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Organic coating of 1-2-nm-size silicon nanoparticles： Effect on particle properties

Nano Research 2015年第6期8卷 2047-2062页

作者： Cristian R. Lillo Juan J. Romero Manuel Llansola Portoles reinaldo pis diez Paula Caregnato Monica C. Gonzalez Instituto de Investigaciones Fisicoquimicas Teoricas y Aplicadas (INIFTA) CCT-La Plata-CONICET Facultad de Ciencias Universidad National de La Plata cc 16 Suc. 4 1900 La Plata Argentina CEQUINOR CCT-La Plata-CONICET Facultad de Ciencias Exactas Universidad Nacional de La Plata cc 9621900 La Plata Argentina Department of Chemistry and Biochemistry Center for Bioenergy and Photosynthesis Arizona State University Tempe Arizona USA

Photoluminescent silicon nanoparticles 1–2 nm in size were synthesized by a wet chemical procedure and derivatized with propylamine (NH2SiNP). Surface NH2 groups were used as linkers for additional poly(ethylene glycol) (PEG) and folic acid (Fo) attachment (PEG-NHSiNP and Fo-NHSiNP, respectively) to enable efficient targeting of the particles to tumors and inflammatory sites. The particles were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ζ potential, dynamic light scattering, and time-resolved anisotropy. The photophysical properties and photosensitizing capacity of the particles and their interaction with proteins was dependent on the nature of the attached molecules. While PEG attachment did not alter the photophysical behavior of NH2SiNP, the attachment of Fo diminished particle photoluminescence. Particles retained the capacity for 1O2 generation; however, efficient 1O2 quenching by the attached surface groups may be a drawback when using these particles as 1O2 photosensitizers. In addition, Fo attachment provided particles with the capacity to generate the superoxide anion radical (O 2 − ). The particles were able to bind tryptophan residues of bovine serum albumin (BSA) within quenching distances. NH2SiNP and PEG–NHSiNP ground state complexes with BSA showed binding constants of (3.1 ± 0.3) × 104 and (1.3 ± 0.4) × 103 M−1, respectively. The lower value observed for PEG-NHSiNP complexes indicates that surface PEGylation leads to a reduction in protein adsorption, which is required to prevent opsonization. An increase in particle luminescence upon BSA binding was attributed to the hydrophobic environment generated by the protein. NH2SiNP-BSA complexes were also capable of resonance energy transfer.

关键词：硅纳米颗粒粒子特性有机涂层傅立叶变换红外光谱仪 X射线光电子能谱超氧阴离子自由基蛋白质吸附透射电子显微镜

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GC/MS Analyses of Thiosemicarbazones Synthesized from Acetophenones: Thermal Decay and Mass Spectra Features

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International Journal of Analytical Mass Spectrometry and Chromatography 2015年第1期3卷 1-13页

作者： Belén Gastaca Gastón Galletti Hernán Rubén Sánchez reinaldo pis diez María de las Mercedes Schiavoni Jorge Javier Pedro Furlong Laboratorio de Estudio de Compuestos Orgánicos (LADECOR) Departamento de Química Facultad de Ciencias Exactas Universidad Nacional de La Plata La Plata Argentina CEQUINOR Centro de Química Inorgánica (CONICET UNLP) Facultad de Ciencias Exactas UNLP La Plata Argentina

The mass spectral fragmentation of thiosemicarbazones synthesized from acetophenones has been studied by CG/MS. These carbonyl compounds exhibit chromatographic peaks which are not observed in aliphatic analogues or those synthesized from aldehydes. The analysis of the corresponding spectra has allowed structural assignment to the dimerization of gas phase neutral fragments. Theoretical calculations (DFT level) also provide evidence to support the experimental observations.

关键词： Thiosemicarbazones Mass Spectrometry Analyses Dimerization of Thiosemicarbazones

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