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1.
Molecules ; 29(3)2024 Jan 30.
Article in English | MEDLINE | ID: mdl-38338398

ABSTRACT

Photonic glasses (PGs) based on the self-assembly of monosized nanoparticles can be an effective tool for realizing disordered structures capable of tailoring light diffusion due to the establishment of Mie resonances. In particular, the wavelength position of these resonances depends mainly on the morphology (dimension) and optical properties (refractive index) of the building blocks. In this study, we report the fabrication and optical characterization of photonic glasses obtained via a self-assembling technique. Furthermore, we have demonstrated that the infiltration of these systems with a green-emitting polymer enhances the properties of the polymer, resulting in a large increase in its photoluminescence quantum yield and a 3 ps growing time of the photoluminescence time decay Finally, the development of the aforementioned system can serve as a suitable low-cost platform for the realization of lasers and fluorescence-based bio-sensors.

2.
ACS Omega ; 7(7): 5962-5971, 2022 Feb 22.
Article in English | MEDLINE | ID: mdl-35224357

ABSTRACT

Raman spectroscopy has long been suggested as a potentially fast and sensitive method to monitor phytoplankton abundance and composition in marine environments. However, the pitfalls of visible detection methods in pigment-rich biological material and the complexity of their spectra have hindered their application as reliable in situ detection methods. In this study we combine 1064 nm confocal Raman spectroscopy with multivariate statistical analysis techniques (principle component analysis and partial leas-squares discriminant analysis) to reliably measure differences in the cell viability of a diatom species (Chaetoceros muelleri) and two haptophyte species (Diacronema lutheri and Tisochrysis lutea) of phytoplankton. The low fluorescence background due to this combined approach of NIR Raman spectroscopy and multivariate data analysis allowed small changes in the overall spectral profiles to be reliably monitored, enabling the identification of the specific spectral features that could classify cells as viable or nonviable regardless of their species. The most significant differences upon cell death were shown by characteristic shifts in the carotenoid bands at 1527 and 1158 cm-1. The contributions from other biomolecules were less pronounced but revealed changes that could be identified using this combination of techniques.

3.
J Phys Chem A ; 122(23): 5121-5131, 2018 Jun 14.
Article in English | MEDLINE | ID: mdl-29745659

ABSTRACT

We describe an unusual in-plane type of porphyrin core distortion, tetragonal elongation (TE), observed experimentally in diboron porphyrins. The vibrational spectra of several of these complexes exhibit shifts that we have assigned to this TE distortion by comparing experimental spectra with DFT computational findings. The influence of TE in porphyrin systems was isolated using DFT analysis of the well-known model compounds Ni(II)porphine and Zn(II)porphine, with the macrocycle ring constrained to eliminate the influence of out-of-plane (OOP) distortions. A significant down-shift in frequencies was observed for porphyrin normal vibrational modes, particularly the in-plane A1g/B1g modes that are dominated by contributions from stretching and bending of Cα-Cm coordinates. In contrast, TE had little effect on the v(Pyrhalfring) and δ(Pyrdef) modes, though the lowered symmetry of the system resulted in significant splitting of the B2u and B3u modes. The impact of the TE distortion upon the diboron porphyrin vibrational spectrum was probed experimentally using Raman spectroscopy of B2O2(BCl3)2(TTP), B2OF2(TTP), and B2OPhOH2(TTP) (TTP = 5,10,15,20-(tetra- p-tolyl)porphyrin). Comparing the experimentally obtained spectral signatures to the computational findings allowed us to assign the large shifts observed for the v2 and v3 modes to the TE distortion in diboron porphyrins.

4.
Anal Bioanal Chem ; 408(16): 4403-11, 2016 Jun.
Article in English | MEDLINE | ID: mdl-27086022

ABSTRACT

Nanostructured gold substrates provide chemically stable, signal-enhancing substrates for the sensitive detection of a variety of compounds through surface-enhanced Raman spectroscopy (SERS). Recent developments in advanced fabrication methods have enabled the manufacture of SERS substrates with repeatable surface nanostructures that provide reproducible quantitative analysis, historically a weakness of the SERS technique. Here, we describe the novel use of gold-sputtered Blu-ray disc surfaces as SERS substrates. The unique surface features and composition of the Blu-ray disc recording surface lead to the formation of gold nano-islands and nanogaps following simple gold sputtering, without any background peaks from the substrate. The SERS performance of this substrate is strong and reproducible with an enhancement factor (EF) of 10(3) for melamine. A limit of detection (LOD) for this compound of 70 ppb and average reproducibility of ±12 % were achieved. Gold-sputtered Blu-ray discs thus offer an excellent alternative to more exotic gold SERS substrates prepared by advanced, time-consuming and expensive methods. Graphical abstract AFM 3D images of 1-µm(2) sections of uncoated and gold-sputtered recordable Blu-ray disc (BD-R) surfaces and the SERS signal obtained on the gold-sputtered surface for a 1000 ppm aqueous solution of melamine.

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