Ultra-fast bacterial inactivation of Cu2O@halloysite nanotubes hybrids with charge adsorption and physical piercing ability for medical protective fabrics

doi:10.1016/j.jmst.2021.12.059

Abstract

Abstract:

Metals have been used for wound treatment and toxicity testing since ancient times. With the development of nanotechnology, metal oxides have been proven to have excellent sterilization and disinfection functions. However, the rapid bacterial inactivation efficiency and trapping physicochemical killing ability remain simultaneously undemonstrated in antibacterial nanohybrids. Here, we demonstrate a method for in-situ reduction of small-sized Cu₂O particles on one-dimensional inorganic halloysite nanotubes (HNTs). The resultant Cu₂O@HNTs hybrids not only give Cu₂O excellent dispersibility, but also exert the synergistic effect of the charge adsorption of metal oxides and the physical piercing effect of the small-sized nanotubes. Furthermore, the release of Cu²⁺ from hybrids damages cell membranes and denatures proteins and DNA. Through this sterilization mechanism, Cu₂O@HNTs allow for the inactivation rate of Escherichia coli to reach 94.5% within 2 min and complete inactivation within 10 min. This excellent sterilization mode makes Cu₂O@HNTs exhibit excellent broad-spectrum antibacterial activity and inactivation efficiency, while shows weak cytotoxicity. These hybrids were further applied in the processing of functional antibacterial fibers and fabrics. Thus, we believe that this excellent antibacterial hybrid is practically attractive in this critical time of the COVID-19 pandemic.

Key words: Cu₂O, Halloysite nanotubes, Antibacterial activity, Efficient inactivation, Protective fabrics

Yaping Wang, Qianqian Wang, Guoyi Wu, Hengxue Xiang, Mugaanire Tendo Innocent, Mian Zhai, Chao Jia, Peng Zou, Jialiang Zhou, Meifang Zhu. Ultra-fast bacterial inactivation of Cu₂O@halloysite nanotubes hybrids with charge adsorption and physical piercing ability for medical protective fabrics[J]. J. Mater. Sci. Technol., 2022, 122: 1-9.

Figures/Tables 8

Fig. 1. (a) Schematic illustration of the synthesis process of Cu2O@HNTs nanohybrids; (b) the process of preparing Cu2O by Cu2+ chelation and in-situ reduction; (c) the sterilization mechanism of Cu2O@HNTs.

Fig. 2. TEM images of (a, b) neat HNTs and (c, d) Cu2O@HNTs hybrids under different magnifications; (e) XRD spectra, (f) FT-IR spectra and (g) XPS survey scan spectra of HNTs and various Cu2O@HNTs hybrids; High-resolution XPS spectrum of (h) Cu 2p and (i) O 1 s for Cu2O@HNTs hybrids. The inset in (d) shows the size distribution for Cu2O on HNTs determined by measuring the diameter of over 30 Cu2O nanoparticles in several SEM images. Curve in blue shows the Gaussian distributions of Cu2O particle sizes.

Fig. 3. Growth curves of (a) E.coli and (b) S.aureus treated with control, HNTs, Cu2O, Cu2O@HNTs, the results were corresponded to means ± SD (SD, standard deviation; n = 3); (c) E.coli and S.aureus killing ratios of HNTs, Cu2O and Cu2O@HNTs. Asterisks indicate significant differences (P values: *P < 0.05, **P < 0.01, ***P < 0.001). All values are expressed as means ± SD, n = 3. (d) Antibacterial activity in PBS: The bacterial suspension in PBS without any substance was named as control. The agar plate photographs of E.coli and S. aureus bacterial cells were re-cultured on it after being treated with HNTs, Cu2O, Cu2O@HNTs. Fluorescent live/dead stain images of control, HNTs, Cu2O, Cu2O@HNTs for E.coli and S. aureus, respectively. Scale bar is 20 μm.

Fig. 4. (a) Inactivation of E. coli treated by Cu2O and Cu2O@HNTs versus the time. (b) Inactivation time of E. coli after treatments by different antibacterial nanomaterials with samples concentration (ZnO-MNSs [52], GO-Ag [53], Ag-CoFe2O4-GO [54], Bi2MoO6 /Ag-AgCl [55], Cu2O [56], Cu-Zn [57], Cu [58]). (c) Photographs of agar plates on which E. coli bacterial cells incubated with Cu2O and Cu2O@HNTs samples at different time.

Fig. 5. (a) Zeta potentials of HNTs, Cu2O and Cu2O@HNTs; SEM images of E. coli cells treated by (b) E. coli cells, (c) HNTs, (d) Cu2O and (e) Cu2O@HNTs hybrids 18 h in LB medium; (f) The soluble protein content of E. coli treated with HNTs and Cu2O@HNTs; (g) QRT-PCR agarose gel electrophoresis; (h) The relative expression of glucokinase GK gene in control and E.coli bacteria treated by Cu2O@HNTs (P values: *P < 0.05, **P < 0.01).

Table 1. Concentrations of K+, Ca2+, Mg2+ and Cu2+ in the extracellular fluid treated with antibacterial materials.

Samples	Time (h)	K⁺ (mg/L)	Ca²⁺ (mg/L)	Mg²⁺ (mg/L)	Cu²⁺ (mg/L)
Blank	0	0.4607	0.2683	0.0000	0.0000
	2	0.3567	0.2561	0.0000	0.0000
	4	0.3353	0.2443	0.0000	0.0000
	6	0.3428	0.2531	0.0000	0.0000
Cu₂O@HNTs	0	0.4485	0.3082	0.0000	0.0388
	2	0.4976	0.3031	0.0000	0.0402
	4	0.533	0.3056	0.0248	0.0279
	6	0.5537	0.4833	0.1054	0.0397

Fig. 6. Schematic illustration of (a) in-situ polymerization procedures of PET/Cu2O@HNTs and (b) melt spinning procedures of CHPET fibers; (c) Mechanical performance of neat PET fiber and series of CHPET fibers; (d) E. coli, S. aureus, V583 and MRSA killing ratios of PET, CHPET-0.2 fibers. All values are expressed as means ± SD, n = 3. (e) Virus viability of HCoV-OC43 in PET, CuO/PET, CuO/PA6 and CHPET-0.2 after cultivation.

Fig. 7. (a) Cell viability of Hela cells in the control group and Cu2O@HNTs after 1, 2 and 3 days of cultivation, respectively; (b) In vitro cytocompatibility of Cu2O@HNTs. Morphology of Hela cells after 1, 2, and 3 days of culture. Scale bar is 100 μm.

References 58

[1]	A. Chouksey, M. Agrawal,Eng. Sci. 15 (2021) 177-186.
[2]	E. Fleming, Y. Luo,ES Food Agrofor. 4 (2021) 5-8.
[3]	P. Tsai,Eng. Sci. 10 (2020) 1-7.
[4]	B. Peng, X.L. Zhang, D. Aarts, R.P.A. Dullens,Nat. Nanotechnol. 13 (2018)478.
[5]	J. Zhou, Z. Hu, F. Zabihi, Z. Chen, M. Zhu,Adv. Fiber Mater. 2 (2020) 123-139. DOI URL
[6]	C. Walsh, Nature406(2000) 775-781.
[7]	E.D. Brown,G.D. Wright,Nature529 (2016) 336-343. DOI URL
[8]	H. Yu, C. Xu, Y. Li, F. Jin, F. Ye, X. Li,ES Energy Environ. 8(2020) 65-77.
[9]	S.A .A.R. Sayyed, N.I. Beedri, P.K. Bhujbal, S.F. Shaikh, H.M. Pathan,ES Mater. Manuf.10 (2020) 45-51.
[10]	P.P. Rade, P.S. Giram, A.A. Shitole, N. Sharma, B. Garnaik,Adv. Fiber Mater. 4 (2022) 76-88. DOI URL
[11]	K. Sunada, M. Minoshima, K. Hashimoto,J. Hazard. Mater. 235-236 (2012) 265-270.
[12]	J.A. Lemire, J.J. Harrison, R.J. Turner,Nat. Rev. Microbiol. 11 (2013) 371-384. DOI URL
[13]	D. Zhang, B. Br, O.L. Williams, V.H. Santos, B.J. Loﬁnk, E.M. Becher, A. Partyka, X. Peng, L. Sun,Eng. Sci. 12 (2020) 106-112.
[14]	L. Zhao, Q.Z. Ge, J.X. Sun, J.S. Peng, X.Z. Yin, L.P. Huang, J.H. Wang, H. Wang, L. X. Wang,Adv. Compos. Hybrid Mater. 2 (2019) 481-491.
[15]	Y. Zhu, Y. Wang, L. Sha, J. Zhao, X. Li,J. Appl. Polym. Sci. 135 (2018) 46755.
[16]	Y. Zhu, Y. Wang, L. Sha, J. Zhao,Appl. Surf. Sci. 425 (2017) 1101-1110. DOI URL
[17]	S.R. Lustig, J.J.H. Biswakarma, D. Rana, S.H. Tilford, W. Hu, M. Su,M.S. Rosen-blatt, ACS Nano 14 (2020) 7651-7658.
[18]	J. Zhou, C. Wang, A.J. Cunningham, Z. Hu, H. Xiang, B. Sun, W. Zuo, M. Zhu,Mater. Sci. Eng. C 101 (2019) 499-504. DOI URL
[19]	J. Zhou, H. Xiang, F. Zabihi, S. Yu, B. Sun, M. Zhu,Nano Res. 12 (2019) 1453-1460. DOI URL
[20]	J. Zhou, Y. Wang, W. Pan, H. Xiang, P. Li, Z. Zhou, M. Zhu,J. Mater. Sci. Technol. 81 (2021) 58-66. DOI URL
[21]	K. Feng, G.-.Y. Hung, J. Liu, M. Li, C. Zhou, M. Liu,Chem. Eng. J. 331 (2018) 744-754. DOI URL
[22]	E. Abdullayev, K. Sakakibara, K. Okamoto, W. Wei, K. Ariga, Y. Lvov,ACS Appl. Mater. Interfaces 3 (2011) 4040-4046. DOI URL
[23]	H. Xiang, J. Zhou, Y. Zhang, M.T. Innocent, M. Zhu,Appl. Clay Sci. 182 (2019) 105249.
[24]	M. Liu, C. Wu, Y. Jiao, S. Xiong, C. Zhou,J. Mater. Chem. B 1 (2013) 2078-2089.
[25]	J. Liu, J. Fu, Y. Zhou, W. Zhu, L.-.P. Jiang, Y. Lin,Nano Lett. 20 (2020) 4823-4828. DOI URL
[26]	L. Dai, Q. Qin, P. Wang, X. Zhao, C. Hu, P. Liu, R. Qin, M. Chen, D. Ou, C. Xu, S. Mo, B. Wu, G. Fu, P. Zhang, N. Zheng,Sci. Adv. 3 (2017) e1701069.
[27]	M.S. Xie, B.Y. Xia, Y. Li, Y. Yan, Y. Yang, Q. Sun, S.H. Chan, A. Fisher, X. Wang,Energy Environ. Sci. 9 (2016) 1687-1695. DOI URL
[28]	Y.H. Tsai, C.Y. Chiu, M.H. Huang,J. Phys. Chem. C 117 (2013) 24611-24617.
[29]	T. Li, W. Zeng, L. Chen, C. Wang,Mater. Lett. 164 (2016) 225-228. DOI URL
[30]	P. Yuan, P.D. Southon, Z. Liu, M.E.R. Green, J.M. Hook, S.J. Antill, C.J. Kepert,J. Phys. Chem. C 112 (2008) 15742-15751. DOI URL
[31]	T. Yu, L.T. Swientoniewski, M. Omarova, M.-.C. Li, I.I. Negulescu, N. Jiang, O. A. Darvish, A. Panchal, D.A. Blake, Q. Wu, Y.M. Lvov, V.T. John, D. Zhang,ACS Appl. Mater. Interfaces 11 (2019) 27944-27953. DOI URL
[32]	K. Giannousi, G. Saraﬁdis, S. Mourdikoudis, A. Pantazaki, C. Dendrinou-Samara,Inorg. Chem. 53 (2014) 9657-9666. DOI URL PMID
[33]	Y. Yang, J. Han, X. Ning, W. Cao, W. Xu, L. Guo,ACS Appl. Mater. Interfaces 6 (2014) 22534-22543. DOI URL
[34]	K. Hu, L. Xie, Y. Zhang, M. Hanyu, Z. Yang, K. Nagatsu, H. Suzuki, J. Ouyang, X. Ji, J. Wei, H. Xu, O.C. Farokhzad, S.H. Liang, L. Wang, W. Tao, M.-.R. Zhang,Nat. Commun. 11 (2020) 2778.
[35]	J.J. Teo, Y. Chang,H.C. Zeng, Langmuir 22 (2006) 7369-7377.
[36]	Z. Duan, Q. Zhao, S. Wang, Q. Huang, Z. Yuan, Y. Zhang, Y. Jiang, H. Tai,Sens. Actuators B 317 (2020) 128204.
[37]	W. Zhang, J. Song, Q. He, H. Wang, W. Lyu, H. Feng, W. Xiong, W. Guo, J. Wu, L. Chen,J. Hazard. Mater. 384 (2020) 121445.
[38]	W. Wang, H. Feng, J. Liu, M. Zhang, S. Liu, C. Feng, S. Chen,Chem. Eng. J. 386 (2020) 124116.
[39]	Y. Yang, X. Wu, C. He, J. Huang, S. Yin, M. Zhou, L. Ma, W. Zhao, L. Qiu, C. Cheng, C. Zhao,ACS Appl. Mater. Interfaces 12 (2020) 13698-13708. DOI URL
[40]	J. Li, H. Ejima, N. Yoshie,ACS Appl. Mater. Interfaces 8 (2016) 19047-19053. DOI URL
[41]	A.H. Geeraerd, C.H. Herremans, J.F. Van Impe,Int. J. Food Microbiol. 59 (2000) 185-209. DOI URL
[42]	E.E. Elemike, D.C. Onwudiwe, M. Singh. J. Inorg,Organomet. Polym. Mater. 30 (2020) 400-409.
[43]	M.A.J.S. van Boekel,Int. J. Food Microbiol. 74 (2002) 139-159. DOI URL
[44]	H.C.D.B. Costa, É.S. Siguemoto, T.A.B.B. Cavalcante, D. de Oliveira Silva, L. G.M. Vieira, J.A.W. Gut,Food Chem. 341 (2021) 128287.
[45]	S. Zhu, O. Campanella, G. Chen,J. Food Eng. 292 (2021) 110364.
[46]	Y.K. Mishra, R. Adelung, C. Röhl, D. Shukla, F. Spors, V. Tiwari,Antivir. Res. 92 (2011) 305-312. DOI URL
[47]	Y.N. Chen, Y.H. Hsueh, C.T. Hsieh, D.Y. Tzou, P.L. Chang,Int. J. Environ. Res. Pub- lic Health 13 (20161) (2022) 430.
[48]	S. Ma, S. Zhan, Y. Jia, Q. Zhou,ACS Appl. Mater. Interfaces 7 (2015) 10576-10586. DOI URL
[49]	M. Li, D. Li, Z. Zhou, P. Wang, X. Mi, Y. Xia, H. Wang, S. Zhan, Y. Li, L. Li,Chem. Eng. J. 382 (2020) 122762.
[50]	L. Xiong, H. Yu, C. Nie, Y. Xiao, Q. Zeng, G. Wang, B. Wang, H. Lv, Q. Li, S. Chen,RSC Adv. 7 (2017) 51822-51830. DOI URL
[51]	S.L. Warnes, Z.R. Little,C.W. Keevil, mBio 6 (2015) e01697-e01715.
[52]	J.O. Noyce, H. Michels, C.W. Keevil,Appl. Environ. Microbiol. 73 (2007) 2748-2750. DOI URL
[53]	X. Sun, M. Dong, Z. Guo, H. Zhang, J. Wang, P. Jia, T. Bu, Y. Liu, L. Li, L. Wang, Int. J. Biol.Macromol. 167 (2021) 10-22.
[54]	X. Cai, J. Zhang, Y. Ouyang, D. Ma, S. Tan,Y. Peng, Langmuir 29 (2013) 5279-5285.
[55]	X. Zhang, Z. Zhang, Q. Shu, C. Xu, Q. Zheng, Z. Guo, C. Wang, Z. Hao, X. Liu, G. Wang, W. Yan, H. Chen, C. Lu,Adv. Funct. Mater. 31 (2021) 2008720.
[56]	J. Zhou, Q. Zhu, W. Pan, H. Xiang, Z. Hu, M. Zhu,Macromol. Rapid Commun. 42 (2021) 2000498.
[57]	J. Zhou, Q. Wang, C. Jia, M.T. Innocent, W. Pan, H. Xiang,M. Zhu, Macro-molecules 54 (2021) 7529-7539.
[58]	Y. Su, X. Zhang, G. Ren, Z. Zhang, Y. Liang, S. Wu, J. Shen,Chem. Eng. J. 400 (2020) 125949.

Ultra-fast bacterial inactivation of Cu₂O@halloysite nanotubes hybrids with charge adsorption and physical piercing ability for medical protective fabrics

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