Nanoemitters and innate immunity: the role of surfactants and bio-coronas in myeloperoxidase-catalyzed oxidation of pristine single-walled carbon nanotubes.

Single-walled carbon nanotubes (SWCNTs) are experimentally utilized in in vivo imaging and photothermal cancer therapy owing to their unique physicochemical and electronic properties. For these applications, pristine carbon nanotubes are often modified by polymer surfactant coatings to improve their biocompatibility, adding more complexity to their recognition and biodegradation by immuno-competent cells. Here, we investigate the oxidative degradation of SWCNTs catalyzed by neutrophil myeloperoxidase (MPO) using bandgap near-infrared (NIR) photoluminescence and Raman spectroscopy. Our results show diameter-dependence at the initial stages of the oxidative degradation of sodium cholate-, DNA-, and albumin-coated SWCNTs, but not phosphatidylserine-coated SWCNTs. Moreover, sodium deoxycholate- and phospholipid-polyethylene glycol coated SWCNTs were not oxidized under the same reaction conditions, indicating that a surfactant can greatly impact the biodegradability of a nanomaterial. Our data also revealed that possible binding between MPO and surfactant coated-SWCNTs was unfavorable, suggesting that oxidation is likely caused by a hypochlorite generated through halogenation cycles of free MPO, and not MPO bound to the surface of SWCNTs. The identification of SWCNT diameters and coatings that retain NIR fluorescence during the interactions with the components of an innate immune system is important for their applications in in vivo imaging.

Defect-Induced Near-Infrared Photoluminescence of Single-Walled Carbon Nanotubes Treated with Polyunsaturated Fatty Acids.

Single-walled carbon nanotubes (SWCNTs) have been incorporated in many emerging applications in the biomedical field including chemical sensing, biological imaging, drug delivery, and photothermal therapy. To overcome inherent hydrophobicity and improve their biocompatibility, pristine SWCNTs are often coated with surfactants, polymers, DNA, proteins, or lipids. In this paper, we report the effect of polyunsaturated fatty acids (PUFAs) on SWCNT photoluminescence. A decrease in the SWCNT bandgap emission (E11) and a new red-shifted emission (E11-) were observed in the presence of PUFAs. We attribute the change in SWCNT photoluminescence to the formation of oxygen-containing defects by lipid hydroperoxides through photo-oxidation. The observed changes in near-infrared emission of SWCNTs are important for understanding the interaction between SWCNTs and lipid biocorona. Our results also indicate that photoexcited SWCNTs can catalyze lipid peroxidation similarly to lipoxygenases.

Enzyme-catalyzed oxidation facilitates the return of fluorescence for single-walled carbon nanotubes.

In this work, we studied enzyme-catalyzed oxidation of single-walled carbon nanotubes (SWCNTs) produced by the high-pressure carbon monoxide (HiPco) method. While oxidation via strong acids introduced defect sites on SWCNTs and suppressed their near-infrared (NIR) fluorescence, our results indicated that the fluorescence of SWCNTs was restored upon enzymatic oxidation, providing new evidence that the reaction catalyzed by horseradish peroxidase (HRP) in the presence of H2O2 is mainly a defect-consuming step. These results were further supported by both UV-vis-NIR and Raman spectroscopy. Therefore, when acid oxidation followed by HRP-catalyzed enzyme oxidation was employed, shortened (<300 nm in length) and NIR-fluorescent SWCNTs were produced. In contrast, upon treatment with myeloperoxidase, H2O2, and NaCl, the oxidized HiPco SWCNTs underwent complete oxidation (i.e., degradation). The shortened, NIR-fluorescent SWCNTs resulting from HRP-catalyzed oxidation of acid-cut HiPco SWCNTs may find applications in cellular NIR imaging and drug delivery systems.

Fluorescence quenching of dyes covalently attached to single-walled carbon nanotubes.

The development of chromophore-carbon nanotube hybrids requires efficient and accurate methods to investigate their photophysical properties. Using the ability of the fluorescence labeling of surface species (FLOSS) technique to determine the density of covalently attached dyes to the surface of single-walled carbon nanotubes (SWCNTs), the luminescence of dye-SWCNT hybrids was quantitatively studied with two chromophores: dansyl hydrazine (DH) and panacyl bromide (PB). The fluorescence intensity of PB-SWCNT hybrids was reduced by 20-80% compared to that of free PB. A strong positive correlation between the degree of quenching and the residual metal impurity content in the SWCNT sample suggests that quenching of fluorescence of PB in PB-SWCNTs may be caused by the metal impurities and not by SWCNTs. On the contrary, the intensity of fluorescence of DH-SWCNT hybrids was reduced by almost 2 orders of magnitude compared to free DH, independent of the residual metal content in the SWCNT sample, suggesting that quenching of fluorescence in DH-SWCNT hybrids might occur via charge transfer from DH chromophores to SWCNTs, and revealing the potential of DH-SWCNT hybrids for solar light harvesting applications.