Size effect of hybrid carbon nanofillers on the synergetic enhancement of the properties of HDPE-based nanocomposites.

High-density polyethylene (HDPE)-based hybrid nanocomposites containing graphene nanoplatelets (GnPs) and multiwall carbon nanotubes (MWCNTs) were fabricated using melt mixing followed by compression molding. The influences of size and weight ratio of both carbon-based nanofillers on the electrical, thermal, and mechanical properties of hybrid nanocomposites were evaluated. This study proves that the size and weight ratio of carbon-based nanofillers play a critical role in determining these properties. The optimum size and weight ratio of GnPs and MWCNTs are determined at the maximum achieved enhancement for each property. The HDPE-based nanocomposites containing GnPs with larger surface area and MWCNTs with higher aspect ratio display the highest electrical conductivity at GnPs/MWCNTs weight ratio of 2/3. The combination of GnPs with larger surface area and MWCNTs with lower aspect ratio provides the maximum Young's modulus enhancement of hybrid nanocomposites at 1/4 weight ratio of GnPs and MWCNTs. The nanocomposite containing GnPs with the largest lateral size and MWCNTs with a higher aspect ratio at a 3/2 weight ratio exhibits the highest thermal conductivity. Also, at around the percolation threshold of GnPs, the incorporation of MWCNTs with larger aspect ratio into the HDPE-based nanocomposites containing GnPs with the largest lateral size shows a distinct synergic effect on the thermal conductivity and Young's modulus, while an additive effect on the electrical conductivity and thermal stability.

c-Jun N-terminal kinase-dependent apoptotic photocytotoxicity of solvent exchange-prepared curcumin nanoparticles.

Indian spice curcumin is known for its anticancer properties, but the anticancer mechanisms of nanoparticulate curcumin have not been completely elucidated. We here investigated the in vitro anticancer effect of blue light (470 nm, 1 W)-irradiated curcumin nanoparticles prepared by tetrahydrofuran/water solvent exchange, using U251 glioma, B16 melanoma, and H460 lung cancer cells as targets. The size of curcumin nanocrystals was approximately 250 nm, while photoexcitation induced their oxidation and partial agglomeration. Although cell membrane in the absence of light was almost impermeable to curcumin nanoparticles, photoexcitation stimulated their internalization. While irradiation with blue light (1-8 min) or nanocurcumin (1.25-10 µg/ml) alone was only marginally toxic to tumor cells, photoexcited nanocurcumin displayed a significant cytotoxicity depending both on the irradiation time and nanocurcumin concentration. Photoexcited nanocurcumin induced phosphorylation of c-Jun N-terminal kinase (JNK), mitochondrial depolarization, caspase-3 activation, and cleavage of poly (ADP-ribose) polymerase, indicating apoptotic cell death. Accordingly, pharmacologial inhibition of JNK and caspase activity rescued cancer cells from photoexcited nanocurcumin. On the other hand, antioxidant treatment did not reduce photocytotoxicity of nanocurcumin, arguing against the involvement of oxidative stress. By demonstrating the ability of photoexcited nanocurcumin to induce oxidative-stress independent, JNK- and caspase-dependent apoptosis, our results support its further investigation in cancer therapy.

Highly Efficient Antibacterial Polymer Composites Based on Hydrophobic Riboflavin Carbon Polymerized Dots.

Development of new types of antimicrobial coatings is of utmost importance due to increasing problems with pathogen transmission from various infectious surfaces to human beings. In this study, new types of highly potent antimicrobial polyurethane composite films encapsulated by hydrophobic riboflavin-based carbon polymer dots are presented. Detailed structural, optical, antimicrobial, and cytotoxic investigations of these composites were conducted. Low-power blue light triggered the composites to eradicate Escherichia coli in 30 min, whereas the same effect toward Staphylococcus aureus was reached after 60 min. These composites also show low toxicity against MRC-5 cells. In this way, RF-CPD composites can be used for sterilization of highly touched objects in the healthcare industry.

Bactericidal and antioxidant bacterial cellulose hydrogels doped with chitosan as potential urinary tract infection biomedical agent.

Therapy of bacterial urinary tract infections (UTIs) and catheter associated urinary tract infections (CAUTIs) is still a great challenge because of the resistance of bacteria to nowadays used antibiotics and encrustation of catheters. Bacterial cellulose (BC) as a biocompatible material with a high porosity allows incorporation of different materials in its three dimensional network structure. In this work a low molecular weight chitosan (Chi) polymer is incorporated in BC with different concentrations. Different characterization techniques are used to investigate structural and optical properties of these composites. Radical scavenging activity test shows moderate antioxidant activity of these biocompatible composites whereas in vitro release test shows that 13.3% of chitosan is released after 72 h. Antibacterial testing of BC-Chi composites conducted on Gram-positive and Gram-negative bacteria causing UTIs and CAUTIs (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae) and encrustation (Proteus mirabilis) show bactericidal effect. The morphology analysis of bacteria after the application of BC-Chi shows that they are flattened with a rough surface, with a tendency to agglomerate and with decreased length and width. All obtained results show that BC-Chi composites might be considered as potential biomedical agents in treatment of UTIs and CAUTIs and as a urinary catheter coating in encrustation prevention.

Photoactive and antioxidant nanochitosan dots/biocellulose hydrogels for wound healing treatment.

Bacterial infection and their resistance to known antibiotics delays wound healing. In this study, nanochitosan dots (nChiD) produced by gamma irradiation have been encapsulated in bacterial cellulose (BC) polymer matrix to study the antibacterial potentials of these nanocomposites and their possible usage in wound healing treatment (scratch assay). Detailed analyses show that nChiDs have disc-like shape and average diameter in the range of 40 to 60 nm depending of the applied dose. All nChiDs as well as BC-nChiD nanocomposites emit green photoluminescence independently on the excitation wavelengths. The new designed nanocomposites do not have a cytotoxic effect; antioxidant analysis shows their moderate radical scavenging activity whereas antibacterial properties show significant growth inhibition of strains mostly found in difficult-to-heal wounds. The obtained results confirm that new designed BC-nChiD nanocomposites might be potential agent in wound healing treatment.

Correction: Gamma ray assisted modification of carbon quantum dot/polyurethane nanocomposites: structural, mechanical and photocatalytic study.

[This corrects the article DOI: 10.1039/C9RA00500E.].

Antibacterial photodynamic activity of carbon quantum dots/polydimethylsiloxane nanocomposites against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae.

Despite great efforts, the design of antibacterial surfaces is still a challenge. In this work, results of structural, mechanical, cytotoxic and antibacterial activities of hydrophobic carbon quantum dots/polydimethylsiloxane surfaces are presented. Antibacterial action of this surface is based on the generation of reactive oxygen species which cause bacteria damage by oxidative stress. At the same time, this surface was not cytotoxic towards the NIH/3T3 cells. Swelling-encapsulation-shrink method is applied for encapsulation of hydrophobic carbon quantum dots in medical grade silicone-polydimethylsiloxane. XPS and photoluminescence spectroscopy analyses confirm that hydrophobic carbon quantum dots have been encapsulated successfully into polydimethylsiloxane polymer matrix. Based on stress-strain test the improvement of mechanical properties of these nanocomposites is established. It is shown by electron paramagnetic resonance spectroscopy and luminescence method that nanocomposite generates singlet oxygen initiated by 470 nm blue light irradiation. Antibacterial testing shows the nanocomposite in the form of foil kills Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae and is very effective after only a 15 min irradiation.

Gamma ray assisted modification of carbon quantum dot/polyurethane nanocomposites: structural, mechanical and photocatalytic study.

In recent years, water pollution and contamination had become a major threat to the ecosystem. However, the use of nanostructured materials has been proven as a very promising approach in the treatment of polluted water. The present study reports the results of the gamma ray-assisted modification of hydrophobic carbon quantum dot (hCQD)/polyurethane nanocomposites for photocatalytic degradation of organic dyes. Different characterization methods were applied to investigate the influence of the different doses of gamma irradiation (1, 10 and 200 kGy) on the physical and chemical properties of nanocomposites (morphology, chemical content, mechanical properties, wettability, and potential for singlet oxygen generation). Surface morphology and mechanical properties analyses showed that gamma rays induced insignificant changes in the structure of nanocomposites, but the potential for singlet oxygen generation increased significantly. Here we also explore, in detail, the photocatalytic properties of gamma-ray modified hCQDs/polyurethane nanocomposites. UV-vis analysis showed that the removal efficiency of the rose bengal dye reached up to 97% for the nanocomposite irradiated with the dose of 200 kGy.

Graphene oxide size and structure pro-oxidant and antioxidant activity and photoinduced cytotoxicity relation on three cancer cell lines.

Photoactive materials called photosensitizers can be used for treatment of different types of cancer in combination with light source. In this paper, we have investigated pro-oxidant and antioxidant potentials of four graphene based nanomaterials (graphene oxide-GO, graphene quantum dots-GQDs, carbon quantum dots-CQDs and N-doped carbon quantum dots-N-CQDs) depending on the presence/absence of visible light source. Structural and optical properties of these materials and their potentials for reactive oxygen species generation/quenching are investigated by applying different microscopy and spectroscopy techniques (transmission electron microscopy, FTIR, UV-Vis, photoluminescence, electron paramagnetic resonance). Results show that all types of quantum dots has pro-oxidant and antioxidant potentials whereas GO demonstrated only moderate antioxidant effect. The best free radical scavenger is CQDs sample in the absence of light. CQDs are the best singlet oxygen generator under blue light irradiation as well. To check photo-cytotoxicity of these materials, photo-cytotoxic concentrations of the GO, GQDs, CQDs and N-CQDs were determined for three cellular lines: human rhabdomyosarcoma (RD), cell line derived from human cervix carcinoma Hep2c (HeLa) and fibroblast cell line from murine (L2OB). Cytotoxicity test has indicated that all samples are much less photocytotoxic than cis-diamminedichloroplatinum (cis-DPP). The production method and doping of quantum dots affect the photodynamic activity of tested samples very much.

Photo-induced antibacterial activity of four graphene based nanomaterials on a wide range of bacteria.

Due to controversial reports concerning antibacterial activity of different graphene based materials it is very important to investigate their antibacterial action on a wide range of Gram-positive and Gram-negative bacteria. In this paper we have investigated the structure induced phototoxic antibacterial activity of four types of graphene based materials: graphene oxide (GO), graphene quantum dots (GQDs), carbon quantum dots (CQDs) and nitrogen doped carbon quantum dots (N-CQDs). Antibacterial activity was tested on 19 types of bacteria. It is found that nanometer-size CQDs and N-CQDs are the most potent agents whereas micrometer-size GO has very poor antibacterial activity. Electron paramagnetic resonance measurements confirmed photodynamic production of singlet oxygen for all types of used quantum dots. Detailed analysis has shown that N-CQDs are an excellent photodynamic antibacterial agent for treatment of bacterial infections induced by Enterobacter aerogenes (E. aerogenes), Proteus mirabilis (P. mirabilis), Staphylococcus saprophyticus (S. saprophyticus), Listeria monocytogenes (L. monocytogenes), Salmonella typhimurium (S. typhimurium) and Klebsiella pneumoniae.

Carbon Quantum Dots Modified Polyurethane Nanocomposite as Effective Photocatalytic and Antibacterial Agents.

Development of new types of antibacterial coatings or nanocomposites is of great importance due to widespread multidrug-resistant infections including bacterial infections. Herein, we investigated biocompatibility as well as structural, photocatalytic, and antibacterial properties of photoactive hydrophobic carbon quantum dots/polyurethane nanocomposite. The swell-encapsulation-shrink method was applied for production of these nanocomposites. Hydrophobic carbon quantum dots/polyurethane nanocomposites were found to be highly effective generator of singlet oxygen upon irradiation by low-power blue light. Analysis of conducted antibacterial tests on Staphyloccocus aureus and Escherichia coli showed 5-log bactericidal effect of these nanocomposites within 60 min of irradiation. Very powerful degradation of dye (rose bengal) was observed within 180 min of blue light irradiation of the nanocomposites. Biocompatibility studies revealed that nanocomposites were not cytotoxic against mouse embryonic fibroblast cell line, whereas they showed moderate cytotoxicity toward adenocarcinomic human epithelial cell line. Minor hemolytic effect of these nanocomposites toward red blood cells was revealed.