We report a novel class of highly water-soluble decacationic methano[60]fullerene decaiodides C60[>M(C3N6+C3)2]-(I−)10 [1-(I−)10] capable of co-producing singlet oxygen (Type-II) and highly reactive hydroxyl radicals, formed from superoxide radicals in Type-I photosensitizing reactions, upon illumination at both UVA and white light wavelengths. The O2‒·-production efficiency of 1-(I−)10 was confirmed by using a O2‒·-reactive bis(2,4-dinitrobenzenesulfonyl)tetrafluorofluorescein probe and correlated to the photoinduced electron-transfer event going from iodide anions to 3C60*[>M(C3N6+C3)2] leading to C60‒·[>M(C3N6+C3)2]. Incorporation of a defined number (ten) of quaternary ammonium cationic charges per C60 in 1 was aimed to enhance its ability to target pathogenic Gram-positive and Gram-negative bacterial cells. We used the well-characterized malonato[60]fullerene diester monoadduct C60[>M(t-Bu)2] as the starting fullerene derivative to provide a better synthetic route to C60[>M(C3N6+C3)2] via transesterification reaction under trifluoroacetic acid catalyzed conditions. These compounds may be used as effective photosensitizers and nano-PDT drugs for photoinactivation of pathogens.
Synthesis of several C60-(antenna)x conjugates was performed to demonstrate high flexibility in the design of organic nonlinear optical (NLO) nanostructures showing broadband characteristics with capability to absorb light over a wide range of wavelengths. It was achieved by covalent attachment of a hybrid combination of two types of light-harvesting fluorescent antenna chromophores on a C60 cage. Ultrafast photoresponsive intramolecular Föster resonance energy-transfer among antenna units and shared excited energy-accepting C60 cage is proposed as a plausible mechanism to enhance the broadband NLO ability. Characterization of the branched triad C60(>DPAF-C18)(>CPAF-C2M) and the tetrad C60(>DPAF-C18)(>CPAF-C2M)2 was carried out by various spectroscopic techniques. These compounds showed approximately equal extinction coefficients of optical absorption over 400‒550 nm that corresponds to near-IR two-photon based excitation wavelengths at 780‒1100 nm. These nanomaterials may be utilized in NLO coatings for achieving efficient light-transmittance reduction at the same NIR wavelengths.
Fullerene derivatives have appealing properties that can potentially be used in materials science and medical applications. In particular, fullerenes are known to produce reactive oxygen species upon their excitation with light. This makes them particularly attractive as photosensitizers for photodynamic therapy (PDT). Photodynamic therapy is a new modality of treatment of cancer as well as some non-cancerous conditions. It involves the combined actions of a drug (photosensitizer) and light to produce a cytotoxic effect. Water-soluble hexa(sulfo-n-butyl)[60]fullerenes (FC4S) was reported recently to generate singlet oxygen (1O2) and superoxide radical (O2-·) upon its excitation with light, making it a promising candidate for PDT treatments. Recently, we synthesized new amphiphilic fullerene derivatives, namely, [60]fullerene-diphenylaminofluorene-oligo(ethylene glycol) conjugates, C60(>DPAF-PEG600) and C60(>DPAF-PEG2000), as potential photosensitizers. In this paper we compare FC4S to PEG-based fullerenes in terms of their singlet oxygen photosensitization ability. We measured time-resolved kinetics of singlet oxygen luminescence photosensitized by excitation of fullerenes via a 10 ns pulsed laser at 523 nm. For FC4S we observed "normal" kinetics with a monoexponential decay profile giving a time constant 3.8 us in water. In contrast, for the case of C60(>DPAF-PEG600) and C60(>DPAF-PEG2000), a non-monoexponential decay profile with a long tail (~ 102 μs) in water was observed. We hypothesize that this is due to formation of vesicles by PEG fullerenes in aqueous solution. To investigate photodynamic activity of these fullerene derivatives in vitro, we used HeLa human adenocarcinoma and B16 mouse melanoma cell lines. FC4S showed clear photodynamic effects in both cell lines. The total fluence required to kill 50% of the cells at the drug concentration of 20 μM was 36 Jcm-2 for HeLa cells and 72 Jcm-2 for B16 cells. Neither PEG-based fullerene derivatives showed any appreciable photodynamic activity, possibly, due to low efficiency of singlet oxygen generation.
KEYWORDS: Carbon nanotubes, Transmission electron microscopy, Nitrogen, Chemical species, Spectroscopy, Chemical elements, Plasmons, Sulfur, Ionization, Signal attenuation
The novel mechanical and electrical properties of carbon nanotubes have potential applications in a variety of fields, and their size makes them appealing for use in biosensors. However, in order to exploit their potential, carbon nanotubes must be functionalized for biologic compatibility. Sulfonated and polyanilinated multi-walled and single-walled carbon nanotubes were investigated by several spectroscopic and microscopic methods to asses their feasibility in characterization of functionalized carbon nanotubes (CNT). Transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS) and energy-dispersive X-ray analysis (EDX) were applied to confirm the presence of heteroatoms that were not present in the parent CNTs. EELS ratio mapping, used in conjunction with bright-field TEM imaging, is an extremely powerful tool for examining functionalized nanotubes and other composites because it provides a means of showing the spatial arrangement of individual elements in a sample. This characterization approach provides clear evidence of functional group incorporation onto the CNT. Subsequent atom mapping along the vicinity of the tube structure also allowed us to illustrate the three dimensional distribution of the heteroatoms along the CNT surface. Other elemental analysis techniques can confirm and possibly quantify the presence of a particular element, but fail to illustrate its spatial distribution in a material. In this study, the presence of nitrogen and sulfur atoms along the surface of a nanotube have been confirmed and shown to be uniform by means of TEM and EELS. EDX plots have been investigated as an additional measure of functionalization.
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