Multifunctional Harmonic Nanoparticles: Synthesis, Optical Properties and Recent Applications in Bio-Imaging

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Biology and Medicines".

Deadline for manuscript submissions: closed (31 October 2021) | Viewed by 9197

Special Issue Editors


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Guest Editor
Universite Grenoble Alpes, Grenoble, France
Interests: harmonic nanoparticles; lanthanide-doped nanocrystals; luminescence; non-linear optics

Special Issue Information

Dear Colleagues,

Non-centrosymmetric metal oxide nanocrystals, also called “harmonic nanoparticles” (HNPs) because of the great richness of their non-linear optical (NLO) response, have attracted substantial interest over the last decade as new exogenous bio-labeling probes as they can be excited in the three biological transparency windows, circumventing the limitations (low penetration depth, photo-bleaching, blinking, optically resonant conditions, etc.) of most fluorescent probes. Based on the known NLO performances of their bulk counterparts, BaTiO3, KTiOPO4 (KTP) and LiNbO3 nanocrystals were first developed and used for several bio-imaging proof-of-concept studies. More recently, other nanocrystals such as BiFeO3, ZnO, La(IO3)3, KNbO3, etc., have been synthesized and studied with the goal of better assessing their spectral NLO response (second, third, or higher-order harmonic generation), increasing their biocompatibility and adding new optical and chemical functionalities. In terms of synthesis methods, various solution-based techniques have been tested, but challenges are still ahead as understanding/controlling the nucleation and growth mechanisms is a prerequisite to the large-scale preparation of HNPs showing size and shape control (in the 5-500 nm range), high crystal quality, colloidal stability, and well-characterized optical properties.

This Special Issue of Nanomaterials will highlight different aspects of HNPs spanning from their chemical preparation to their specific optical properties but will also focus on more recent breakthroughs. Research articles and reviews can thus address (but are not limited to) the wet-chemical routes leading to the HNP synthesis, their growth mechanisms, the preparation of new non-centrosymmetric hosts, the incorporation of luminescent species opening additional properties like up-conversion processes, scattering of harmonic signals from suspensions or at the single-particle level, Mie and plasmonic resonances, surface functionalization, bio-imaging, and multi-photon microscopy studies.

Dr. Yannick Mugnier
Dr. Geraldine Dantelle
Guest Editors

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Keywords

  • non-centrosymmetric metal oxides
  • synthesis and growth mechanisms
  • size and shape control
  • second and third harmonic scattering
  • spectroscopy
  • luminescence from rare-earth ions
  • up-conversion
  • plasmonic enhancement
  • polarization-resolved studies
  • multi-photon microscopy

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Published Papers (3 papers)

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Research

13 pages, 5461 KiB  
Article
NIR-to-NIR Imaging: Extended Excitation Up to 2.2 μm Using Harmonic Nanoparticles with a Tunable hIGh EneRgy (TIGER) Widefield Microscope
by Laura Vittadello, Jan Klenen, Karsten Koempe, Laura Kocsor, Zsuzsanna Szaller and Mirco Imlau
Nanomaterials 2021, 11(12), 3193; https://doi.org/10.3390/nano11123193 - 25 Nov 2021
Cited by 15 | Viewed by 2819
Abstract
Near-infrared (NIR) marker-based imaging is of growing importance for deep tissue imaging and is based on a considerable reduction of optical losses at large wavelengths. We aim to extend the range of NIR excitation wavelengths particularly to values beyond 1.6 μm in [...] Read more.
Near-infrared (NIR) marker-based imaging is of growing importance for deep tissue imaging and is based on a considerable reduction of optical losses at large wavelengths. We aim to extend the range of NIR excitation wavelengths particularly to values beyond 1.6 μm in order to profit from the low loss biological windows NIR-III and NIR-IV. We address this task by studying NIR-excitation to NIR-emission conversion and imaging in the range of 1200 up to 2400 nm at the example of harmonic Mg-doped lithium niobate nanoparticles (i) using a nonlinear diffuse femtosecond-pulse reflectometer and (ii) a Tunable hIGh EneRgy (TIGER) widefield microscope. We successfully demonstrate the existence of appropriate excitation/emission configurations in this spectral region taking harmonic generation into account. Moreover, NIR-imaging using the most striking configurations NIR-III to NIR-I, based on second harmonic generation (SHG), and NIR-IV to NIR-I, based on third harmonic generation (THG), is demonstrated with excitation wavelengths from 1.6–1.8 μm and from 2.1–2.2 μm, respectively. The advantages of the approach and the potential to additionally extend the emission range up to 2400 nm, making use of sum frequency generation (SFG) and difference frequency generation (DFG), are discussed. Full article
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13 pages, 2458 KiB  
Article
Luminescent Yb3+,Er3+-Doped α-La(IO3)3 Nanocrystals for Neuronal Network Bio-Imaging and Nanothermometry
by Géraldine Dantelle, Valérie Reita and Cécile Delacour
Nanomaterials 2021, 11(2), 479; https://doi.org/10.3390/nano11020479 - 13 Feb 2021
Cited by 8 | Viewed by 2731
Abstract
Dual-light emitting Yb3+,Er3+-codoped α-La(IO3)3 nanocrystals, known to exhibit both second harmonic signal and photoluminescence (PL), are evaluated as optical nanoprobes and thermal sensors using both conventional microscopes and a more sophisticated micro-PL setup. When loaded in [...] Read more.
Dual-light emitting Yb3+,Er3+-codoped α-La(IO3)3 nanocrystals, known to exhibit both second harmonic signal and photoluminescence (PL), are evaluated as optical nanoprobes and thermal sensors using both conventional microscopes and a more sophisticated micro-PL setup. When loaded in cortical and hippocampal neurons for a few hours at a concentration of 0.01 mg/mL, a visible PL signal arising from the nanocrystals can be clearly detected using an epifluorescent conventional microscope, enabling to localize the nanocrystals along the stained neurons and to record PL variation with temperature of 0.5% K−1. No signal of cytotoxicity, associated with the presence of nanocrystals, is observed during the few hours of the experiment. Alternatively, a micro-PL setup can be used to discriminate the different PL lines. From ratiometric PL measurements, a relative thermal sensitivity of 1.2% K−1 was measured. Full article
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18 pages, 7400 KiB  
Article
On the Reaction Pathways and Growth Mechanisms of LiNbO3 Nanocrystals from the Non-Aqueous Solvothermal Alkoxide Route
by Mathias Urbain, Florian Riporto, Sandrine Beauquis, Virginie Monnier, Jean-Christophe Marty, Christine Galez, Christiane Durand, Yann Chevolot, Ronan Le Dantec and Yannick Mugnier
Nanomaterials 2021, 11(1), 154; https://doi.org/10.3390/nano11010154 - 9 Jan 2021
Cited by 13 | Viewed by 2897
Abstract
Phase-pure, highly crystalline sub-50 nm LiNbO3 nanocrystals were prepared from a non-aqueous solvothermal process for 72 h at 230 °C and a commercial precursor solution of mixed lithium niobium ethoxide in its parent alcohol. A systematic variation of the reaction medium composition [...] Read more.
Phase-pure, highly crystalline sub-50 nm LiNbO3 nanocrystals were prepared from a non-aqueous solvothermal process for 72 h at 230 °C and a commercial precursor solution of mixed lithium niobium ethoxide in its parent alcohol. A systematic variation of the reaction medium composition with the addition of different amounts of co-solvent including butanol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol resulted in the formation of nanocrystals of adjustable mean size and shape anisotropy, as demonstrated from XRD measurements and TEM imaging. Colloidal stability of ethanol- and water-based suspensions was evaluated from dynamic light scattering (DLS)/zeta potential studies and correlated with FTIR data. Thanks to the evolution in the nanocrystal size and shape distribution we observed, as well as to the available literature on the alkoxide chemistry, the reaction pathways and growth mechanisms were finally discussed with a special attention on the monomer formation rate, leading to the nucleation step. The polar, non-perovskite crystalline structure of LiNbO3 was also evidenced to play a major role in the nanocrystal shape anisotropy. Full article
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