Carbon Nanodisks Decorated with Guanidinylated Hyperbranched Polyethyleneimine Derivatives as Efficient Antibacterial Agents.

Non-toxic carbon-based hybrid nanomaterials based on carbon nanodisks were synthesized and assessed as novel antibacterial agents. Specifically, acid-treated carbon nanodisks (oxCNDs), as a safe alternative material to graphene oxide, interacted through covalent and non-covalent bonding with guanidinylated hyperbranched polyethyleneimine derivatives (GPEI5K and GPEI25K), affording the oxCNDs@GPEI5K and oxCNDs@GPEI25K hybrids. Their physico-chemical characterization confirmed the successful and homogenous attachment of GPEIs on the surface of oxCNDs, which, due to the presence of guanidinium groups, offered them improved aqueous stability. Moreover, the antibacterial activity of oxCNDs@GPEIs was evaluated against Gram-negative E. coli and Gram-positive S. aureus bacteria. It was found that both hybrids exhibited enhanced antibacterial activity, with oxCNDs@GPEI5K being more active than oxCNDs@GPEI25K. Their MIC and MBC values were found to be much lower than those of oxCNDs, revealing that the GPEI attachment endowed the hybrids with enhanced antibacterial properties. These improved properties were attributed to the polycationic character of the oxCNDs@GPEIs, which enables effective interaction with the bacterial cytoplasmic membrane and cell walls, leading to cell envelope damage, and eventually cell lysis. Finally, oxCNDs@GPEIs showed minimal cytotoxicity on mammalian cells, indicating that these hybrid nanomaterials have great potential to be used as safe and efficient antibacterial agents.

Multi-Walled Carbon Nanotubes Decorated with Guanidinylated Dendritic Molecular Transporters: An Efficient Platform for the Selective Anticancer Activity of Doxorubicin.

An efficient doxorubicin (DOX) drug delivery system with specificity against tumor cells was developed, based on multi-walled carbon nanotubes (MWCNTs) functionalized with guanidinylated dendritic molecular transporters. Acid-treated MWCNTs (oxCNTs) interacted both electrostatically and through hydrogen bonding and van der Waals attraction forces with guanidinylated derivatives of 5000 and 25,000 Da molecular weight hyperbranched polyethyleneimine (GPEI5K and GPEI25K). Chemical characterization of these GPEI-functionalized oxCNTs revealed successful decoration with GPEIs all over the oxCNTs sidewalls, which, due to the presence of guanidinium groups, gave them aqueous compatibility and, thus, exceptional colloidal stability. These GPEI-functionalized CNTs were subsequently loaded with DOX for selective anticancer activity, yielding systems of high DOX loading, up to 99.5% encapsulation efficiency, while the DOX-loaded systems exhibited pH-triggered release and higher therapeutic efficacy compared to that of free DOX. Most importantly, the oxCNTs@GPEI5K-DOX system caused high and selective toxicity against cancer cells in a non-apoptotic, fast and catastrophic manner that cancer cells cannot recover from. Therefore, the oxCNTs@GPEI5K nanocarrier was found to be a potent and efficient nanoscale DOX delivery system, exhibiting high selectivity against cancerous cells, thus constituting a promising candidate for cancer therapy.

Cytotoxicity Effects of Water-Soluble Multi-Walled Carbon Nanotubes Decorated with Quaternized Hyperbranched Poly(ethyleneimine) Derivatives on Autotrophic and Heterotrophic Gram-Negative Bacteria.

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.

Enzymatic Conversion of Oleuropein to Hydroxytyrosol Using Immobilized ß-Glucosidase on Porous Carbon Cuboids.

In the present study, we developed novel ß-glucosidase-based nano-biocatalysts for the bioconversion of oleuropein to hydroxytyrosol. Using non-covalent or covalent immobilization approaches, ß-glucosidases from almonds and Thermotoga maritima were attached for the first time on oxidized and non-oxidized porous carbon cuboids (PCC). Various methods were used for the characterization of the bio-nanoconjugates, such as Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and fluorescence spectroscopy. The oxidation state of the nanο-support and the immobilization procedure play a key role for the immobilization efficiency or the catalytic activity of the immobilized ß-glucosidases. The nano-biocatalysts were successfully used for the hydrolysis of oleuropein, which leads to the formation of its bioactive derivative, hydroxytyrosol (up to 2.4 g L-1), which is a phenolic compound with numerous health benefits. The bio-nanoconjugates exhibited high thermal and operational stability (up to 240 hours of repeated use), which indicated that they are efficient tools for various bio-transformations.