Supramolecular Switching Surface for Antifouling and Bactericidal

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Supramolecular Switching Surface for Antifouling and Bactericidal Activities Lingda Zeng, Yukun Wu, Jiangfei Xu, Shu Wang, and Xi Zhang ACS Appl. Bio Mater., Just Accepted Manuscript • DOI: 10.1021/acsabm.8b00831 • Publication Date (Web): 24 Jan 2019 Downloaded from http://pubs.acs.org on January 27, 2019

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Supramolecular Switching Surface for Antifouling and Bactericidal Activities Lingda Zeng#†, Yukun Wu#†, Jiang-Fei Xu*†, Shu Wang‡, Xi Zhang*† † Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, P.R. China ‡ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China

Keywords: Supramolecular Chemistry at Interfaces, Biomaterial, Supramolecular Switch, Bactericidal Surface, Antifouling

Abstract: Antibacterial materials are often bothered by the problems of drugresistance-induction and adhesion-to-invalidation, coming from the exposure of reusable bactericidal materials before or after utilization. Herein, an efficient and easily transformable supramolecular switching surface for anti-fouling and bactericidal was successfully fabricated, through introducing a negatively charged macrocyclic host S6-corona[3]arene[3]pyridazine (S6-CAP) to a 1 ACS Paragon Plus Environment

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contact killing surface constructed by a positively charged amphiphilic bactericide. The S6-CAP was able to fully switch off the bactericidal activity and make the surfaces antifouling. After switched on by simply washing off much of S6-CAP, the bactericidal activity was even better than the original contact killing surfaces.

Multifunctional biointerfaces designed and constructed by introducing supramolecular chemistry strategies onto surfaces have been demonstrated great potentials in drug release,1 photoswitchable bioelectrocatalysis,2-3 reversible adsorption and resistance of peptides, proteins and cells,4-5 and so on.6-7 However, it is important to note that, whereas many supramolecular switches and molecular devices work well in solution, problems can arise when they are transferred onto solid surfaces. Therefore, the development of supramolecular chemistry at interfaces can result in a deeper understanding of material science, and further guide us to develop biomaterials and medicines.

Contact-killing surface, which can be constructed by grafting biocides to a surface through self-assembled monolayer (SAMs),8-9 is one of the biomaterials that benefit a lot from the progress of supramolecular chemistry at interfaces.1011

In contrast with solution-type sterilizing agents, it is reusable as well as

emissions and residues free, thus suiting for some daily usages like raw food 2 ACS Paragon Plus Environment

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sterilization and antibacterial products for outdoor adventure. Previous works about contact-killing system usually focus on how to improve the efficiency12-13 or renew the surfaces.14-17 However, the conditions of the contact-killing surfaces before or after utilization are also vital for reusable bactericidal materials, as the exposure of bactericidal activity of contact-killing surfaces may lead to drug resistance.18 Furthermore, long-term adhesive bacteria can make the surfaces difficult to be cleaned and ineffective.19 Therefore, it is important for contact-killing surfaces to be antifouling20-21 before or after utilization and switch bactericidal activity on demand. In addition, it will be more practical if the transition procedure to applied states can be simply achieved without complicated stimuli, such as acid or base.

For solution-type sterilizing agents, the bactericidal activities can be tuned by two methods. One is screening biocidal groups with macrocyclic hosts;22-23 the other is changing the interfacial charges of the bactericides.24 Both methods may influence the interactions between bactericides and bacteria for contactkilling systems. However, neither of them can achieve deactivation and reactivation in an easy, dynamic and complete manner.

We wondered if we could combine the two methods together and fabricate a supramolecular switching surface for antifouling and bactericidal activities. To this end, as a proof-of-concept, a charge-reversal host-guest complex was 3 ACS Paragon Plus Environment


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constructed on gold surfaces. As shown in Scheme 1, we designed and synthesized a positively charged amphiphilic bactericide NpAAS (Scheme 1a). It was grafted to gold surfaces with the chemisorption of Au-S bonds to offer Np surfaces. The Np surfaces were expected to be contact-killing with a strong adhesion property because of the positive charge. To protect the materials from bacteria before or after utilization, a water-soluble macrocyclic host S6corona[3]arene[3]pyridazine (S6-CAP, Scheme 1a) was employed to interact with Np surfaces, thus changing the surfaces into CAP surfaces. S6-CAP was first synthesized by Wang et al and proven to be able to incorporate ethylenediamine bisquaternary ammonium group with binding constant as high as 106 M-1.25-26 Inspired by these works, we used S6-CAP on the surfaces to fabricate host-guest complex. The binding of S6-CAP may not only screen the naphthylmethyl quaternary ammonium group but also change the surface potential to be negative. As a result, the CAP surfaces should become bactericidal deactivated. Furthermore, we expected that such surfaces with negative charges could be antifouling at the same time. To switch on the bactericidal activity, the S6-CAP could be removed by simply washing the CAP surfaces to afford Np-CAP surfaces. Through constructing a host-guest complex with S6-CAP and NpAAS on gold surfaces, we are able to fabricate a supramolecular switching surface for antifouling and bactericidal activities. It is anticipated that such a strategy can shed light on solving the drug-resistance

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and adhesion-to-invalidation problems caused by exposure of reusable bactericidal materials before or after utilization.

The modification of surfaces can be reflected from the change of surface wettability. As shown in Figure 1a, the contact angles (CAs) of Au surfaces (produced by immersing Plasma-treated gold substrates into methanol) were about 76 °. The Plasma-treated gold surfaces possess large surface energy, which immensely facilitate the interaction with other molecules. Thus, the methanol molecules adsorbed to gold,27-28 making Au surfaces much more hydrophobic

than

Plasma-treated

gold

surfaces,

which

are

almost

superhydrophilic. The CAs of Np surfaces were about 39 °, indicating Np surfaces are more hydrophilic than the Au surfaces, which should arise from the chemisorption of amphiphilic NpAAS on gold surfaces. NpAAS displaced methanol molecules and formed SAMs on gold surfaces. As for the CAP surfaces, they possessed CAs of about 25 °. The host-guest interaction between S6-CAP and ethylenediamine bisquaternary ammonium group is able to tie S6-CAP on the surfaces so that CAP surfaces become even more hydrophilic than Np surfaces on account of the high water-solubility of S6-CAP. The CAs of Np-CAP surfaces were about 37 °, where the wettability of the NpCAP surfaces recovered to that of the Np surfaces, suggesting the removal of S6-CAP. Therefore, all the four surfaces as shown in Scheme 1b are



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hydrophilic and the CAP surfaces are the most hydrophilic ones, which may benefit the antifouling property.

As the wettability is not only influenced by the chemical composition but also by the micro-nano structure of the surfaces, atom force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) techniques were used to reveal the mechanism behind the changes of wettability as discussed above. The three-dimensional height diagrams of the four surfaces are shown in Figure S2. The roughness of the four surfaces are Au ≈ Np ≈ Np-CAP > CAP as indicated by the Rq value. For hydrophilic surfaces, the decrease of roughness always leads to the decrease of hydrophilicity, so the roughness change is not the main reason for wettability change. Therefore, it must come from the change of chemical composition, which was investigated by TOFSIMS. The full spectra of TOF-SIMS for the four surfaces are exhibited in Figure S3. The peak at m/z ≈ 141 (Figure 2a) found on Np, CAP and Np-CAP surfaces was ascribed to the peak of naphthylmethyl cation (C11H9+), which belonged to NpAAS. Although there was noise at m/z ≈ 141 on Au surfaces, it should not be naphthylmethyl cation because of the different peak shape and value. This result indicates that Np surfaces are successfully modified by NpAAS after immersion. As for the peak at m/z ≈ 326, which was only found on CAP and Np-CAP surfaces, it may come from S6-CAP. It is noted that there seems to be


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still some S6-CAP remaining on the Np-CAP surfaces, after washing. However, more evidence is necessary to make sure that S6-CAP binds to NpAAS.

The binding of S6-CAP to NpAAS was further verified by Nuclear Magnetic Resonance (NMR) spectrometer of model molecules and by in-situ characterization of Biomolecular Interaction Analysis (BIACORE). The chemical shift of the hydrogen on model guest (Figure S4) exhibits clear upfield shifting, hence indicating the pseudortaxane structure of the guest and host. BIACORE is a method to study biomacromolecular interactions. Taking the advantage of the high sensitivity, it can also be utilized to study the adsorption and desorption on a surface with well-designed chips. Figure 2b shows the adsorption-desorption curve of Np surfaces in aqueous solution of S6-CAP. It is clear that S6-CAP can be adsorbed on Np surfaces on account of the hostguest interaction between S6-CAP and NpAAS. The kinetics of adsorption and desorption cannot be obtained as the curve is too steep to be accurately fitted. Both the adsorption and desorption are fast and at the level of second, which accords with small molecule binding model in BIACORE experiment. By analyzing the result referring to Reynolds diagram method (Figure S5), the absorption density is calculated to be 279 pg/mm2 based on the absorption curve and 278 pg/mm2 based on the desorption curve. The uniform amount of absorption and desorption indicates that S6-CAP can easily be removed by flowing water. In addition, a cyclic BIACORE experiment shows that this 7 ACS Paragon Plus Environment


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binding/release process is repeatable (Figure S7). The desorption curve of Np-

CAP surfaces was also measured (Figure 2c). The density of S6-CAP residue is 18 pg/mm2, exhibiting that there is about 6% of residual S6-CAP on Np-CAP surfaces. Combining the results of AFM, TOF-SIMS and BIACORE, it is confirmed that the surface modification is successful as designed. The chemical compositions of the four surfaces have been identified, well supporting the previous interpretation of wettability.

To study if the adhesion and bactericidal behaviors of the designed surfaces were antifouling as well as bactericidal deactivated on switch-off states (represented by CAP surfaces) and bactericidal on switch-on states (represented by Np and Np-CAP surfaces), we evaluated the adhesion property of the surfaces with E. coli as demonstration. Figure 3 shows typical SEM images of E. coli adhering to the four surfaces. Au, Np and Np-CAP surfaces are covered with a large amount of E. coli; whereas for CAP surfaces, almost no E. coli is adhered. This difference of anti-adhesion performance arises from the different wettability and charges on these surfaces. For Au surfaces, they are electrically neutral and not very hydrophilic. Thus, bacteria can stick on them. For Np and Np-CAP surfaces, although they are more hydrophilic, the positive surface charge would attract negatively charged species such as E.

coli. Both surfaces are “magnet” for bacteria, which is in favor of killing bacteria. The CAP surfaces are the most hydrophilic surfaces among the four ones and 8 ACS Paragon Plus Environment

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covered by the negatively charged S6-CAP. Thus, the bacteria, exhibiting negative charges on the membrane, have a strong repulsive effect on the CAP surfaces. Therefore, the CAP surfaces exhibit antifouling ability, which meets the requirements for reusable bactericidal materials before or after utilization.

In addition to antifouling, we were curious if the bactericidal activity of the materials could be efficiently switched on/off. To answer this question, the bactericidal properties of the four surfaces were analyzed with colony forming units (CFUs) and Live/Dead staining assay, as shown in Figure 4a-d and Figure S8. In contrast with non-bactericidal Au surfaces, the Np surfaces exhibited bactericidal activity with a bactericidal rate of 79.8% (Figure 4e). As Np surfaces were built through constructing SAMs with a positively charged amphiphilic bactericide NpAAS on gold surfaces, the bactericidal mechanism is destroying the cell membrane like other amphiphilic quaternary ammonium salts as shown in Figure S9. The bactericidal rate of CAP surfaces decreased dramatically to 3.6%. The contact-killing activity is almost completely switched off, as S6-CAP widely screens the biocidal naphthylmethyl quaternary ammonium groups and changes the interfacial potential of the surfaces to be negative. Besides, it is worth noting that S6-CAP does not show significant cytotoxicity even at the concentration of 200 μM (Figure S10), which is much higher than the releasing concentration of S6-CAP in solution. To our surprise, Np-CAP surfaces displayed excellent sterilizing activity with bactericidal rate of 97.6%, which was 9 ACS Paragon Plus Environment


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17.8% higher than that of the original Np surfaces. The reason may be that the carboxyl groups of remaining S6-CAP compete for the hydrogen bonds or bind Mg2+ and Ca2+ within the bacterial cell wall. Therefore, cell wall permeability is increased, and that enhances bacteria killing.24, 29-30 Considering the adhesion behaviors of the four surfaces, we have successfully fabricated a supramolecular switching surface for antifouling and bactericidal activities on demand taking the advantage of the dynamic nature of the host-guest complex with S6-CAP and NpAAS constructed on gold surfaces. It is anticipated such a strategy can provide an effective option of solving the drug-resistance and adhesion-to-invalidation problems caused by the exposure of reusable bactericidal materials before or after utilization.

In summary, we have successfully designed and constructed a supramolecular switching surface for antifouling and bactericidal activities. The surface is antifouling and non-bactericidal when it is switched off by screening biocidal groups and changing the interfacial charges to be negative through the hostguest complexation of S6-CAP; while the bactericidal activity can be switched on by simply washing off the host S6-CAP. Both switches are highly efficient and the Np-CAP surface displays excellent sterilizing activity. Such a strategy of surface modification may further be applied to porous silica and shed light on the design of reusable bactericidal products to solve the drug resistance and


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adhesion-to-invalidation problems. In addition, this study can enrich the application of supramolecular chemistry at interfaces.

Scheme 1. (a) Chemical structure of NpAAS and S6-CAP. (b) Schematic representation of fabricating of supramolecular switching surface for antifouling (CAP) and bactericidal (Np & Np-CAP) activities with S6-CAP and NpAAS.



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Figure 1. Contact angles of Au, Np, CAP and Np-CAP surface. The photos on the top of each bar show the shapes of water drops.


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Figure 2. (a) TOF-SIMS of Au, Np, CAP and Np-CAP surfaces. (b) The adsorption-desorption curve of Np surfaces in aqueous solution of S6-CAP. (c) The desorption curve of Np-CAP surfaces. The Np-CAP surfaces were produced by washing CAP surfaces though immersion method other than flushing method to get better control of the variables.



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Figure 3. SEM images of E. coli adhere to (a) Au, (b) Np, (c) CAP and (d) NpCAP surfaces.


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Figure 4. Colony forming units (CFUs) for E. coli treated with (a) Au, (b) Np, (c) CAP and (d) Np-CAP surfaces. (e) Bactericidal rates of Np, CAP and Np-CAP surfaces analyzed by CFUs.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Synthesis of NpAAS and model molecule NpAA; operation of surface modification; operation of adhesion test and bactericidal test; roughness of surfaces (AFM); full TOF-SIMS spectra; NMR spectra of model guest, S6CAP and their 1:1 complex; amending method of BIACORE curves (PDF); mechanism of contact-killing; cell viability assay of S6-CAP

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected]



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Present Addresses † Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, P.R. China ‡ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the ﬁnal version of the manuscript. Author Contributions # Lingda

Zeng and Yukun Wu contributed equally.

Funding Sources The Foundation for Innovative Research Groups of NSFC (21821001). The Tsinghua University Initiative Research Project (20181080084).


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Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENT This work was financially supported by the Foundation for Innovative Research Groups of NSFC (21821001) and the Tsinghua University Initiative Research Project (20181080084). We want to thank Prof. Mei-Xiang Wang for his guidance in the synthesis of S6-CAP, Mr. Shuai Zhang for his help in SEM experiments, Mr. Haitao Yuan for his help in bacterial experiment, Mr. Chen Zhou for his help for images of fluorescence microscope and Dr. Yincheng Chang for his assistance of cytotoxicity tests. We also thank Dr. Haotian Bai and Mr. Yuchong Yang for their constructive discussions.

ABBREVIATIONS AFM, Atom Force Microscopy; TOF-SIMS, Time-of-Flight Secondary Ion Mass Spectrometry; NMR, Nuclear Magnetic Resonance; BIACORE, Biomolecular Interaction Analysis; CFUs, Colony Forming Units; CAs, Contact Angles; S6-CAP, S6-Corona[3]arene[3]pyridazine; SAMs, Self-Assembled Monolayer.



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Supramolecular Switching Surface for Antifouling and Bactericidal

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