Abstract

Oxidized multi-walled carbon nanotubes (oxCNTs) were functionalized by a simple non-covalent modification procedure using quaternized hyperbranched poly(ethyleneimine) derivatives (QPEIs), with various quaternization degrees. Structural characterization of these hybrids using a variety of techniques, revealed the successful and homogenous anchoring of QPEIs on the oxCNTs’ surface. Moreover, these hybrids efficiently dispersed in aqueous media, forming dispersions with excellent aqueous stability for over 12 months. Their cytotoxicity effect was investigated on two types of gram(−) bacteria, an autotrophic (cyanobacterium Synechococcus sp. PCC 7942) and a heterotrophic (bacterium Escherichia coli). An enhanced, dose-dependent antibacterial and anti-cyanobacterial activity against both tested organisms was observed, increasing with the quaternization degree. Remarkably, in the photosynthetic bacteria it was shown that the hybrid materials affect their photosynthetic apparatus by selective inhibition of the Photosystem-I electron transport activity. Cytotoxicity studies on a human prostate carcinoma DU145 cell line and 3T3 mouse fibroblasts revealed that all hybrids exhibit high cytocompatibility in the concentration range, in which they also exhibit both high antibacterial and anti-cyanobacterial activity. Thus, QPEI-functionalized oxCNTs can be very attractive candidates as antibacterial and anti-cyanobacterial agents that can be used for potential applications in the disinfection industry, as well as for the control of harmful cyanobacterial blooms.

Highlights

  • Carbon nanotubes (CNTs) have attracted significant scientific and technological interest due to their unique structural characteristics and their excellent electronic, mechanical, and thermal properties [1,2]

  • The introduction of α-hydroxyamine moieties, together with the trimethylammonium groups, to PEI was achieved by the reaction of the PEI primary amines with appropriate amounts of glycidyltrimethylammonium chloride, yielding three PEI derivatives, i.e., 30-quaternized hyperbranched poly(ethyleneimine) derivatives (QPEIs), 50-QPEI, and 80-QPEI (Scheme 1)

  • Based on the interpretation of the experimental data using a non-linear regression of the four-parameter logistic function (Figure S6), it is obvious that cell proliferation is concentration dependent, while Oxidized multi-walled carbon nanotubes (oxCNTs)@80-QPEI exhibited the most promising anti-cyanobacterial activity, compared to the other two hybrid materials

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Summary

Introduction

Carbon nanotubes (CNTs) have attracted significant scientific and technological interest due to their unique structural characteristics and their excellent electronic, mechanical, and thermal properties [1,2]. Non-covalent functionalization, based on π–π stacking and ionic interactions between various molecules and the CNTs graphitic surface [9,10,11] does not affect their electronic structure, and has been achieved using a multitude of surfactants [6,7] and polymers [8,10], resulting in modified CNTs, compatible with specific solvents or targeted applications In this context, their functionalization with dendritic polymers such as dendrons, dendrimers, and hyperbranched polymers, is expected to be a very promising strategy, when aiming to achieve increased water solubility. In this study, aiming to develop water soluble MWCNTs with enhanced antibacterial/anticyanobacteria properties, oxidized multi-walled carbon nanotubes (oxCNTs) were non-covalently functionalized using a series of partially quaternized hyperbranched poly(ethyleneimine) derivatives, yielding novel water-soluble hybrid materials. PCC 7942) and a heterotrophic (bacterium Escherichia coli), while their cytocompatibility was investigated on eukaryotic cell lines

Synthesis and Characterization of QPEI-Functionalized oxCNTs
Evaluation of Antibacterial and Anti-Cyanobacterial Activity
Cell Viability Assay
Preparation of QPEI-Functionalized oxCNTs
Characterization of QPEI-Functionalized oxCNTs
Escherichia coli Growth Inhibition Assay
SEM Analysis of the Cellular Morphology
Measurements of Photosystem I and II Electron Transport Activities
3.10. Cell Cytotoxicity
Conclusions
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