Pulsed laser reshaping and fragmentation of upconversion nanoparticles — from hexagonal prisms to 1D nanorods through “Medusa”-like structures
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01.04.2021 |
Sajti L.
Karimov D.N.
Rocheva V.V.
Arkharova N.A.
Khaydukov K.V.
Lebedev O.I.
Voloshin A.E.
Generalova A.N.
Chichkov B.N.
Khaydukov E.V.
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Nano Research |
10.1007/s12274-020-3163-4 |
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© 2020, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature. One dimensional (1D) nanostructures attract considerable attention, enabling a broad application owing to their unique properties. However, the precise mechanism of 1D morphology attainment remains a matter of debate. In this study, ultrafast picosecond (ps) laser-induced treatment on upconversion nanoparticles (UCNPs) is offered as a tool for 1D-nanostructures formation. Fragmentation, reshaping through recrystallization process and bioadaptation of initially hydrophobic (β-Na1.5Y1.5F6: Yb3+, Tm3+/β-Na1.5Y1.5F6) core/shell nanoparticles by means of one-step laser treatment in water are demonstrated. “True” 1D nanostructures through “Medusa”-like structures can be obtained, maintaining anti-Stokes luminescence functionalities. A matter of the one-dimensional UCNPs based on direction of energy migration processes is debated. The proposed laser treatment approach is suitable for fast UCNP surface modification and nano-to-nano transformation, that open unique opportunities to expand UCNP applications in industry and biomedicine. [Figure not available: see fulltext.].
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A microwave-triggered opening of the multifunctional polyelectrolyte capsules with nanodiamonds in the shell composition
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06.01.2021 |
Borodina T.
Yurina D.
Sokovikov A.
Karimov D.
Bukreeva T.
Khaydukov E.
Shchukin D.
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Polymer |
10.1016/j.polymer.2020.123299 |
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© 2020 Microcapsules are ideal cargo platform for variety of applications such as drug delivery, sensing and imaging due to the combination of a simplicity fabrication and flexibility in the design. We developed remotely collapsing polymer capsules to response to external microwave treatment. The multilayer structure of the capsules was designed to create a polyfunctional system intercalating with nanodiamonds (NDs) and upconversion nanoparticles (UCNPs) into the polyelectrolyte shell. NDs empower local overheating to the microcapsules, while UCNPs provide opportunity to luminescent thermal sensing. UCNPs consist of inorganic crystalline host matrix - hexagonal β-phase NaYF4, doped with pairs of trivalent lanthanide ions, which play role of sensitizer (Yb3+) and activator (Er3+). The microwave triggering followed by the capsule heating results in the controlled destruction of the polyelectrolyte shell with subsequent cargo release. UCNPs luminescence was utilized to determine the local temperature of the capsule shell at nanoscale under GHz ultrasonic treatment. Our novel approach provides on demand microcapsule system destruction, which can be used in the development of nanotheranostic platform for the unification of diagnosis and treatment of various diseases.
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Tracing upconversion nanoparticle penetration in human skin
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01.12.2019 |
Khabir Z.
Guller A.
Rozova V.
Liang L.
Lai Y.
Goldys E.
Hu H.
Vickery K.
Zvyagin A.
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Colloids and Surfaces B: Biointerfaces |
10.1016/j.colsurfb.2019.110480 |
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© 2019 Elsevier B.V. Due to their unique optical properties upconversion nanoparticles (UCNPs) provide exceptionally high contrast for imaging of true nanoparticle distribution in excised human skin. It makes possible to show penetration of solid nanoparticles in skin treated with chemical enhancers. We demonstrated tracing upconversion nanoparticles in excised human skin by means of optical microscopy at the discrete particle level sensitivity to obtain their penetration profiles, which was validated by laser-ablation inductively-coupled-plasma mass-spectrometry. To demonstrate utilities of our method, UCNPs were coated with polymers, formulated in water and chemical enhancers, and applied on excised human skin mounted on Franz cells, followed by imaging using a custom-built laser-scanning microscope. To evaluate the toxicity impact on skin by polymer-coated UCNPs, we introduced a tissue engineering model of viable epidermis made of decellularized chick embryo skin seeded with keratinocytes. UCNPs formulated in water stopped in stratum corneum, whereas UCNPs formulated in ethanol-water solution crossed stratum corneum and reached viable epidermis – hence, the enhancement effect for solid nanoparticles was detected by optical microscopy. All polymer-coated UCNPs were found nontoxic within the accepted safety levels. The keratinocyte resilience to polyethyleneimine-coated UCNPs was surprising considering cytotoxicity of polyethyleneimine to two-dimensional cell cultures.
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Radioactive (<sup>90</sup>Y) upconversion nanoparticles conjugated with recombinant targeted toxin for synergistic nanotheranostics of cancer
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25.09.2018 |
Guryev E.
Volodina N.
Shilyagina N.
Gudkov S.
Balalaeva I.
Volovetskiy A.
Lyubeshkin A.
Sen A.
Ermilov S.
Vodeneev V.
Petrov R.
Zvyagin A.
Alferov Z.
Deyev S.
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Proceedings of the National Academy of Sciences of the United States of America |
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10 |
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© 2018 National Academy of Sciences. All rights reserved. We report combined therapy using upconversion nanoparticles (UCNP) coupled to two therapeutic agents: beta-emitting radionuclide yttrium-90 (90Y) fractionally substituting yttrium in UCNP, and a fragment of the exotoxin A derived from Pseudomonas aeruginosa genetically fused with a targeting designed ankyrin repeat protein (DARPin) specific to HER2 receptors. The resultant hybrid complex UCNP-R-T was tested using human breast adenocarcinoma cells SK-BR-3 overexpressing HER2 receptors and immunodeficient mice, bearing HER2-positive xenograft tumors. The photophysical properties of UCNPs enabled background-free imaging of the UCNP-R-T distribution in cells and animals. Specific binding and uptake of UCNP complexes in SK-BR-3 cells was observed, with separate 90Y- and PE40-induced cytotoxic effects characterized by IC50 140 μg/mL (UCNP-R) and 5.2 μg/mL (UCNP-T), respectively. When both therapeutic agents were combined into UCNP-R-T, the synergetic effect increased markedly, ∼2200-fold, resulting in IC50 = 0.0024 μg/mL. The combined therapy with UCNP-R-T was demonstrated in vivo.
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Rational Surface Design of Upconversion Nanoparticles with Polyethylenimine Coating for Biomedical Applications: Better Safe than Brighter?
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10.09.2018 |
Guller A.
Nadort A.
Generalova A.
Khaydukov E.
Nechaev A.
Kornienko I.
Petersen E.
Liang L.
Shekhter A.
Qian Y.
Goldys E.
Zvyagin A.
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ACS Biomaterials Science and Engineering |
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2 |
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Copyright © 2018 American Chemical Society. Upconversion nanoparticles (UCNPs) coated with polyethylenimine (PEI) are popular background-free optical contrast probes and efficient drug and gene delivery agents attracting attention in science, industry, and medicine. Their unique optical properties are especially useful for subsurface nanotheranostics applications, in particular, in skin. However, high cytotoxicity of PEI limits safe use of UCNP@PEI, and this represents a major barrier for clinical translation of UCNP@PEI-based technologies. Our study aims to address this problem by exploring additional surface modifications to UCNP@PEI to create less toxic and functional nanotheranostic materials. We designed and synthesized six types of layered polymer coatings that envelop the original UCNP@PEI surface, five of which reduced the cytotoxicity to human skin keratinocytes under acute (24 h) and subacute (120 h) exposure. In parallel, we examined the photoluminescence spectra and lifetime of the surface-modified UCNP@PEI. To quantify their brightness, we developed original methodology to precisely measure the colloidal concentration to normalize the photoluminescence signal using a nondigesting mass spectrometry protocol. Our results, specified for the individual coatings, show that, despite decreasing the cytotoxicity, the external polymer coatings of UCNP@PEI quench the upconversion photoluminescence in biologically relevant aqueous environments. This trade-off between cytotoxicity and brightness for surface-coated UCNPs emphasizes the need for the combined assessment of the viability of normal cells exposed to the nanoparticles and the photophysical properties of postmodification UCNPs. We present an optimized methodology for rational surface design of UCNP@PEI in biologically relevant conditions, which is essential to facilitate the translation of such nanoparticles to the clinical applications.
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Real-time tracking of Yb<sup>3+</sup>, Tm<sup>3+</sup> doped NaYF<inf>4</inf> nanoparticles in living cancer cells
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01.01.2018 |
Kostyuk A.
Guryev E.
Vorotnov A.
Sencha L.
Peskova N.
Sokolova E.
Liang L.
Vodeneev V.
Balalaeva I.
Zvyagin A.
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Sovremennye Tehnologii v Medicine |
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0 |
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© 2018, Nizhny Novgorod State Medical Academy. All rights reserved. The aim of the study was to demonstrate the possibility of real-time tracking of polyethylenimine-coated NaYF4 :Yb,Tm upconversion nanoparticles (UCNPs) in living cancer cells using wide-field microscopy technique. Materials and Methods. Human breast adenocarcinoma SK-BR-3 cells and Yb3+ , Tm3+ doped NaYF4 nanoparticles with anti-Stokes photoluminescence were used in the study. The nanoparticles were visualized using wide-field microscope with excitation at 975 nm and signal detection in 420–842 spectral range. The analysis of the displacement of UCNPs was performed by fitting the point spread function of the photoluminescent spots corresponding to UCNP location by the Gaussian function, and calculation of mean square displacement. Results. UCNPs were rapidly internalized by SK-BR-3 cells and retained in the cells for at least 12 h. Two types of the particles motion were registered: (i) isotropic random spatial fluctuations with relatively small amplitudes and low rate of displacement, and (ii) flick and directional movements with rates up to 1.2 µm/s and total displacement up to tens of microns. The registered types of motion can be attributed to diffusion in local area and intracellular transport of nanoparticles encapsulated in vesicles, respectively. Conclusion. The demonstrated tracking of UCNPs in human breast adenocarcinoma cells showed that Yb3+ , Tm3+ doped NaYF4 nanoparticles are an advanced agent for dynamic studies of intracellular processes. The implemented scheme for UCNPs tracking provides long-term observation with preservation of cell viability for at least several hours. In total, almost complete absence of cell autofluorescence and UCNPs photobleaching, low invasiveness, fast rate of image acquisition allow us to consider the proposed approach as useful for a variety of tasks in biomedical research.
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