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Encapsulation strategies for improving the biological behavior of CdS@ZIF-8 nanocomposites

  • Archana Kumary , Nisha G. Pillai , Kyong Yop Rhee EMAIL logo , Soo-Jin Park EMAIL logo and Asif Abdul Azeez EMAIL logo
Published/Copyright: July 18, 2022
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 11 Issue 1

Abstract

Herein we report encapsulation approaches for Cadmium Sulfide (CdS) encapsulated zeolitic imidazolate framework (ZIF)-8 (CdS@ZIF-8), such as “bottle-around-the-ship” and “ship-in-the-bottle.” In this study, these composites were evaluated for antibacterial and DNA-binding properties. To the best of our knowledge, this is the first report on the synthesis of CdS nanoparticles using ZIF-8 as a capping agent. The as-synthesized nanocomposites were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), Brunauer–Emmett–Teller surface area analysis, field emission-scanning electron microscopy, and high-resolution transmission electron microscopy. Characterization studies revealed that both encapsulation approaches provided different morphologies to the encapsulated framework. The antibacterial activity of the as-fabricated nanocomposite, in which ZIF-8 acts as a capping agent, was more effective against Escherichia coli (E. coli) than Staphylococcus aureus (S. aureus) and Bacillus subtilis (B. subtilis). Furthermore, DNA-binding studies of nanocomposites performed by UV absorption spectroscopic titration method in E. coli genomic DNA indicated that DNA binding occurs along with cleavage. Therefore, the designed nanocomposites demonstrate great promise for future anticancer research.

Keywords: encapsulation; nanocomposite; antibacterial; DNA binding; ship-in-the-bottle; bottle-around-the-ship

1 Introduction

Metal-organic frameworks (MOFs) are a class of porous, crystalline coordination polymers derived from metals or metallic clusters (known as “secondary building units,” SBUs) and organic linkers via strong coordinate bonds [1,2]. Recently, MOF nanocomposites have gained attention because of their intriguing physicochemical properties and broader practical applications than those of traditional MOFs. Interestingly, MOFs possess high specific surface areas [3], well-defined pore size distributions [4], and tailored internal surface characteristics [5]. MOFs are classified into several classes and subclasses [6]. One of the emerging subclasses of MOFs is the zeolitic imidazolate framework (ZIF), which has structural features similar to that of aluminosilicate zeolites, wherein the bridging and tetrahedral Si(Al) bonds in aluminosilicate zeolites are replaced with organic linkers and transition metal ions, respectively [7]. ZIF-based hybrid materials such as CelloZIFs [8] find applications in the field of reduction of 4-nitrophenol [9], multifunctional environmental remediation [10], heavy metal removal, and electrochemical sensing [11].

Cadmium sulfide (CdS) is a semiconductor quantum dot with remarkable features such as high stability, ease of preparation and handling, excellent physical, chemical, and structural properties, and a wide range of applications including catalysis, water splitting, and hydrogen evolution [12,13,14,15]. CdS nanoparticles play a significant role in developing anticancer drugs because they damage DNA in cancer cells via DNA oligomer binding [16,17]. In 2007, Li and his coworkers reported enhancement of drug uptake by cancer cells through the combination of anticancer drug doxorubicin with CdS nanoparticles [18]. It is observed that CdS nanoparticles cause death of affected cells in the form of Cd2+. Further, the exposure of Cd2+ in an oxidative environment causes their release as Cd atoms [19]. The particle size and stability of nanoparticles are crucial factors that regulate their potential applications. Therefore, the size and stability of nanoparticles are generally regulated by matrices, including zeolites, silica, polymers, glasses, reverse micelles, vesicles, capping agents, and stabilizers [20,21,22,23,24,25,26,27]. Agglomeration of CdS nanoparticles can be effectively prevented using capping agents such as long-chain alkylammonium salts (for example, cetyl trimethyl ammonium bromide [CTAB]). Recently, nanoparticle encapsulated MOFs have attracted attention because they exhibit the characteristic properties of both MOF and nanoparticles. They can be synthesized using two different methods: “bottle-around-the-ship” [28] and “ship-in-the-bottle” [29]. In the former method, pre-synthesized nanoparticles stabilized by capping agents are encapsulated in the cavities of growing MOFs, [7,30] whereas in the latter method, precursors of nanoparticles are allowed to grow inside the cavities of the MOF, which act as a template or capping agent [31]. Zeng et al. [32] and Malik et al. [33] have demonstrated the synthesis of CdS@ZIF-8 using the “bottle-around-the-ship” encapsulation strategy. It is reported that Fe3O4@ZIF-8 nanocomposite can be used as a contrast agent in bioimaging [34]. In vivo experiments on this composite material showed that the composite material displayed contrast enhancement, distinguishing the normal and tumor tissues under MRI. In the case of Ceftazidime @ZIF-8 composite, where ceftazidime is an antibacterial agent showed bacterial activity against Escherichia coli (E. coli) [35]. Similar to this study, physcion (PHY) drug encapsulated ZIF-8 exhibited enhanced antibacterial activity in comparison to the pure PHY drug [36]. Table 1 summarizes the encapsulation strategy, Brunauer–Emmett–Teller (BET) surface area, pore volume values, and applications of certain nanocomposites in previously published results.

Table 1

Encapsulation strategy, BET surface area, pore volume, and applications of certain composites

Composite Encapsulation strategy BET surface area (m2 g−1) Pore volume (cm3 g−1) Application Ref.
CdS@ZIF-8 Bottle-around-the-ship No data available No data available Showed increased photocatalytic selectivity for H2 generation from formic acid [32]
CdS@ZIF-8 Bottle-around-the-ship 1294.15 0.753 Showed potential to be used as an antibacterial agent against E. coli and Staphylococcus aureus (S. aureus) [33]
Fe3O4@ZIF-8 Bottle-around-the-ship No data available No data available Used as a contrast agent in bioimaging. In vivo studies showed that the composite material displayed contrast enhancement enabling distinguishing the normal and tumor tissues under MRI [34]
Ceftazidime@ZIF-8 Bottle-around-the-ship 1,509 No data available Showed bactericidal activity against E. coli upon sustained release of the antibacterial cargo [35]
PHY@ZIF-8 Bottle-around-the-ship No data available No data available Exhibited enhanced antibacterial activity in comparison to the pure PHY drug [36]
CdS@ZIF-8 Bottle-around-the-ship 74.0 No data available Showed higher efficiency and better selectivity in photocatalytic reduction of CO2 to CO [37]

In this study, we synthesized CdS@ZIF-8 nanocomposites via the “bottle-around-the-ship” and “ship-in-the-bottle” methods to compare the properties of composites obtained using both approaches. As the CdS nanoparticles act as anticancer agents [19], the composites CdS@ZIF-8 were further tested for their antibacterial and DNA-binding properties. The morphological, physical, chemical, and textural properties of the fabricated nanocomposites were compared using Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), nitrogen sorption isotherms, BET surface area analysis, the Barrett–Joyner–Halenda (BJH) method for pore size distribution, field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM). Finally, the fabricated nanocomposites were evaluated by assessing their antibacterial activities against E. coli, S. aureus, and Bacillus subtilis (B. subtilis). In addition, DNA-binding analysis was performed with E. coli genomic DNA using the UV absorption spectroscopy.

2 Experimental

2.1 Materials

Zn(NO3)2·6H2O, CTAB, and methanol of analytical grade were purchased from RANKEM. In addition, 2-methylimidazole (Hmim) was purchased from TCI, and Cd(NO3)2·4H2O (Spectrum), Na2S·9H2O (HIMEDIA), HCl (NICE), and double-distilled water were used without further purification.

2.2 Synthesis of CdS and CTAB-capped CdS

Cd(NO3)2·4H2O (1.5423 g) was dissolved in 50 mL of methanol and a 1:1 mixture of HCl and water. Na2S·9H2O (0.3902 g) dissolved in methanol (50 mL) was added dropwise to the metal salt solution and stirred for 3 h. The greenish-yellow precipitate of CdS was obtained by sequential washing with the ethanol-water solution, then centrifuged and dried at 80°C for 48 h. CTAB-capped CdS was prepared according to the above procedure, except a methanolic solution of CTAB (0.2904 g in 10 mL of methanol) was added to the acidified metal salt solution.

2.3 Synthesis of ZIF-8

Zn(NO3)2·6H2O (2.888 g in 25 mL of methanol) was mixed with a methanolic solution of 2-methylimidazole (6.5196 g in 25 mL of methanol) and stirred for 4 h. Next the contents were transferred into a Teflon-lined autoclave and heated at 65°C for 24 h. After cooling, the obtained material was centrifuged, washed with an ethanol-water mixture, and dried in an oven at 80°C for 48 h. The white solid powder was stored in a vial for further analysis.

2.4 Synthesis of CdS@ZIF-8 (ship-in-the-bottle)

In the “ship-in-the-bottle” approach, pre-synthesized ZIF-8 was redispersed in 50 mL of methanol. The precursors of CdS (cadmium nitrate and sodium sulfide) were added to the redispersed solution of ZIF-8, and the procedure previously described for the synthesis of CdS was followed. A pale greenish-yellow CdS-encapsulated ZIF-8 solid was obtained, which was dried and stored for further analysis.

2.5 Synthesis of CTAB-capped CdS@ZIF-8 (bottle-around-the-ship)

In the “‘bottle-around-the-ship’” approach, pre-synthesized CTAB-capped CdS was redispersed in 5 mL of methanol. To this solution, the precursors of the ZIF-8 framework (zinc nitrate and 2-methylimidazole) were added, and a similar procedure to that of the synthesis of ZIF-8 was continued. A greenish-yellow CTAB-capped CdS@ZIF-8 solid was obtained and stored for further analysis.

2.6 Well-diffusion assay (antibacterial assay)

The agar well diffusion method is generally used to assess the antimicrobial activity of the prepared materials. In this method, autoclaved 15–20 mL of Mueller Hinton agar was poured onto glass Petri plates and allowed to solidify. The standardized inoculum of the test organism was uniformly spread on the surface of the plates using a sterile cotton swab. Four wells with a diameter of 8 mm (20 mm apart from one another) were punched aseptically in each plate using a sterile cork borer. Out of the 4 wells, 3 wells contained a compound solution (40 and 80 µL) and one contained gentamycin (80 μg per well) as a positive control and compound solvent as a negative control. The agar plates were incubated at 37°C for 24 h. After the incubation, a clear zone was observed. The inhibition of bacterial growth was measured in millimeters.

2.7 DNA-binding studies (UV-visible experiment)

For DNA-binding studies, a similar concentration of DNA (E. coli genome) was incubated (37°C for 2 h) using different prepared compounds (50 μg CdS, CdS@ZIF-8, CTAB-capped CdS, and CTAB-capped CdS@ZIF-8) in a phosphate buffer (pH 7.0).

2.8 Characterization

All prepared samples (ZIF-8, CdS nanoparticles, CTAB-capped CdS, CdS@ZIF-8, and CTAB-capped CdS@ZIF-8) were characterized using different instrumental techniques. The surface functionalities of the dried samples were determined using FTIR with an FTIR Shimadzu IRPrestige21 spectrophotometer with KBr pellets in the range of 4,000–400 cm−1. The crystallographic nature was obtained from the PXRD patterns of the dried samples recorded by a Bruker AXS D8 advance diffractometer using Cu Kα (λ = 1.5406 Å) radiation in the range of 3–80° in 2θ scale at high temperatures. The thermal stability and thermal decomposition nature of as-fabricated samples were determined using TGA with Perkin Elmer, STA 6000 instrument at a heating rate of 20°C min−1 under a nitrogen atmosphere over a temperature range of 40–860℃. The microstructure and morphologies of the prepared materials were observed using FE-SEM with a LEO SUPRA 55, GENESIS 2000 (Carl Zeiss, EDAX) and HR-TEM using a JEM-2100F (JEOL). Textural properties were obtained from N2 adsorption–desorption isotherms at 77 K. The BET and BJH methods were carried out with the aid of BELSORP max (MP). Antibacterial and DNA-binding studies were performed using an AquaMate 8000 UV-VIS spectrophotometer (Thermo Scientific).

3 Results and discussion

3.1 Bonding characteristics and functional group identification

The bonding characteristics and functional groups of the as-prepared samples were determined using FTIR. A prominent shift was observed in the characteristic ZIF-8 at 651 cm−1 (Figure S1), indicating out-of-plane bending of the methyl group in 2-methylimidazole. In the “ship-in-the-bottle” approach, the peak corresponding to the out-of-plane bending of the methyl group in 2-methylimidazole shifted to 751 cm−1, as evident in the FTIR spectrum of CdS@ZIF-8 (Figure 1). This can be attributed to the presence of CdS nanoparticles in the pores of ZIF-8, which increased the energy for the out-of-plane bending of the methyl group in 2-methylimidazole. Furthermore, the characteristic absorption of the Zn–N peak at 445 cm−1 in ZIF-8 shifted to 430 cm−1 in CdS@ZIF-8. This is caused by the elongation of the Zn–N bond in the interaction of the ZIF-8 framework with the encapsulated CdS during composite formation [38,39]. The peak at 734 cm−1, corresponding to the Cd–S stretching frequency (Figure S1), was downshifted to 711 cm−1 in the CdS@ZIF-8 composite [40,41]. This is attributed to the interaction of sulfur in the CdS nanoparticles with zinc in the ZIF-8 framework. Peaks in the region of 3,100–3,600 cm−1 and at 1,628 cm−1 of CdS@ZIF-8 revealed the presence of hydroxyl (–OH) groups of H2O and adsorbed CO2 on the CdS surface, respectively [42]. The presence of these characteristic peaks confirmed the formation of the CdS@ZIF-8 composite. The FTIR spectrum of CTAB-capped CdS@ZIF-8 (synthesized by the ”bottle-around-the-ship” method) is shown in Figure 1. The vibrational frequency of the Zn–N peak at 445 cm−1 is retained exactly at the same position as that of ZIF-8 (Figure S1) [43], indicating the absence of the interaction of sulfur in CdS with zinc. This indicates that the morphology of ZIF-8 was retained during the synthesis of the CTAB-capped CdS@ZIF-8 composite. In addition, other characteristic peaks corresponding to ZIF-8- and CTAB-capped CdS (Figure S1) were retained in the CTAB-capped CdS@ZIF-8 nanocomposites, confirming its formation.

Figure 1 FTIR spectra of CdS@ZIF-8 and CTAB-capped CdS@ZIF8.
Figure 1

FTIR spectra of CdS@ZIF-8 and CTAB-capped CdS@ZIF8.

3.2 Crystallographic nature

The X-ray diffraction (XRD) patterns of CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 nanocomposites are shown in Figure 2. The diffraction pattern of the as-synthesized nanocomposites showed a peak at 7.4°, which is characteristic of ZIF-8 (Figure S2) [44,45,46,47]. In the CdS@ZIF-8 nanocomposite, 3 prominent peaks of CdS were observed at 26.6, 43.7, and 52.1°, which is similar to the XRD pattern of CdS (Figure S2) [32,37,48,49]. The decrease in the intensities of the peaks corresponding to CdS nanoparticles in CdS@ZIF-8 indicates the encapsulation of nanoparticles in the MOF [50]. The diffraction pattern of the CTAB-capped CdS@ZIF-8 nanocomposite (Figure 2) shows 2θ values at 7.4, 10.5, 12.8, 18.1, 22.6, 26.6, 43.7, and 52.1°, where the first 5 peaks are attributed to ZIF-8 and the remaining peaks correspond to CTAB-capped CdS (Figure S2). The signal-to-noise (S/N) ratio of CdS particles was found to be lower in the encapsulated frameworks than in ZIF-8. This is attributed to the decrease in the particle size below 10 nm, which in turn broadens the peaks and results in a low S/N ratio [51]. Comparative analysis of the XRD patterns of ZIF-8, CdS, CdS@ZIF-8, and CTAB-capped CdS@ZIF-8 further confirmed the successful formation of CdS-encapsulated MOF nanocomposites via two different strategies, “bottle-around-the-ship” and “ship-in-the-bottle.”

Figure 2 XRD patterns of CdS@ZIF-8 and CTAB-capped CdS@ZIF8.
Figure 2

XRD patterns of CdS@ZIF-8 and CTAB-capped CdS@ZIF8.

3.3 TGA

The thermogravimetric analyses of CdS@ZIF-8- and CTAB-capped CdS@ZIF-8 nanocomposites are shown in Figure 3(a) and (b), respectively. Both nanocomposites showed approximately 10% weight loss between 40 and 150°C, which could be attributed to the removal of the adsorbed water molecules [52,53,54,55]. This observation is consistent with the FTIR peaks in the region 3,100–3,600 cm−1. The TG/DTA curves of CdS@ZIF-8 (Figure 2(a)) revealed the multi-step decomposition and high thermal stability of the nanocomposite up to 430°C. The thermal decomposition seems to occur in two stages. The first decomposition in the region of 430–530°C corresponds to ZIF-8 decomposition (Figure S3(a)) [56]. The second decomposition step starts at 535°C, which corresponds to the decomposition of CdS (Figure S3(b)). This two-step thermal decomposition is an indication of the encapsulation of CdS nanoparticles into the pores of the ZIF-8 framework. In contrast, the CTAB-capped CdS@ZIF-8 composite (Figure 2(b)) was stable up to 240°C. The decomposition between 240 and 320°C corresponds to the degradation of the capping agent CTAB, which prevents the agglomeration of the CdS nanoparticles [57] (Figure S3(c and d)). Further degradation in the range 450–530°C was ascribed to the decomposition of the ZIF-8 framework. The region above 530°C corresponds to the decomposition of the CdS nanoparticles encapsulated in the ZIF-8 framework. Therefore, strategies such as “bottle-around-the-ship” and “ship-in-the-bottle” have proven to be equally effective in encapsulating CdS nanoparticles.

Figure 3 TG/DTA curves of (a) CdS@ZIF-8 and (b) CTAB-capped CdS@ZIF-8.
Figure 3

TG/DTA curves of (a) CdS@ZIF-8 and (b) CTAB-capped CdS@ZIF-8.

3.4 Textural analysis

Textural features of the nanocomposites (CdS@ZIF-8 and CTAB-capped CdS@ZIF-8) were obtained from nitrogen adsorption isotherms and BJH plots (Figure 4(a–d)). The adsorption isotherms of both nanocomposites show a combination of type I and IV isotherms [58,59,60]. The type I isotherm arises because of the presence of the ZIF-8 framework (Figure S4), whereas type IV was owing to CdS (Figure S4). The specific surface areas obtained by the BET method for CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 nanocomposites were 221.96 and 977.73 m2 g−1, respectively. Furthermore, the pore volumes of the CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 nanocomposites were 0.1182 and 0.5385 cm3 g−1, respectively. The decrease in the surface area and pore volume of the composites compared to pristine ZIF-8 (specific surface area 2,026 m2 g−1 and pore volume 0.6698 cm3 g−1) further confirms the encapsulation of CdS into the cavities of the MOFs.

Figure 4 Nitrogen adsorption/desorption isotherms of (a) CdS@ZIF-8 and (b) CTAB-capped CdS@ZIF-8; BJH plots of (c) CdS@ZIF-8 and (d) CTAB-capped CdS@ZIF-8.
Figure 4

Nitrogen adsorption/desorption isotherms of (a) CdS@ZIF-8 and (b) CTAB-capped CdS@ZIF-8; BJH plots of (c) CdS@ZIF-8 and (d) CTAB-capped CdS@ZIF-8.

The BJH plots of the nanocomposites are depicted in Figure 4(c) and (d). Both CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 possessed pore diameters of 2.5 nm. This pore diameter was slightly larger than that of ZIF-8 (2 nm). The BJH plots of ZIF-8, CdS, and CTAB-capped CdS are shown in Figure S5. The larger pore diameter (2.5 nm) in both nanocomposites suggests the presence of a small percentage of mesopores, which is further confirmed by the shape of the nitrogen adsorption/desorption isotherms.

3.5 Structural and morphological analysis

FE-SEM images of ZIF-8 (Figure S6(a and b)) display both hexagonal and cubic morphologies. The average particle size was found to be 340 nm. However, the FE-SEM images of the CdS@ZIF-8 nanocomposite (Figure 5(a and b)) show a small elongation in the morphology. This elongation is attributed to the “ship-in-the-bottle” approach, wherein the formation of CdS nanoparticles inside the cavities of ZIF-8 causes an expansion of the framework. SEM images also show the encapsulated CdS nanoparticles, which are observed as dark spots inside the ZIF-8 framework. This indicates the encapsulation of the CdS nanoparticles into the ZIF-8 pores. The average particle size of the CdS@ZIF-8 nanocomposite was found to be 320 nm. Furthermore, as the growth of the CdS nanoparticles occurred inside the pores of the framework, the particle size of CdS did not grow beyond the pore diameter, and the ZIF-8 framework indirectly acted as a capping agent. In contrast, the FESEM images of the CTAB-capped CdS@ZIF-8 composite (Figure 5(c and d)) prepared using the “bottle-around-the-ship” method showed perfect cubic and hexagonal morphologies. This strategy of preparation retained the morphology because the development of the framework occurred along with encapsulation of CTAB-capped CdS nanoparticles. The images clearly indicate that CTAB-capped CdS nanoparticles were found inside as well as on the surfaces of the framework. The composite had an average particle size of 400 nm. This increase in the particle size of ZIF-8 was caused by the encapsulation of CTAB-capped CdS (average size of 3 nm) (Figure S6(e and f)) in the pores of the ZIF-8 framework. Detailed information regarding the morphology and size of the as-synthesized samples was obtained from the TEM images. The TEM images of ZIF-8, CdS, and CTAB-capped CdS are shown in Figure S7. The TEM images of CdS@ZIF-8 (Figure 6(a–c)) show an elongated hexagonal morphology, as indicated in FE-SEM. The dark region inside the framework (Figure 6c) indicates the encapsulation of CdS nanoparticles less than 5 nm in the core cavities of the framework composite, CdS@ZIF-8. This observation confirms the role of ZIF-8 as a capping agent for CdS nanoparticles, which helps prevent its agglomeration. The TEM images of the CTAB-capped CdS@ZIF-8 nanocomposites (Figure 6(d–f)) show cubic and hexagonal geometries. The average particle size in the TEM images was found to be the same as that in the FE-SEM images [61]. In Figure 6(d) and (e), CdS nanoparticles are observed on the surface cavities as well as in the core cavities of the cubic framework of the CTAB-capped CdS@ZIF-8 as dark regions. The TEM images show that both strategies, “bottle-around-the-ship” and “ship-in-the-bottle,” are equally effective in the successful encapsulation of CdS nanoparticles in the framework composites. These results are in agreement with the data obtained from BET analysis and BJH pore size distributions.

Figure 5 FE-SEM images of (a and b) CdS@ZIF-8 and (c and d) CTAB-capped CdS@ZIF-8.
Figure 5

FE-SEM images of (a and b) CdS@ZIF-8 and (c and d) CTAB-capped CdS@ZIF-8.

Figure 6 HR-TEM images of (a–c) CdS@ZIF-8 and (d–f) CTAB-capped CdS@ZIF-8.
Figure 6

HR-TEM images of (a–c) CdS@ZIF-8 and (d–f) CTAB-capped CdS@ZIF-8.

4 Applications

4.1 Antimicrobial activity and DNA binding

The results of the antibacterial activity of all the prepared samples (CdS@ZIF-8, CTAB-capped CdS@ZIF-8, ZIF-8, CdS, and CTAB-capped CdS) were determined by a well-diffusion assay against E. coli, S. aureus, and B. subtilis and listed in Table 2 and Table S1. The results revealed that the antibacterial activity of the same compound against different bacteria is different and depends on the structural components of the bacteria [62,63]. Similarly, the same bacteria against different compounds show different antibacterial activities, likely because of differences in the structural components of the compounds [64,65]. The antibacterial activity of ZIF-8, even at higher concentrations, was very low, which might be because E. coli is not sufficiently sensitive to ZIF-8 [66,67]. However, the composite CdS@ZIF-8 showed higher antibacterial activity against E. coli compared with the CTAB-capped CdS@ZIF-8 composite. This is because in the CdS@ZIF-8 composite, the Zn2+ ions were more easily available than in the ZIF-8- and CTAB-capped CdS@ZIF-8 nanocomposites. The antibacterial activities of CTAB-capped CdS@ZIF-8 against S. aureus and B. subtilis were higher than those against E. coli. This is because the liposomes of gram-positive bacteria (S. aureus and B. subtilis, which are fatty acid-enriched) were destroyed by the CTAB-capped CdS@ZIF-8 nanocomposite [64]. Thus, it can be concluded that the composite CdS@ZIF-8 synthesized via “ship-in-the-bottle” is more effective against E. coli than CTAB-capped CdS@ZIF-8.

Table 2

Antibacterial activities of CdS@ZIF-8 and CTAB-capped CdS@ZIF-8

Sample Organism Diameter of zone (mean value ± SD) (in mm)
+(80 μg) (control) T1 (400 µg) T2 (800 µg)
CdS@ZIF-8 E. coli 33.1 ± 0.16 12.2 ± 0.29 22.0 ± 0.24
S. aureus 30.0 ± 0.20 13.1 ± 0.16 14.9 ± 0.12
Bacillus subtilis 35.1 ± 0.20 16.1 ± 0.12 19.8 ± 0.62
CTAB capped CdS@ZIF-8 E. coli 30.6 ± 0.54 15.0 ± 0.12 17.9 ± 0.08
S. aureus 30.0 ± 0.05 17.9 ± 0.08 26.0 ± 0.08
Bacillus subtilis 35.2 ± 0.46 17.1 ± 0.05 21.2 ± 0.17

Numerous scientific studies have shown that DNA is a major intracellular target of anticancer drugs. Interactions between tiny molecules and DNA can induce damage in cancer cells, preventing cell division and ultimately leading to cell death [68,69]. The DNA-binding studies of CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 are summarized in Table 3 and those of ZIF-8, CdS, and CTAB-capped CdS are presented in Table S2. With respect to the control, both CdS@ZIF-8 and CTAB-capped CdS@ZIF-8 nanocomposites and CdS nanoparticles showed a redshift and hyperchromic effects, whereas ZIF-8 showed a blueshift. The hyperchromic effects and variation in wavelength (either redshift or blueshift) illustrate that intercalation occurs through electrostatic interactions or groove binding [41] between the composite material and E. coli genomic DNA.

Table 3

DNA-binding studies of CdS@ZIF-8 and CTAB-capped CdS@ZIF-8

Absorbance Inference Wavelength (nm) Inference
CdS@ZIF-8 (50 µg) + E. coli genomic DNA 0.259 Hyperchromic 270 Red shift
CTAB capped CdS@ZIF-8 (50 µg) + E. coli genomic DNA 0.333 Hyperchromic 270 Red shift

5 Conclusion

In this study, we successfully developed CdS-encapsulated ZIF-8 nanocomposites via two strategic approaches: “ship-in-the-bottle” and “bottle-around-the-ship.” Nanocomposites derived from the “ship-in-the-bottle approach” showed good thermal stability; however, their morphology was distorted owing to the growth of CdS nanoparticles inside the cavities, which expanded the framework to a certain extent and prevented agglomeration. The framework indirectly acted as a capping agent. On the other hand, the “bottle-around-the-ship” approach retained the morphology as the framework developed along with the encapsulation of CTAB-capped CdS. CTAB-capped CdS was also present on the surface of the framework. FTIR, XRD, and BET analyses confirmed the formation of composites through both strategies. The surface morphology was confirmed by FE-SEM and HR-TEM. Future anticancer studies could benefit from leveraging the antibacterial and DNA-binding properties of these composites.

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Acknowledgments

The authors are thankful to UGC, Government of India for providing research grant (No. 2348-MRP/15-16/KLKE029/UGC-SWRO) and are also thankful to Kyung Hee University, Republic of Korea and SAIF-Cochin, for characterisation. The authors extend their thanks to Athmic Biotech Solutions Pvt Ltd, Kerala for application studies.

  1. Funding information: The authors are thankful to UGC, Government of India for providing research grant (No. 2348-MRP/15-16/KLKE029/UGC-SWRO).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2022-03-04
Revised: 2022-06-14
Accepted: 2022-06-26
Published Online: 2022-07-18

© 2022 Archana Kumary et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  99. Encapsulation strategies for improving the biological behavior of CdS@ZIF-8 nanocomposites
  100. Biosynthesis of ZnO NPs from pumpkin seeds’ extract and elucidation of its anticancer potential against breast cancer
  101. Preliminary trials of the gold nanoparticles conjugated chrysin: An assessment of anti-oxidant, anti-microbial, and in vitro cytotoxic activities of a nanoformulated flavonoid
  102. Effect of micron-scale pores increased by nano-SiO2 sol modification on the strength of cement mortar
  103. Fractional simulations for thermal flow of hybrid nanofluid with aluminum oxide and titanium oxide nanoparticles with water and blood base fluids
  104. The effect of graphene nano-powder on the viscosity of water: An experimental study and artificial neural network modeling
  105. Development of a novel heat- and shear-resistant nano-silica gelling agent
  106. Characterization, biocompatibility and in vivo of nominal MnO2-containing wollastonite glass-ceramic
  107. Entropy production simulation of second-grade magnetic nanomaterials flowing across an expanding surface with viscidness dissipative flux
  108. Enhancement in structural, morphological, and optical properties of copper oxide for optoelectronic device applications
  109. Aptamer-functionalized chitosan-coated gold nanoparticle complex as a suitable targeted drug carrier for improved breast cancer treatment
  110. Performance and overall evaluation of nano-alumina-modified asphalt mixture
  111. Analysis of pure nanofluid (GO/engine oil) and hybrid nanofluid (GO–Fe3O4/engine oil): Novel thermal and magnetic features
  112. Synthesis of Ag@AgCl modified anatase/rutile/brookite mixed phase TiO2 and their photocatalytic property
  113. Mechanisms and influential variables on the abrasion resistance hydraulic concrete
  114. Synergistic reinforcement mechanism of basalt fiber/cellulose nanocrystals/polypropylene composites
  115. Achieving excellent oxidation resistance and mechanical properties of TiB2–B4C/carbon aerogel composites by quick-gelation and mechanical mixing
  116. Microwave-assisted sol–gel template-free synthesis and characterization of silica nanoparticles obtained from South African coal fly ash
  117. Pulsed laser-assisted synthesis of nano nickel(ii) oxide-anchored graphitic carbon nitride: Characterizations and their potential antibacterial/anti-biofilm applications
  118. Effects of nano-ZrSi2 on thermal stability of phenolic resin and thermal reusability of quartz–phenolic composites
  119. Benzaldehyde derivatives on tin electroplating as corrosion resistance for fabricating copper circuit
  120. Mechanical and heat transfer properties of 4D-printed shape memory graphene oxide/epoxy acrylate composites
  121. Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts
  122. Graphene-oxide-reinforced cement composites mechanical and microstructural characteristics at elevated temperatures
  123. Gray correlation analysis of factors influencing compressive strength and durability of nano-SiO2 and PVA fiber reinforced geopolymer mortar
  124. Preparation of layered gradient Cu–Cr–Ti alloy with excellent mechanical properties, thermal stability, and electrical conductivity
  125. Recovery of Cr from chrome-containing leather wastes to develop aluminum-based composite material along with Al2O3 ceramic particles: An ingenious approach
  126. Mechanisms of the improved stiffness of flexible polymers under impact loading
  127. Anticancer potential of gold nanoparticles (AuNPs) using a battery of in vitro tests
  128. Review Articles
  129. Proposed approaches for coronaviruses elimination from wastewater: Membrane techniques and nanotechnology solutions
  130. Application of Pickering emulsion in oil drilling and production
  131. The contribution of microfluidics to the fight against tuberculosis
  132. Graphene-based biosensors for disease theranostics: Development, applications, and recent advancements
  133. Synthesis and encapsulation of iron oxide nanorods for application in magnetic hyperthermia and photothermal therapy
  134. Contemporary nano-architectured drugs and leads for ανβ3 integrin-based chemotherapy: Rationale and retrospect
  135. State-of-the-art review of fabrication, application, and mechanical properties of functionally graded porous nanocomposite materials
  136. Insights on magnetic spinel ferrites for targeted drug delivery and hyperthermia applications
  137. A review on heterogeneous oxidation of acetaminophen based on micro and nanoparticles catalyzed by different activators
  138. Early diagnosis of lung cancer using magnetic nanoparticles-integrated systems
  139. Advances in ZnO: Manipulation of defects for enhancing their technological potentials
  140. Efficacious nanomedicine track toward combating COVID-19
  141. A review of the design, processes, and properties of Mg-based composites
  142. Green synthesis of nanoparticles for varied applications: Green renewable resources and energy-efficient synthetic routes
  143. Two-dimensional nanomaterial-based polymer composites: Fundamentals and applications
  144. Recent progress and challenges in plasmonic nanomaterials
  145. Apoptotic cell-derived micro/nanosized extracellular vesicles in tissue regeneration
  146. Electronic noses based on metal oxide nanowires: A review
  147. Framework materials for supercapacitors
  148. An overview on the reproductive toxicity of graphene derivatives: Highlighting the importance
  149. Antibacterial nanomaterials: Upcoming hope to overcome antibiotic resistance crisis
  150. Research progress of carbon materials in the field of three-dimensional printing polymer nanocomposites
  151. A review of atomic layer deposition modelling and simulation methodologies: Density functional theory and molecular dynamics
  152. Recent advances in the preparation of PVDF-based piezoelectric materials
  153. Recent developments in tensile properties of friction welding of carbon fiber-reinforced composite: A review
  154. Comprehensive review of the properties of fly ash-based geopolymer with additive of nano-SiO2
  155. Perspectives in biopolymer/graphene-based composite application: Advances, challenges, and recommendations
  156. Graphene-based nanocomposite using new modeling molecular dynamic simulations for proposed neutralizing mechanism and real-time sensing of COVID-19
  157. Nanotechnology application on bamboo materials: A review
  158. Recent developments and future perspectives of biorenewable nanocomposites for advanced applications
  159. Nanostructured lipid carrier system: A compendium of their formulation development approaches, optimization strategies by quality by design, and recent applications in drug delivery
  160. 3D printing customized design of human bone tissue implant and its application
  161. Design, preparation, and functionalization of nanobiomaterials for enhanced efficacy in current and future biomedical applications
  162. A brief review of nanoparticles-doped PEDOT:PSS nanocomposite for OLED and OPV
  163. Nanotechnology interventions as a putative tool for the treatment of dental afflictions
  164. Recent advancements in metal–organic frameworks integrating quantum dots (QDs@MOF) and their potential applications
  165. A focused review of short electrospun nanofiber preparation techniques for composite reinforcement
  166. Microstructural characteristics and nano-modification of interfacial transition zone in concrete: A review
  167. Latest developments in the upconversion nanotechnology for the rapid detection of food safety: A review
  168. Strategic applications of nano-fertilizers for sustainable agriculture: Benefits and bottlenecks
  169. Molecular dynamics application of cocrystal energetic materials: A review
  170. Synthesis and application of nanometer hydroxyapatite in biomedicine
  171. Cutting-edge development in waste-recycled nanomaterials for energy storage and conversion applications
  172. Biological applications of ternary quantum dots: A review
  173. Nanotherapeutics for hydrogen sulfide-involved treatment: An emerging approach for cancer therapy
  174. Application of antibacterial nanoparticles in orthodontic materials
  175. Effect of natural-based biological hydrogels combined with growth factors on skin wound healing
  176. Nanozymes – A route to overcome microbial resistance: A viewpoint
  177. Recent developments and applications of smart nanoparticles in biomedicine
  178. Contemporary review on carbon nanotube (CNT) composites and their impact on multifarious applications
  179. Interfacial interactions and reinforcing mechanisms of cellulose and chitin nanomaterials and starch derivatives for cement and concrete strength and durability enhancement: A review
  180. Diamond-like carbon films for tribological modification of rubber
  181. Layered double hydroxides (LDHs) modified cement-based materials: A systematic review
  182. Recent research progress and advanced applications of silica/polymer nanocomposites
  183. Modeling of supramolecular biopolymers: Leading the in silico revolution of tissue engineering and nanomedicine
  184. Recent advances in perovskites-based optoelectronics
  185. Biogenic synthesis of palladium nanoparticles: New production methods and applications
  186. A comprehensive review of nanofluids with fractional derivatives: Modeling and application
  187. Electrospinning of marine polysaccharides: Processing and chemical aspects, challenges, and future prospects
  188. Electrohydrodynamic printing for demanding devices: A review of processing and applications
  189. Rapid Communications
  190. Structural material with designed thermal twist for a simple actuation
  191. Recent advances in photothermal materials for solar-driven crude oil adsorption
https://doi.org/10.1515/ntrev-2022-0152
Keywords for this article
encapsulation; nanocomposite; antibacterial; DNA binding; ship-in-the-bottle; bottle-around-the-ship
Creative Commons
BY 4.0

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  43. Molecular dynamics study of deformation mechanism of interfacial microzone of Cu/Al2Cu/Al composites under tension
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  98. A comparative study of the elasto-plastic properties for ceramic nanocomposites filled by graphene or graphene oxide nanoplates
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  101. Preliminary trials of the gold nanoparticles conjugated chrysin: An assessment of anti-oxidant, anti-microbial, and in vitro cytotoxic activities of a nanoformulated flavonoid
  102. Effect of micron-scale pores increased by nano-SiO2 sol modification on the strength of cement mortar
  103. Fractional simulations for thermal flow of hybrid nanofluid with aluminum oxide and titanium oxide nanoparticles with water and blood base fluids
  104. The effect of graphene nano-powder on the viscosity of water: An experimental study and artificial neural network modeling
  105. Development of a novel heat- and shear-resistant nano-silica gelling agent
  106. Characterization, biocompatibility and in vivo of nominal MnO2-containing wollastonite glass-ceramic
  107. Entropy production simulation of second-grade magnetic nanomaterials flowing across an expanding surface with viscidness dissipative flux
  108. Enhancement in structural, morphological, and optical properties of copper oxide for optoelectronic device applications
  109. Aptamer-functionalized chitosan-coated gold nanoparticle complex as a suitable targeted drug carrier for improved breast cancer treatment
  110. Performance and overall evaluation of nano-alumina-modified asphalt mixture
  111. Analysis of pure nanofluid (GO/engine oil) and hybrid nanofluid (GO–Fe3O4/engine oil): Novel thermal and magnetic features
  112. Synthesis of Ag@AgCl modified anatase/rutile/brookite mixed phase TiO2 and their photocatalytic property
  113. Mechanisms and influential variables on the abrasion resistance hydraulic concrete
  114. Synergistic reinforcement mechanism of basalt fiber/cellulose nanocrystals/polypropylene composites
  115. Achieving excellent oxidation resistance and mechanical properties of TiB2–B4C/carbon aerogel composites by quick-gelation and mechanical mixing
  116. Microwave-assisted sol–gel template-free synthesis and characterization of silica nanoparticles obtained from South African coal fly ash
  117. Pulsed laser-assisted synthesis of nano nickel(ii) oxide-anchored graphitic carbon nitride: Characterizations and their potential antibacterial/anti-biofilm applications
  118. Effects of nano-ZrSi2 on thermal stability of phenolic resin and thermal reusability of quartz–phenolic composites
  119. Benzaldehyde derivatives on tin electroplating as corrosion resistance for fabricating copper circuit
  120. Mechanical and heat transfer properties of 4D-printed shape memory graphene oxide/epoxy acrylate composites
  121. Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts
  122. Graphene-oxide-reinforced cement composites mechanical and microstructural characteristics at elevated temperatures
  123. Gray correlation analysis of factors influencing compressive strength and durability of nano-SiO2 and PVA fiber reinforced geopolymer mortar
  124. Preparation of layered gradient Cu–Cr–Ti alloy with excellent mechanical properties, thermal stability, and electrical conductivity
  125. Recovery of Cr from chrome-containing leather wastes to develop aluminum-based composite material along with Al2O3 ceramic particles: An ingenious approach
  126. Mechanisms of the improved stiffness of flexible polymers under impact loading
  127. Anticancer potential of gold nanoparticles (AuNPs) using a battery of in vitro tests
  128. Review Articles
  129. Proposed approaches for coronaviruses elimination from wastewater: Membrane techniques and nanotechnology solutions
  130. Application of Pickering emulsion in oil drilling and production
  131. The contribution of microfluidics to the fight against tuberculosis
  132. Graphene-based biosensors for disease theranostics: Development, applications, and recent advancements
  133. Synthesis and encapsulation of iron oxide nanorods for application in magnetic hyperthermia and photothermal therapy
  134. Contemporary nano-architectured drugs and leads for ανβ3 integrin-based chemotherapy: Rationale and retrospect
  135. State-of-the-art review of fabrication, application, and mechanical properties of functionally graded porous nanocomposite materials
  136. Insights on magnetic spinel ferrites for targeted drug delivery and hyperthermia applications
  137. A review on heterogeneous oxidation of acetaminophen based on micro and nanoparticles catalyzed by different activators
  138. Early diagnosis of lung cancer using magnetic nanoparticles-integrated systems
  139. Advances in ZnO: Manipulation of defects for enhancing their technological potentials
  140. Efficacious nanomedicine track toward combating COVID-19
  141. A review of the design, processes, and properties of Mg-based composites
  142. Green synthesis of nanoparticles for varied applications: Green renewable resources and energy-efficient synthetic routes
  143. Two-dimensional nanomaterial-based polymer composites: Fundamentals and applications
  144. Recent progress and challenges in plasmonic nanomaterials
  145. Apoptotic cell-derived micro/nanosized extracellular vesicles in tissue regeneration
  146. Electronic noses based on metal oxide nanowires: A review
  147. Framework materials for supercapacitors
  148. An overview on the reproductive toxicity of graphene derivatives: Highlighting the importance
  149. Antibacterial nanomaterials: Upcoming hope to overcome antibiotic resistance crisis
  150. Research progress of carbon materials in the field of three-dimensional printing polymer nanocomposites
  151. A review of atomic layer deposition modelling and simulation methodologies: Density functional theory and molecular dynamics
  152. Recent advances in the preparation of PVDF-based piezoelectric materials
  153. Recent developments in tensile properties of friction welding of carbon fiber-reinforced composite: A review
  154. Comprehensive review of the properties of fly ash-based geopolymer with additive of nano-SiO2
  155. Perspectives in biopolymer/graphene-based composite application: Advances, challenges, and recommendations
  156. Graphene-based nanocomposite using new modeling molecular dynamic simulations for proposed neutralizing mechanism and real-time sensing of COVID-19
  157. Nanotechnology application on bamboo materials: A review
  158. Recent developments and future perspectives of biorenewable nanocomposites for advanced applications
  159. Nanostructured lipid carrier system: A compendium of their formulation development approaches, optimization strategies by quality by design, and recent applications in drug delivery
  160. 3D printing customized design of human bone tissue implant and its application
  161. Design, preparation, and functionalization of nanobiomaterials for enhanced efficacy in current and future biomedical applications
  162. A brief review of nanoparticles-doped PEDOT:PSS nanocomposite for OLED and OPV
  163. Nanotechnology interventions as a putative tool for the treatment of dental afflictions
  164. Recent advancements in metal–organic frameworks integrating quantum dots (QDs@MOF) and their potential applications
  165. A focused review of short electrospun nanofiber preparation techniques for composite reinforcement
  166. Microstructural characteristics and nano-modification of interfacial transition zone in concrete: A review
  167. Latest developments in the upconversion nanotechnology for the rapid detection of food safety: A review
  168. Strategic applications of nano-fertilizers for sustainable agriculture: Benefits and bottlenecks
  169. Molecular dynamics application of cocrystal energetic materials: A review
  170. Synthesis and application of nanometer hydroxyapatite in biomedicine
  171. Cutting-edge development in waste-recycled nanomaterials for energy storage and conversion applications
  172. Biological applications of ternary quantum dots: A review
  173. Nanotherapeutics for hydrogen sulfide-involved treatment: An emerging approach for cancer therapy
  174. Application of antibacterial nanoparticles in orthodontic materials
  175. Effect of natural-based biological hydrogels combined with growth factors on skin wound healing
  176. Nanozymes – A route to overcome microbial resistance: A viewpoint
  177. Recent developments and applications of smart nanoparticles in biomedicine
  178. Contemporary review on carbon nanotube (CNT) composites and their impact on multifarious applications
  179. Interfacial interactions and reinforcing mechanisms of cellulose and chitin nanomaterials and starch derivatives for cement and concrete strength and durability enhancement: A review
  180. Diamond-like carbon films for tribological modification of rubber
  181. Layered double hydroxides (LDHs) modified cement-based materials: A systematic review
  182. Recent research progress and advanced applications of silica/polymer nanocomposites
  183. Modeling of supramolecular biopolymers: Leading the in silico revolution of tissue engineering and nanomedicine
  184. Recent advances in perovskites-based optoelectronics
  185. Biogenic synthesis of palladium nanoparticles: New production methods and applications
  186. A comprehensive review of nanofluids with fractional derivatives: Modeling and application
  187. Electrospinning of marine polysaccharides: Processing and chemical aspects, challenges, and future prospects
  188. Electrohydrodynamic printing for demanding devices: A review of processing and applications
  189. Rapid Communications
  190. Structural material with designed thermal twist for a simple actuation
  191. Recent advances in photothermal materials for solar-driven crude oil adsorption
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