RESUMO
By means of the density functional theory calculations, two C88(D2:35)-based endohedral fullerenes, Lu3C2@C88(D2:35) and Lu3N@C88(D2:35) which encapsulate tri-lutetium carbide and tri-lutetium nitride cluster were investigated. For the cores in Lu3C2@C88 and Lu3N@C88, the trivalent C2 and N respectively template a butterfly-shaped endohedral moiety and a planar tri-lutetium cluster within the same D2-symmetric C88 cage. Moreover, Lu3N@C88 - D2 has a closed-shell electronic structure but for LuC3C2@C88 - D2, it owns an unpaired electron mainly localized on the internal Lu3C2 cluster. These results clearly showed that the core unit C2(3) as well as N3- play an important role in constructing molecular structures and electronic features of metallofullerenes. Furthermore, the electrochemical redox potentials, and vibrational frequencies of the two endofullerenes agree well with our experimental results. The electronic structures, ionization energies, electron affinities, inner clusters' dynamic motions of them have been predicted to further disclose the characters of these two metallofullerenes.
RESUMO
The endohedral fullerene Sc(3)NC@C(80)-I(h) has been synthesized and characterized; it has an unprecedented planar quinary cluster in a fullerene cage. It is also the first chemical compound in which the presence of an unprecedented (NC)(3-) trianion has been disclosed. The fascinating intramolecular dynamics in Sc(3)NC@C(80)-I(h) enables the whole molecule to display high polarity and promising ferroelectricity. This finding inspires the possibility that such a planar quinary cluster may be useful in constructing many other endohedral fullerenes.
RESUMO
In this communication, we describe the successful encapsulation of (177)Lu into the endohedral metallofullerene (177)Lu(x)Lu(3-x)N@C(80) (x = 1-3) starting with (177)LuCl(3) in a modified quartz Kraschmer-Huffman electric generator. We demonstrate that the (177)Lu (beta-emitter) in this fullerene cage is not significantly released for a period of up to at least one-half-life (6.7 days). We also demonstrate that this agent can be conjugated with an interleukin-13 peptide that is designed to target an overexpressed receptor in glioblastoma multiforme tumors. This nanoparticle delivery platform provides flexibility for a wide range of radiotherapeutic and radiodiagnostic multimodal applications.
Assuntos
Fulerenos/química , Interleucina-13/química , Lutécio/química , Radioisótopos/química , Marcação por IsótopoRESUMO
For the first time, we have produced the stable compound Sc(4)C(2)@C(80)-I(h) and characterized it as a metal carbide endofullerene by FTIR and Raman spectroscopies in combination with DFT calculations. Furthermore, DFT calculations have demonstrated that this molecule has a Russian-doll-type structure, C(2)@Sc(4)@C(80).
RESUMO
Two new water-soluble Gd-containing endohedral metallofullerenes [ScxGd3-xN@C80OmOHn (x = 1, 2; m approximately 12; n approximately 26)] were synthesized in a simple one-step reaction and characterized by Fourier transform (FT)-IR as well as X-ray photoelectron spectroscopy (XPS). Their observed longitudinal relaxivities (R1) for water protons are 20.7 and 17.6 mM(-1) s(-1), respectively, which are significantly higher than that of the commercial magnetic resonance imaging (MRI) contrast agent (Gd-DTPA, 3.2 mM(-1) s(-1)). These results indicate these trimetallic nitride endohedral fullerenols are potential next-generation high-efficiency MRI contrast agents.
RESUMO
The aggregation behavior of the newly synthesized gadofullerene magnetic resonance imaging (MRI) contrast agent, i.e., Gd@C(82)O(6)(OH)(16)(NHCH(2)CH(2)COOH)(8) (abbreviated as AAD-EMF), was studied in detail by dynamic light scattering, scanning electron microscopy, T(1)-weighted magnetic resonance, and atomic force microscopy. It was revealed that the AAD-EMF aggregation in aqueous solution is pH-dependent. At pH 2, the AAD-EMF first self-assemble to form ca. 30 nm small clusters, and then dozens of the small clusters further aggregate to form large grapelike particles. At pH 7, the aggregates are also ca. 30 nm small clusters, but they are hard to further aggregate except for forming some cluster dimers or trimers, so AAD-EMF aggregates have a narrow size distribution by this time. At pH 9, the AAD-EMF aggregations cover a large range of continuous hydrodynamic diameters from 30 to 2000 nm. On the basis of the above observations, the aggregating mechanism of AAD-EMF under different pH values was proposed by concurrently considering the hydrogen-bonding effect and the dipolar interactions between AAD-EMF.
Assuntos
Meios de Contraste/química , Fulerenos/química , Gadolínio/química , Imageamento por Ressonância Magnética , Compostos Organometálicos/química , Concentração de Íons de Hidrogênio , Compostos Organometálicos/síntese química , Tamanho da Partícula , Solubilidade , Água/químicaRESUMO
A FAR over-expressed tumor targeting multifunctional imaging probe has been fabricated based on gadofulleride nanoplatform. The combination of highly efficient MRI contrast enhancement and sensitive fluorescence imaging along with the preferential uptake toward FAR tumor cells suggest that the obtained multifunctional imaging probe possesses complementary capabilities for anatomical resolution and detection sensitivity.
RESUMO
BACKGROUND: Glioblastoma multiforme is the most common and most lethal primary brain tumor in humans, with median survival of approximately 1 year. Owing to the ability of glioma cells to aggressively infiltrate normal brain tissue and survive exposure to current adjuvant therapies, there is a great need for specific targeted nanoplatforms capable of delivering both therapeutic and imaging agents directly to invasive tumor cells. METHOD: Gadolinium-containing endohedral fullerenes, highly efficient contrast agents for MRI, were functionalized and conjugated with a tumor-specific peptide and assessed for their ability to bind to glioma cells in vitro. RESULTS: We report the successful conjugation of the carboxyl functionalized metallofullerene Gd(3)N@C(80)(OH)(-26)(CH(2)CH(2)COOH)(-16) to IL-13 peptides and the successful targeting ability towards brain tumor cells that overexpress the IL-13 receptor (IL-13Rα2). CONCLUSION: These studies demonstrate that IL-13 peptide-conjugated gadolinium metallofullerenes could serve as a platform to deliver imaging and therapeutic agents to tumor cells.
Assuntos
Neoplasias Encefálicas/diagnóstico , Neoplasias Encefálicas/tratamento farmacológico , Complexos de Coordenação/uso terapêutico , Fulerenos/uso terapêutico , Glioblastoma/diagnóstico , Glioblastoma/tratamento farmacológico , Interleucina-13/metabolismo , Nanoconchas , Sequência de Aminoácidos , Animais , Meios de Contraste , Complexos de Coordenação/química , Sistemas de Liberação de Medicamentos , Fulerenos/química , Humanos , Interleucina-13/química , Imageamento por Ressonância Magnética , Camundongos , Camundongos Nus , Dados de Sequência Molecular , Peptídeos/química , Peptídeos/metabolismo , Receptores de Interleucina-13/metabolismo , Rodaminas/químicaRESUMO
Water-soluble gadofullerides exhibited high efficiency as magnetic resonance imaging (MRI) contrast agents. In this paper, we report the conjugation of the newly synthesized gadofulleride, Gd@C82O6(OH) 16(-)(NHCH2CH2COOH)8, with the antibody of green fluorescence protein (anti-GFP), as a model for "tumor targeted" imaging agents based on endohedral metallofullerenes. In this model system, the activity of the anti-GFP conjugate can be conveniently detected by green fluorescence protein (GFP), leading to in vitro experiments more direct and facile than those of tumor antibodies. Objective-type total internal reflection fluorescence microscopy revealed that each gadofulleride aggregate conjugated on average five anti-GFPs, and the activity of anti-GFPs was preserved after conjugation. In addition, the gadofulleride/antibody conjugate exhibited higher water proton relaxivity (12.0 mM (-1) s (-1)) than the parent gadofulleride aggregate (8.1 mM (-1) s (-1)) in phosphate buffered saline at 0.35 T, as also confirmed by T1-weighted images of phantoms. These observations clearly indicate that the synthesized gadofulleride/antibody conjugate not only has targeting potential, but also exhibits higher efficiency as an MRI contrast agent.
Assuntos
Anticorpos/química , Meios de Contraste/síntese química , Gadolínio/química , Imageamento por Ressonância Magnética/métodos , Biotina/química , Fenômenos Químicos , Físico-Química , Proteínas de Fluorescência Verde/imunologia , Indicadores e Reagentes , Conformação Molecular , Peso Molecular , Soroalbumina Bovina/química , Solubilidade , Espectrometria de Fluorescência , Estreptavidina/química , ÁguaRESUMO
Unconventional fullerenes are those smaller than C(60) or those intermediate between C(60) and C(70), which are not stable in structure as none of the unconventional fullerene isomers satisfying the "isolated-pentagon-rule" (IPR). Below we report the synthesis of a stable unconventional fullerene derivative C(64)H(4) by introducing methane in the fullerene productions with the normal Krätschmer-Huffman method. We also applied various spectroscopic measurements such as mass spectrometry, (13)C NMR, IR, UV-vis absorption spectrometry, etc. to characterize the structural and electronic properties of this molecule, revealing an unprecedented fullerene cage with a triplet of directly fused pentagons in the framework of C(64)H(4). Four hydrogen atoms are added to the carbons at vertexes of fused pentagons to allow the bond angles at these sites close to the sp(3) tetrahedral angle, which essentially release the sp(2) bond strains on the abutting-pentagon sites of C(64). Ab initio calculations were performed to explore the electronic property and simulate the (13)C NMR and IR spectra of this fulleride, which reproduced well the experimental results and confirmed the structural assignment of the C(64)H(4).