine the catalyst’s true heterogeneity. At the midway point (15 min, 67%), the catalyst was recovered by centrifugation, and the reaction was then allowed to continue in that state. The yield of the reaction was highly heterogeneous and did not further develop.

Reusability of the ZnO@PDA/Au NPs in the model reaction.
Figure 5.
Reusability of the ZnO@PDA/Au NPs in the model reaction.

3.4. Study of reaction mechanism

A likely approach for the ZnO@PDA/Au NPs catalyzed Sonogashira coupling of phenyl acetylene and aryl halides has been suggested when examining the reaction sequence (Scheme 2). According to the mechanism, the reaction pathway follows oxidative addition and subsequent reductive elimination. The Et3N base promotes the abstraction of the terminal hydrogen of phenyl acetylene, which starts the suggested reaction process. The Au-phenyl acetylide intermediate is produced when the corresponding acetylide ion attaches to the Au NP catalytic site. Aryl halide is then added to this catalytic site through oxidative addition, converting Au0 to AuI. The coupling with acetylide intermediate immediately follows the breaking of the Ar-X link within the adsorbed aryl halide, which is the critical step in this process. Reductive elimination leads to its eventual release from the catalyst surface. The DMF solvent is expected to be an excellent reducing agent, helping to regenerate the catalyst by reducing Au(I) back to metallic gold.

Plausible pathway for Sonogashira coupling catalyzed by ZnO@PDA/Au NPs.
Scheme 2.
Plausible pathway for Sonogashira coupling catalyzed by ZnO@PDA/Au NPs.

3.5. Investigation of antioxidant potency and cytotoxicity of ZnO@PDA/AuNPs

Numerous in vitro studies have shown Au nanocomposites to possess remarkable antioxidant qualities. Because they may fight oxidative stress, antioxidant compounds linked to Au NPs have demand in the top-notch health management sector. Several studies have demonstrated the strong antioxidant potential of materials with remarkable anti-tumor properties and the capacity to cause cell death in cancer. This study used the well-known DPPH assay to demonstrate ZnO@PDA/Au NPs’ antioxidant capacity. The DPPH solution and the suggested antioxidant sample were mixed in equal parts (150 µL, 0.04 mg/mL, EtOH) at six distinct doses (31.25-1000 μg/mL). When the radical was finally extinguished, the purple hue changed to a light yellow. To ascertain the material’s antioxidant capacity, its UV absorbance was then measured. The percentage of inhibitions was subsequently calculated using equation 1. The GO-CS/Au nanocomposite’s IC50 value against DPPH was evaluated as 198 µg/mL, as shown in Figure 6.

Antioxidant activity of ZnO@PDA/Au NPs nanocomposite.
Figure 6.
Antioxidant activity of ZnO@PDA/Au NPs nanocomposite.

Following a noteworthy antioxidant capability observed in the MTT experiment, the cytotoxicity of the ZnO@PDA/Au nanocomposite against the BC cell lines (5637 and TCCSUP) was examined. Since absorbance and cellular activity have a proportional relation, the MTT test, which gauges cell growth rate, may identify cell proliferation with high sensitivity and precision. Because of its cationic and lipophilic properties, the inner mitochondrial membrane of an organism is one of the several cell membranes that the MTT reagent can cross. Additionally, cells that are metabolically active convert it to formazan. After cells have been exposed to MTT for a few hours, it is standard procedure to perform the MTT assay. The subsequent procedure has been outlined in section 2.5.

The proportion of toxicity drops as the load of ZnO@PDA/Au material gets enhanced, as seen in Figures 7-8. TCCSUP and 5637 cell lines were found to have IC50 values of 195 and 208 µg/mL, respectively. The data showed that the cell line with the smallest IC50 value, TCCSUP, produced better results. Therefore, our research clearly shows that ZnO@PDA/Au NPs significantly inhibit the growth of human BC cells. Accordingly, ZnO@PDA/Au was treated on the human umbilical vein endothelial cell (HUVEC) cell line to examine the effect of this cytotoxic substance on normal cells. It was shown that the cells suffered minutely damaged, which strongly supports its effectiveness against malignant bladder cells. ZnO@PDA/Au nanocomposite mechanistically caused mitochondrial damage by drastically reducing the amount of adenosine tri phosphate (ATP) in the cell. Furthermore, Au NPs have become more cytotoxic due to their significant ability to create reactive oxygen species (ROS). Because the dead cells lacked the enzyme that keeps them colorless, formazan, when introduced to the growing cells, was not produced by the ZnO@PDA/Au nanocomposite.

In vitro toxicity analysis of ZnO@PDA/Au NPson TCCSUP.
Figure 7.
In vitro toxicity analysis of ZnO@PDA/Au NPson TCCSUP.
In vitro toxicity analysis of ZnO@PDA/Au NPs on 5637.
Figure 8.
In vitro toxicity analysis of ZnO@PDA/Au NPs on 5637.

4. Conclusions

In summary, the catalytic and biological efficiency of the ZnO@PDA/Au nanocomposite has been successfully demonstrated in this study. ZnO NPs functionalized with the PDA biomolecule were used to create Au NPs in a green-metric manner. The successful synthesis and essential properties of the nanocomposite were determined by characterization using FE-SEM, TEM, EDX, elemental mapping, and XRD. According to a TEM analysis, tiny Au NPs with sizes ranging from 15 to 20 nm are embedded throughout the PDA-functionalized ZnO surface without clumping together. Furthermore, standards-supported XRD examination revealed a crystalline, high-purity substance. The material’s potential application in chemical catalysis, specifically in the Sonogashira coupling-mediated C-C bond formation reaction, was examined. Several stilbene compounds were synthesized with remarkable yields, with very good TON and TOF in comparatively less time. Without a noticeable drop-in activity, the catalyst was recovered by centrifugation and reused for eight consecutive runs. The cytotoxic properties of the ZnO@PDA/Au nanocomposite were further examined in a biological study using BC cell lines (5637 and TCCSUP). Based on the results of the MTT experiment, the material’s corresponding IC50 was found to be 208 and 195 µg/mL, respectively. Using the DPPH assay, the material’s relative IC50 value of 198 µg/mL demonstrated that it was once again a potent antioxidant.

Acknowledgment

The authors are thankful to Shanxi Hospital Affiliated to Cancer Hospital, Shanxi Province Cancer Hospital for providing technical support.

CRediT authorship contribution statement

Wei Wang: Conceptualization, writing original draft, Kai Wu: Investigation, software, Tianjun Xing: Validation, review original draft, Chao Zhang: Project supervision, administration.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Declaration of Generative AI and AI-assisted technologies in the writing process

The authors confirm that there was no use of artificial intelligence (AI)-assisted technology for assisting in the writing or editing of the manuscript and no images were manipulated using AI.

References

  1. , , , , . Enhanced catalytic properties of palladium nanoparticles deposited on a silanized ceramic membrane support with a flow-through method. Industrial & Engineering Chemistry Research. 2013;52:14099-14106. https://doi.org/10.1021/ie401903v
    [Google Scholar]
  2. , , , , , , , . Nanocomposite coatings with stimuli-responsive catalytic activity. RSC Advances. 2014;4:17579-17586. https://doi.org/10.1039/c4ra02098g
    [Google Scholar]
  3. , , , , , . Shape control of silver nanoparticles by stepwise citrate reduction. The Journal of Physical Chemistry C. 2009;113:6573-6576. https://doi.org/10.1021/jp900775b
    [Google Scholar]
  4. , , , . Selective hydrogenation by Pd nanoparticles embedded in polyelectrolyte multilayers. Journal of the American Chemical Society. 2004;126:2658-2659. https://doi.org/10.1021/ja038804c
    [Google Scholar]
  5. , , . Efficient degradation of azo dyes using Ag and Au nanoparticles stabilized on graphene oxide functionalized with PAMAM dendrimers. New Journal of Chemistry. 2014;38:1551. https://doi.org/10.1039/c3nj01050c
    [Google Scholar]
  6. , , , . Preparation of alumina supported gold catalysts: Influence of washing procedures, mechanism of particles size growth. Applied Catalysis A: General. 2006;298:57-64. https://doi.org/10.1016/j.apcata.2005.09.020
    [Google Scholar]
  7. , , , , . Degradation of decabromodiphenyl ether by nano zero-valent iron immobilized in mesoporous silica microspheres. Journal of Hazardous Materials. 2011;193:70-81. https://doi.org/10.1016/j.jhazmat.2011.07.024
    [Google Scholar]
  8. , , , , , . Preparation of nano-gold in zeolites for CO oxidation: Effects of structures and number of ion exchange sites of zeolites. Applied Catalysis A: General. 2005;291:162-169. https://doi.org/10.1016/j.apcata.2005.02.038
    [Google Scholar]
  9. , , , , , , . In situ controlled growth of well-dispersed Au nanoparticles inside the channels of SBA-15 using a simple, bio-inspired method for surface-enhanced Raman spectroscopy. RSC Advances. 2013;3:10154. https://doi.org/10.1039/c3ra41338a
    [Google Scholar]
  10. , , , , , , . A highly efficient catalyst: In situ growth of Au nanoparticles on graphene oxide–Fe3O4 nanocomposite support. Chemical Engineering Journal. 2014;236:1-8. https://doi.org/10.1016/j.cej.2013.09.080
    [Google Scholar]
  11. , , , , , , . Supported Pd NPs over polydopamine modified-ordered mesoporous carbon (CMK-3) as an efficient and recyclable nanocatalyst for oxidative esterification of arylaldehydes. Inorganic Chemistry Communications. 2024;160:111869. https://doi.org/10.1016/j.inoche.2023.111869
    [Google Scholar]
  12. , , , , , , , . Investigation of catalytic potential of Au NPs adorned surface modified mesoporous silica towards the reduction of 4-nitrophenol. Inorganic Chemistry Communications. 2024;159:111902. https://doi.org/10.1016/j.inoche.2023.111902
    [Google Scholar]
  13. , , , , , . Synthesis of pomegranate peel extract functionalized magnetic graphene oxide: Production of biodiesel and quantitative determination of harmful organic colorant in environmental waters. Journal of Physics and Chemistry of Solids. 2023;183:111566. https://doi.org/10.1016/j.jpcs.2023.111566
    [Google Scholar]
  14. , , , , , . Fabrication and characterization of Fe/Ni nanoparticles supported by polystyrene resin for trichloroethylene degradation. Chemical Engineering Journal. 2016;283:730-739. https://doi.org/10.1016/j.cej.2015.07.076
    [Google Scholar]
  15. , , , , . Journal of Physical Chemistry. 2017;121:14083-14087.
  16. , . Industrial and Engineering Chemical Research. 2017;56:7184-7191.
  17. , , . Bioinspired catecholic chemistry for surface modification. Chemical Society Reviews. 2011;40:4244-4258. https://doi.org/10.1039/c1cs15026j
    [Google Scholar]
  18. , , , . Mussel-inspired surface chemistry for multifunctional coatings. Science (New York, N.Y.). 2007;318:426-430. https://doi.org/10.1126/science.1147241
    [Google Scholar]
  19. , , , , . Palladium nanoparticles anchored polydopamine-coated graphene oxide/Fe3O4 nanoparticles (GO/Fe3O4@PDA/Pd) as a novel recyclable heterogeneous catalyst in the facile cyanation of haloarenes using K4[Fe(CN)6] as cyanide source. Journal of Industrial and Engineering Chemistry. 2020;90:379-388. https://doi.org/10.1016/j.jiec.2020.06.030
    [Google Scholar]
  20. , , , . In situ decoration of Au NPs over polydopamine encapsulated GO/Fe3O4 nanoparticles as a recyclable nanocatalyst for the reduction of nitroarenes. Scientific Reports. 2021;11:12362. https://doi.org/10.1038/s41598-021-90514-x
    [Google Scholar]
  21. , , , , , . Synthesis of silver and gold nanoparticles using antioxidants from blackberry, blueberry, pomegranate, and turmeric extracts. ACS Sustainable Chemistry & Engineering. 2014;2:1717-1723. https://doi.org/10.1021/sc500237k
    [Google Scholar]
  22. , , , , , . Effect of substrates on catalytic activity of biogenic palladium nanoparticles in C–C cross-coupling reactions. ACS Omega. 2019;4:3329-3340. https://doi.org/10.1021/acsomega.8b02697
    [Google Scholar]
  23. , , . Plant‐mediated biogenic synthesis of palladium nanoparticles: Recent trends and emerging opportunities. ChemBioEng Reviews. 2017;4:18-36. https://doi.org/10.1002/cben.201600017
    [Google Scholar]
  24. , , , , , , , . Biogenic flower-shaped Au–Pd nanoparticles: Synthesis, SERS detection and catalysis towards benzyl alcohol oxidation. Journal of Materials Chemistry A. 2014;2:1767-1773. https://doi.org/10.1039/c3ta13922k
    [Google Scholar]
  25. , , , . Pd-based nanoparticles: Plant-assisted biosynthesis, characterization, mechanism, stability, catalytic and antimicrobial activities. Advances in Colloid and Interface Science. 2020;276:102103. https://doi.org/10.1016/j.cis.2020.102103
    [Google Scholar]
  26. , , , . Green synthesis of the Cu/sodium borosilicate nanocomposite and investigation of its catalytic activity. Journal of Alloys and Compounds. 2018;763:1024-1034. https://doi.org/10.1016/j.jallcom.2018.05.012
    [Google Scholar]
  27. , , . Melissa Officinalis L. leaf extract assisted green synthesis of CuO/ZnO nanocomposite for the reduction of 4-nitrophenol and Rhodamine B. Separation and Purification Technology. 2018;191:295-300. https://doi.org/10.1016/j.seppur.2017.09.044
    [Google Scholar]
  28. , , . Achillea millefolium L. extract mediated green synthesis of waste peach kernel shell supported silver nanoparticles: Application of the nanoparticles for catalytic reduction of a variety of dyes in water. Journal of Colloid and Interface Science. 2017;493:85-93. https://doi.org/10.1016/j.jcis.2017.01.012
    [Google Scholar]
  29. , , , . Green synthesis of Ag nanoparticles/clinoptilolite using Vaccinium macrocarpon fruit extract and its excellent catalytic activity for reduction of organic dyes. Journal of Alloys and Compounds. 2017;719:82-88. https://doi.org/10.1016/j.jallcom.2017.05.135
    [Google Scholar]
  30. , . Green synthesis of Pd nanoparticles mediated by Euphorbia thymifolia L. leaf extract: Catalytic activity for cyanation of aryl iodides under ligand-free conditions. Journal of Colloid and Interface Science. 2016;469:191-195. https://doi.org/10.1016/j.jcis.2016.02.024
    [Google Scholar]
  31. , , , , . Biosynthesis of the palladium/sodium borosilicate nanocomposite using Euphorbia milii extract and evaluation of its catalytic activity in the reduction of chromium(VI), nitro compounds and organic dyes. Materials Research Bulletin. 2018;102:24-35. https://doi.org/10.1016/j.materresbull.2018.01.032
    [Google Scholar]
  32. , , , , , . Cuscuta reflexa leaf extract mediated green synthesis of the Cu nanoparticles on graphene oxide/manganese dioxide nanocomposite and its catalytic activity toward reduction of nitroarenes and organic dyes. Journal of the Taiwan Institute of Chemical Engineers. 2018;86:158-173. https://doi.org/10.1016/j.jtice.2017.12.017
    [Google Scholar]
  33. , , , , . Green synthesis of silver nanoparticles using Eucalyptus leucoxylon leaves extract and evaluating the antioxidant activities of extract. Natural Product Research. 2014;28:1964-1969. https://doi.org/10.1080/14786419.2014.918124
    [Google Scholar]
  34. , , , . Procedure optimization for green synthesis of silver nanoparticles by aqueous extract of Eucalyptus oleosa. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy. 2015;136:1249-1254. https://doi.org/10.1016/j.saa.2014.10.010
    [Google Scholar]
  35. , , , , , . Facile synthesis of silver nanoparticles using Tribulus longipetalus extract and their antioxidant and antibacterial activities. International Journal of Food Properties. 2017;20:922-930.
    [Google Scholar]
  36. , , , , , , , , . Investigation of the synergic effect of silver on the photodegradation behavior of copper chromite nanostructures. Journal of Material Science : Material of Electronics. 2019;30:13994-14006.
    [Google Scholar]
  37. , , , . Facile synthesis of imidazoles by an efficient and eco-friendly heterogeneous catalytic system constructed of Fe3O4 and Cu2O nanoparticles, and guarana as a natural basis. Inorganic Chemistry Communications. 2021;125:108465. https://doi.org/10.1016/j.inoche.2021.108465
    [Google Scholar]
  38. , , , , , , . Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles. Journal of Environmental Sciences (China). 2017;55:236-246. https://doi.org/10.1016/j.jes.2016.05.044
    [Google Scholar]
  39. , , . Biogenic gold nanoparticles synthesis mediated by Mangifera indica seed aqueous extracts exhibits antibacterial, anticancer and anti-angiogenic properties. Biomedicine & Pharmacotherapy = Biomedecine & Pharmacotherapie. 2018;105:440-448. https://doi.org/10.1016/j.biopha.2018.05.151
    [Google Scholar]
  40. , , , . Biogenic gold nanoparticle supplementation to plant beneficial Pseudomonas monteilii was found to enhance its plant probiotic effect. Current Microbiology. 2019;76:503-509. https://doi.org/10.1007/s00284-019-01649-0
    [Google Scholar]
  41. , , , , , , . Simple size-controlled synthesis of Au nanoparticles and their size-dependent catalytic activity. Scientific Reports. 2018;8:4589. https://doi.org/10.1038/s41598-018-22976-5
    [Google Scholar]
  42. , , . Catalytic, antioxidant and anticancer activities of gold nanoparticles synthesized by kaempferol glucoside from Lotus leguminosae. Arabian Journal of Chemistry. 2020;13:3112-3122. https://doi.org/10.1016/j.arabjc.2018.09.003
    [Google Scholar]
  43. . Engineered gold-based nanomaterials: Morphologies and functionalities in biomedical applications. A mini review. Bioengineering (Basel, Switzerland). 2019;6:53. https://doi.org/10.3390/bioengineering6020053
    [Google Scholar]
  44. , , . Metal organic frameworks as versatile hosts of Au nanoparticles in heterogeneous catalysis. American Chemical Society Catalysis. 2017;7:2896-2919.
    [Google Scholar]
  45. , . Gold catalysis: Fundamentals and Recent Developments. American Chemical Society Symposium Series. 2019;1317:19-55. https://doi.org/10.1021/bk-2019-1317.ch002
    [Google Scholar]
  46. , . Supported gold nanoparticles as catalysts for organic reactions. Chemical Society Reviews. 2008;37:2096-2126. https://doi.org/10.1039/b707314n
    [Google Scholar]
  47. , , , . Fabrication of sulfamic acid functionalized magnetic nanoparticles with denderimeric linkers and its application for microextraction purposes, one-pot preparation of pyrans pigments and removal of malachite green. Journal of the Taiwan Institute of Chemical Engineers. 2021;118:342-354. https://doi.org/10.1016/j.jtice.2020.12.025
    [Google Scholar]
  48. , , . Captopril supported on magnetic graphene nitride, a sustainable and green catalyst for one-pot multicomponent synthesis of 2-amino-4H-chromene and 1,2,3,6-tetrahydropyrimidine. Scientific Reports. 2023;13:20562. https://doi.org/10.1038/s41598-023-47794-2
    [Google Scholar]
  49. , , , . Triethylenetetramine-grafted magnetic graphene oxide (Fe3O4@GO-NH2) as a reusable heterogeneous catalyst for the one-pot synthesis of 2-amino-4H-benzopyran derivatives. Polycyclic Aromatic Compounds. 2023;43:7853-7869. https://doi.org/10.1080/10406638.2022.2140683
    [Google Scholar]
  50. . Carbon-carbon bond formation. New York: Marcel Dekker; . https://doi.org/10.1007/08247-6787-x
  51. . Applied cross-coupling reactions. Heidelberg, Germany: Springer; . https://doi.org/10.1007/978-3-642-32368-3
  52. . New trends in cross-coupling: theory and applications. Cambridge, U.K.: Royal Society of Chemistry; . https://doi.org/10.1007/978-3-527-81917-1
  53. , . , , eds. Metal-Catalyzed Cross-Coupling Reactions. Vol 99. Weinheim, Germany: Wiley-VCH; . p. :166. https://doi.org/10.1007/978-3-319-93755-7
  54. , , , . Cancer statistics, 2021. CA: A Cancer Journal for Clinicians. 2021;71:7-33. https://doi.org/10.3322/caac.21654
    [Google Scholar]
  55. , , . Current and innovative approaches in the treatment of non-muscle invasive bladder cancer: The role of transurethral resection of bladder tumor and organoids. Radiology and Oncology. 2020;54:135-143. https://doi.org/10.2478/raon-2020-0025
    [Google Scholar]
  56. , . Bladder cancer: Current challenges and future directions. Medicina (Kaunas, Lithuania). 2021;57:749. https://doi.org/10.3390/medicina57080749
    [Google Scholar]
  57. . The epidemiology of bladder cancer. Hematology/Oncology Clinics of North America. 2021;35:445-455. https://doi.org/10.1016/j.hoc.2021.02.001
    [Google Scholar]
  58. , . Current trends in bladder cancer treatment. Annales Chirurgiae et Gynaecologiae. 2000;89:234-241.
    [Google Scholar]
  59. , , , , , , , , , . Bladder cancer: Narrowing the gap between evidence and practice. Journal of Clinical Oncology : Official Journal of the American Society of Clinical Oncology. 2009;27:5680-5684. https://doi.org/10.1200/JCO.2009.23.6901
    [Google Scholar]

Fulltext Views
820

PDF downloads
503
View/Download PDF
Download Citations
BibTeX
RIS
Show Sections

Suggested read for related articles: