Search

In the late 1990s, the unique possibilities application of inorganic nanocrystals with anti-Stokes photoluminescence were demonstrated. In a fairly short period, a significant breakthrough has been achieved in this field due to the development of new and modification of existing methods for the synthesis of these nanomaterials, and the expansion of understanding of the photophysical processes occurring in nanocrystals. The interest from the scientific community is due to the exceptional luminescence properties of upconversion nanomaterials, which can convert photons of the near-infrared spectrum to radiation in the visible and UV ranges. This multiquantum process takes place under low-intensity excitation, which largely determines the use of this class of nanomaterials in high-tech fields, including biotechnology, photochemistry, medicine, solar energy, nanosensorics, etc. The goals of this review are to consider the mechanisms of anti-Stokes luminescence, to analyze the synthesis methods, and to demonstrate the applications of fluoride upconversion nanomaterials, in which they have formed a stable scientific and technological niche.

The photocatalytic degradation of organic molecules is one of the effective ways for water purification. At this point, photocatalytic microreactor systems seem to be promising to enhance the versatility of the photoassisted degradation approach. Herein, we propose photoresponsive microcapsules prepared via layer-by-layer assembly of polyelectrolytes on the novel CaCO3/TiO2 composite template cores. The preparation of CaCO3/TiO2 composite particles is challenging because of the poor compatibility of TiO2 and CaCO3 in an aqueous medium. To prepare stable CaCO3/TiO2 composites, TiO2 nanoparticles were loaded into mesoporous CaCO3 microparticles with a freezing-induced loading technique. The inclusion of TiO2 nanoparticles into CaCO3 templates was evaluated with scanning electron microscopy and elemental analysis with respect to their type, concentration, and number of loading iterations. Upon polyelectrolyte shell assembly, the CaCO3 matrix was dissolved, resulting in microreactor capsules loaded with TiO2 nanoparticles. The photoresponsive properties of the resulted capsules were tested by photoinduced degradation of the low-molecule dye rhodamine B in aqueous solution and fluorescently labeled polymer molecules absorbed on the capsule surface under UV light. The exposure of the capsules to UV light resulted in a pronounced degradation of rhodamine B in capsule microvolume and fluorescent molecules on the capsule surface. Finally, the versatility of preparation of multifunctional photocatalytic and magnetically responsive capsules was demonstrated by iterative freezing-induced loading of TiO2 and magnetite Fe3O4 nanoparticles into CaCO3 templates.

We demonstrate a novel approach to the controlled loading of inorganic nanoparticles and proteins into submicron- and micron-sized porous particles. The approach is based on freezing/thawing cycles, which lead to high loading densities. The process was tested for the inclusion of Au, magnetite nanoparticles, and bovine serum albumin in biocompatible vaterite carriers of micron and submicron sizes. The amounts of loaded nanoparticles or substances were adjusted by the number of freezing/thawing cycles. Our method afforded at least a three times higher loading of magnetite nanoparticles and a four times higher loading of protein for micron vaterite particles, in comparison with conventional methods such as adsorption and coprecipitation. The capsules loaded with magnetite nanoparticles by the freezing-induced loading method moved faster in a magnetic field gradient than did the capsules loaded by adsorption or coprecipitation. Our approach allows the preparation of multicomponent nanocomposite materials with designed properties such as remote control (e.g. via the application of an electromagnetic or acoustic field) and cargo unloading. Such materials could be used as multimodal contrast agents, drug delivery systems, and sensors.

In modern biomedical science and developmental biology, there is significant interest in optical tagging to study individual cell behavior and migration in large cellular populations. However, there is currently no tagging system that can be used for labeling individual cells on demand in situ with subsequent discrimination in between and long-term tracking of individual cells. In this article, we demonstrate such a system based on photoconversion of the fluorescent dye rhodamine B co-confined with carbon nanodots in the volume of micron-sized polyelectrolyte capsules. We show that this new fluorescent convertible capsule coding system is robust and is actively uptaken by cell lines while demonstrating low toxicity. Using a variety of cellular lines, we demonstrate how this tagging system can be used for code-like marking and long-term tracking of multiple individual cells in large cellular populations.

Background: Over the past decades, significant advances have been made in the field of creating nanobioreagents for solving modern medicine problems (Grebenik et al., JBO, 2013). However, the problem of their low accumulation rate in pathological tissue in vivo experiments still remains. First of all, it is associated with the adsorption of blood proteins on the surface of nanobioreagents and the protein layer formation, which significantly changes the surface properties, which leads to their rapid excretion by the reticuloendothelial system. In particular, it is possible to reduce the blood plasma proteins adsorption and increase the time spent in the circulatory system by forming a coating of proteins. Methods: In situ cryоelectron tomography (Cryo-ET) is the only method that allows the experimental observation of protein structures on the nanoparticle’s surface in their natural functional state. The basic principle of the method is to obtain a series of projections of a vitrified sample thin lamella at different tilt angles related to an incident electron beam. Their further processing leads to obtaining the volumetric information about the structure of the sample. The use of a cryo-focused ion beam (Cryo-FIB) in specimen thinning makes it possible to carry out experiments with thin sections of cellular structures and observe the penetration of nanoparticles into the intracellular environment. Results: Upconverting nanophosphors (AN) were used as a nanoplatform for creating a protein coating. To create a protein coating on the AN surface, they were functionalized using an amphiphilic polymer containing carboxyl groups. Then, conjugation with protein molecules from the class of immunoglobulins was carried out by the method of carbodiimide activation. At each stage of synthesis and modification, AN solutions with different size distribution were vitrified for subsequent tomography. After a series of experiments to study the morphology of nanoparticles, an experiment on their successful absorption by cells of the cancer line A549 was carried out. Conclusion: Within this work, a series of in situ Cryo-ET methods were proposed and applied for structural characterization and visualization of the processes of synthesis, modification, and engulfment of nanoparticles into cellular systems. For the first time in its native form, the engulfment of ANF into the internal environment of the A549 cancer line cells was demonstrated.

A procedure has been proposed for the preparation of capsules with shells composed of titanium dioxide nanoparticles and polymers via the formation of Pickering emulsions (colloidosomes) followed by layer-by-layer deposition of polyelectrolytes. The feasibility of stabilizing oil droplets of emulsions by spontaneous adsorption of partly hydrophobized nanoparticles of anatase-form titanium dioxide at the oil/water interface has been studied. Conditions have been determined for the formation of stable colloidosomes and the subsequent layer-by-layer deposition of oppositely charged polyelectrolytes onto their surfaces. It has been shown that hydrophobic dyes may be encapsulated using the procedure developed for the preparation of the capsules. The photocatalytic activity of TiO2 particles occurring in the shell has been demonstrated by the example of degradation of Nile red which is incorporated in the oil core of a capsule.

Photopolymerization of nanocomposite materials using near infrared light is one of the unique technologies based on the luminescent properties of lanthanide-doped upconversion nanoparticles (UCNPs). We explored the UCNP-triggered radical polymerization both in oligomer bulk and on the nanoparticle surface in aqueous dispersion. Core/shell UCNPs NaYF4:Yb3+ and Tm3+/NaYF4 with emitting lines in the ultraviolet and blue regions were used to activate a photoinitiator. The study of the bulk photopolymerization in an initially homogeneous reaction mixture showed the UCNP redistribution due to gradient density occurring in the volume, which led to formation of UCNP superlattices and spheres &ldquo, frozen&rdquo, in a polymer matrix. We also developed a strategy of &ldquo, grafting from&rdquo, the surface, providing polymer shell growth directly on the nanoparticles. The photosensitization of the endogenous water-soluble photoinitiator riboflavin by the resonance energy transfer from UCNPs was demonstrated in the course of monomer glycidyl methacrylate polymerization followed by photocrosslinking with poly(ethylene glycol) diacrylate on the nanoparticle surface.

High intensity focused ultrasound (HIFU) is widely used in medical practice, including cancer therapy. Also this approach is promising for remote release of encapsulated drugs in various other biomedical applications where local treatment is needed. Our approach underpins the minimization of HIFU impact on possible degradation of biological tissues and expand the use of HIFU in the controlled release of encapsulated drugs. We demonstrated the efficient ultrasound-induced release of labeled protein (Cy7-BSA) from elaborated nanocomposite microcapsules in vitro an in vivo. The capsule fabrication was done using combination of recently developed freezing-induced loading (FIL) technique and Layer-by-Layer assembly (LbL) used for the preparation of complex multilayer BSA/tannic acid nanocomposite capsules sensitive to HIFU. These capsules contain NIR fluorescent Cy7-labeled BSA in the shell for tracking in vivo and the high concentration of labels inside the capsules resulted in self-quenching provides the real-time detection of the protein once it is released from the capsule. Ultrasound-induced release in vivo of Cy7-labeled BSA initially quenched by magnetite nanoparticles was confirmed by fluorescent tomography. The significant decrease of Cy7 fluorescence under HIFU treatment in vitro was found to be due to a generation of reactive oxygen species and fast dye oxidation. Our results demonstrate that adapted HIFU setup can be used for the directed release of encapsulated substances in vivo under tissue compatible NIR monitoring by fluorescent tomography.

Au nanoparticles were loaded into halloysite nanotubes by freezing-induced loading method. The loading efficiency and Au nanoparticle distribution were studied by UV–Vis absorption spectroscopy and transmission electron microscopy and compared to those of vacuum impregnation and adsorption from solution loading methods. The freezing-induced loading was found to be the most effective with the loading efficiency up to 85% after 5 loading cycles and the best Au nanoparticle distribution into halloysite nanotubes.

A novel type of microcontainers based on hollow silver alginate microspheres and magnetite nanoparticles is reported as development of recently published technology. Magnetite nanoparticles were incorporated by two methods - co-precipitation with porous calcium carbonate during template formation and adsorption onto CaCO3 particles or microcontainers' shell. Amount of magnetite loaded and microshells size (4.6 to 6.9 μm) were found to depend on the chosen method for magnetite nanoparticles incorporation. Stability of hollow microshells in saline, phosphate buffer and culturing media was studied. Microcontainers' susceptibility to magnetic field was investigated in solutions of varied viscosity, and their group movement velocity under constant magnetic field was evaluated by sequential optical microscopy imaging. Cell viability tests with prepared microshells were performed that demonstrated negligible cytotoxicity effect on human dermal fibroblasts cells. With HeLa cells moderate viability inhibition was found at high carriers:cells ratio at early time points which is attributed to more active and receptor-mediated endocytosis of carriers as well as known cytotoxicity of magnetite in some cancer cells. At 24 and 48 h time points HeLa cells proliferation fully recovers. Reported data opens perspectives for further biomedical-oriented studies and application of this novel kind of microcontainers with a number of techniques applicable for imaging, control and triggered cargo release provided by presence of silver and magnetite nanoparticles in the carriers and their suitability for further versatile functionalization by traditional LbL approach if needed.

We present the concept and the experimental demonstration of near-infrared photopolymerization assisted by specially designed upconversion nanophosphors. The principle of this technique is based on conversion of 980 nm laser irradiation to ultraviolet photons subsequently absorbed by photoinitiator. The nonlinearity of upconversion allows for activation of the process locally in the laser beam waist. This approach enables precise fabrication of 3D constructs directly in the volume of photocurable composition. Furthermore, the presented technique is suitable for polymerization of a wide range of photocurable resins as well as gelation of hydrogels for biomedical applications.

Adsorption of Mo(VI) and W(VI) ions from water with nanosized anatase has been studied. This process depends on sorption conditions (temperature, contact duration, etc.) and sample characteristics (composition, specific surface area, coherent scattering regions, etc.). Maximal recovery efficiency for Mo(VI) and W(VI) was achieved with the use of the samples of commercial Hombifine N (RMo = 99.90 %) and Degussa P25 (RMo = 99.99 %, RW = 99.75 %) and nanosized anatase modified with H2O2 (RMo,W = 99.75 %) under optimal conditions of sorption.

Nanoparticulate anatase and η-TiO2 prepared via a sulfate route have been shown (using powder X-ray diffraction, scanning electron microscopy, X-ray microanalysis, and IR spectroscopy) to differ in micro- and nanoparticle size and elemental composition. The degree of As(V), V(V), and Bi(III) extraction from aqueous solutions (for the last element, a content below its maximum allowable concentration has been reached) using nanoparticulate titania adsorbents depends on their composition, crystal structure, crystallinity, and microstructure. The synthesized anatase and η-TiO2 powders are shown to be potentially attractive carriers of PdCl2-CuCl2/TiO2 catalysts for low-temperature carbon monoxide oxidation in air.

Samples containing anatase and η-TiO2 nanoparticles have been prepared from titanyl sulfate solutions and characterized by X-ray diffraction, transmission electron microscopy, and electron diffraction. Unit-cell parameters of η-TiO2 have been proposed that do not rule out a relationship between the anatase and η-TiO2 structures. The samples containing anatase and η-TiO2 differ in crystallite size and specific surface area and consist of agglomerates of particles of various sizes covered with an amorphous layer. We have studied the effect of synthesis conditions on the ability to prepare a particular titania polymorph with various functional characteristics.

Polyelectrolyte microcapsules functionalized by Fe3O4 nanoparticles have proved to be perspective magnetic resonance (MR) contrast agents. Here we report about submicron-sized capsules with a shell made of poly-L-arginine and dextran sulfate. Such polymers are biodegradable, thus they are suitable to use as components of drug delivery carriers. To functionalize submicrocapsules by magnetite freezing and layer-by-layer method were used. MR study of obtained samples was carried out, and signal intensity change dependencies on submicrocapsules concentration by mass amount of iron oxide (III) nanoparticles were shown. The sample with optimal MR contrast characteristics was found as well, and an ability to use it as a bimodal MR agent was demonstrated.