RESUMO
A bent crystal Laue analyser (BCLA) is an X-ray energy analyser used for fluorescence X-ray absorption fine-structure (XAFS) spectroscopy to separate the fluorescence X-ray emission line of a target atom from the elastic scattering X-rays and other fluorescence emission lines. Here, the feasibility of the BCLA for total reflection fluorescence XAFS (TRF-XAFS), which has a long X-ray footprint on the substrate surface owing to grazing incidence, was tested. The focal line of the BCLA was adjusted on the X-ray footprint and the XAFS signal for one monolayer of Pt deposited on a 60â nm Au film with high sensitivity was obtained. Although range-extended XAFS was expected by the rejection of Au fluorescence arising from the Au substrate, a small glitch was found in the Au L3 edge because of the sudden change of the complex refraction index of the Au substrate at the Au edge. This abnormal spectrum feature can be removed by reflectivity correction using Au foil absorption data. BCLA combined with TRF-XAFS spectroscopy (BCLA + TRF-XAFS) is a new technique for the in situ surface analysis of highly dispersed systems even in the presence of a liquid overlayer.
RESUMO
A newly developed electrochemical biosensor composed of a topological insulator (TI) and metallic DNA (mDNA) is fabricated. The bismuth selenide nanoparticle (Bi2 Se3 NP) is synthesized and sandwiched between the gold electrode and another Au-deposited thin layer (Bi2 Se3 @Au). Then, eight-silver-ion mediated double-stranded DNA (mDNA) is immobilized onto the substrate (Bi2 Se3 @Au-mDNA) for the further detection of hydrogen peroxide. The Bi2 Se3 NP acts as the electrochemical-signal booster, while unprecedentedly its encapsulation by the Au thin layer keeps the TI surface states protected, improves its electrochemical-signal stability and provides an excellent platform for the subsequent covalent immobilization of the mDNA through Au-thiol interaction. Electrochemical results show that the fabricated biosensor represents much higher Ag+ redox current (≈10 times) than those electrodes prepared without Bi2 Se3 @Au. The characterization of the Bi2 Se3 @Au-mDNA film is confirmed by atomic force microscopy, scanning tunneling microscopy, and cyclic voltammetry. The proposed biosensor shows a dynamic range of 00.10 × 10-6 m to 27.30 × 10-6 m, very low detection limit (10 × 10-9 m), unique current response (1.6 s), sound H2 O2 recovery in serum, and substantial capability to classify two breast cancer subtypes (MCF-7 and MDA-MB-231) based on their difference in the H2 O2 generation, offering potential applications in the biomedicine and pharmacology fields.
Assuntos
Técnicas Biossensoriais/métodos , Neoplasias da Mama/metabolismo , DNA/química , Técnicas Eletroquímicas/métodos , Peróxido de Hidrogênio/metabolismo , Prata/química , Linhagem Celular Tumoral , Feminino , Ouro/química , Humanos , Células MCF-7 , Nanopartículas Metálicas/químicaRESUMO
For the first time, topological insulator bismuth selenide nanoparticles (Bi2 Se3 NP) are core-shelled with gold (Au@Bi2 Se3 ) i) to represent considerably small-sized (11 nm) plasmonic nanoparticles, enabling accurate bioimaging in the near-infrared region; ii) to substantially improve Bi2 Se3 biocompatibility, iii) water dispersibility, and iv) surface functionalization capability through straightforward gold-thiol interaction. The Au@Bi2 Se3 is subsequently functionalized for v) effective targeting of SH-SY5Y cancer cells, vi) disrupting the endosome/lysosome membrane, vii) traceable delivery of antagomiR-152 and further synergetic oncomiR knockdown and photothermal therapy (PTT). Unprecedentedly, it is observed that the Au shell thickness has a significant impact on evoking the exotic plasmonic features of Bi2 Se3 . The Au@Bi2 Se3 possesses a high photothermal conversion efficiency (35.5%) and a remarkable surface plasmonic effect (both properties are approximately twofold higher than those of 50 nm Au nanoparticles). In contrast to the siRNA/miRNA delivery methods, the antagomiR delivery is based on strand displacement, in which the antagomiR-152 is displaced by oncomiR-152 followed by a surface-enhanced Raman spectroscopy signal drop. This enables both cancer cell diagnosis and in vitro real-time monitoring of the antagomiR release. This selective PTT nanoparticle can also efficiently target solid tumors and undergo in vivo PTT, indicating its potential clinical applications.
Assuntos
Antagomirs/química , Ouro/química , Nanopartículas Metálicas/química , Compostos Organosselênicos/química , Fototerapia/métodos , Bismuto , MicroRNAs/genética , RNA Interferente Pequeno/genética , Compostos de Selênio , Nanomedicina Teranóstica/métodosRESUMO
Nanoparticle-based cell differentiation therapy has attracted increasing research interest as it is a promising substitute for conventional cancer treatment methods. Here, the topological insulator bismuth selenide nanoparticle (Bi2Se3 NP) was core-shelled with silver (Ag@Bi2Se3) to represent remarkable biocompatibility and plasmonic features (ca. 2.3 times higher than those of Ag nanoparticle). Moreover, a newly developed RNA three-way junction (3WJ) structure was designed for the quad-functionalization of any type of nanoparticle and surface. One leg of the 3WJ was attached to the Ag@Bi2Se3, and the other leg harbored a cell-penetrating RNA and a florescence tag. The third leg was designed to inhibit micro-RNA-17 (miR-17) and to further release retinoic acid (RA). A new drug delivery mechanism was developed for the slow release of RA inside the cytosol based on the prerequisite inhibition of miR-17 using a strand displacement strategy. In this paper, we report a simple methodology for resolving the hydrophobicity challenges of RA by its conjugation with a RNA strand (RA/R) through a stimulus-responsive cross-linker. The developed nanobiohybrid material could fully differentiate SH-SY5Y cancer cells into neurons and stop their growth in 6 days without requiring sequential treatments which has not been reported yet. Using a surface-enhanced Raman spectroscopy technique, the RA delivery and the cell differentiation process were monitored nondestructively in real time. The fabricated nanobiohybrid material could open the new horizons in the fabrication of different diagnostic/therapeutic agents.
Assuntos
Nanopartículas Metálicas/química , MicroRNAs/metabolismo , Compostos Organosselênicos/química , Prata/química , Tretinoína/química , Bismuto , Diferenciação Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Portadores de Fármacos/química , Endocitose , Humanos , MicroRNAs/antagonistas & inibidores , Microscopia Confocal , Neuroblastoma/metabolismo , Neuroblastoma/patologia , Oligonucleotídeos/química , Povidona/química , Compostos de Selênio , Análise Espectral Raman , Tretinoína/metabolismo , Tretinoína/farmacologiaRESUMO
Nitric oxide (NO) is one of the most important molecules in living things due to its role as a signaling molecule in influencing pathological and physiological mechanisms including neurotransmission. In this study, the electrochemical biosensor based on the amine-modified molybdenum disulfide nanoparticles (MoS2), graphene oxide (GO) and myoglobin (Mb) hybrid material (amine-modified MoS2/GO/Mb hybrid) is developed to achieve the accurate detection of NO with electrochemical signal improvement. For the first time, the synthesis of MoS2 accompanying the amine-modification of the surface of MoS2 is done to hybridize with GO efficiently through the short linkage. After the amine-modification of MoS2, it is enclosed with GO directly (amine-modified MoS2/GO). Then, Mb which can induce the reduction of NO is immobilized on the amine-modified MoS2/GO to fabricate the amine-modified MoS2/GO/Mb hybrid for NO detection. The prepared hybrid shows the signal improved redox properties relative to the result of the electrode prepared without hybrid. Furthermore, upon addition of NO, the electrode prepared with hybrid shows the improved amperometric response compared with that of the electrode without hybrid. This amine-modified MoS2/GO/Mb hybrid can be used in the development of the biosensor platform accompanying the electrochemical signal improvement and accurate detection of target materials.