Fluoride nanocrystals co-doped with lanthanide ions are well known due to the possibility of conversion near-infrared (NIR) radiation into photoluminescence with large anti-Stokes shift. Owing to upconversion effect, such nanomaterials have shown great potential in photonics and biomedicine. However, fluoride nanoparticles can be reconfigured to photoluminescence with a Stokes shift into the near-infrared region of the spectrum. In this work, we focused on the properties of NaRF4: Yb3+, Er3+, Ce3+ (R = Y, Lu) nanoparticles exhibiting intense stokes luminescence in the vicinity of 1530 nm at 975 nm excitation. Photoluminescence quantum efficiency of synthesized nanoparticles was evaluated as 28% at 0.6 W/cm2 excitation intensity. Based on the photoluminescent properties of nanoparticles we designed compact waveguide amplifier for C-band telecommunication and developed time gated imaging system for NIR-to-NIR biovisualization.

Upconversion nanoparticle (UCNP)-driven polymerization attracts great attention due to the ability of near-infrared light to penetrate deeper into biological media and synthetic materials than ultraviolet or visible light. Despite significant progress, the limitation of near-infrared light-triggered polymerization is associated with a key element of the photocurable composition, a UCNP/photoinitiator complex or a nanoinitiator. To determine the impact of resonance energy transfer from UCNPs to photoinitiator (PI) and its effect on polymerization, we developed two different photocurable compositions consisting of the polyethylene glycol diacrylate (PEG-DA), ultraviolet- and blue-emitting NaYF4: Yb3+, Tm3+ UCNPs with hydrophobic surface combined with water-soluble or insoluble PI. We found that transfer energy in these nanoinitiators proceeds differently: in UCNP/water-soluble PI (lithium phenyl-2,4,6-trimethylbenzoylphosphinate or LAP), it occurs through the photon-mediated transfer while in UCNP/water-insoluble PI (2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone or Irgacure 369), it takes place via the non-radiative resonant energy transfer. The impact of these processes in homolytic decomposition of initiator is extremely important in terms of the precisely controlled fabrication of polymer structures. PEG-DA facilitates the affinity between hydrophilic and hydrophobic components of the photocurable composition, which provides UCNP-driven cross-linking of biopolymers such as methacrylated hyaluronic acid and gelatin. 3D structures were prototyped to demonstrate the one-step rapid procedure of nanoinitiator preparation and emphasize the control of the energy transfer in UCNP/PI complexes for further development of UCNP-driven polymerization.

Технология 3D-печати стала ключевой движущей силой в изменении парадигмы производственного процесса в различных отраслях промышленности. Новой вехой в 3D-печати может стать технология инфракрасной полимеризации, основанная на достижениях в области синтеза наноматериалов, способных эффективно преобразовывать излучение ближнего ИК-диапазона спектра в УФ-свет. Эта инновационная технология может проложить путь к разработке множества решений в промышленности и предвещает новые рубежи для фотоники, оптоэлектроники и биомедицины. В обзоре представлено краткое обобщение имеющихся достижений, а также ограничения, сдерживающие развитие технологии ИК-фотополимеризации.

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.

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.

Local overheating of biotissue is a critical step for biomedical applications, such as photothermal therapy, enhancement of vascular permeability, remote control of drug release, and so on. Overheating of biological tissue when exposed to light is usually realized by utilizing the materials with a high-absorption cross section (gold, silica, carbon nanoparticles, etc.). Here, we demonstrate core/shell NaYF4:Yb3+, Tm3+/NaYF4 upconversion nanoparticles (UCNPs) commonly used for bioimaging as promising near-infrared (NIR) absorbers for local overheating of biotissue. We assume that achievable temperature of tissue labeled with nanoparticles is high enough because of Yb3+ resonance absorption of NIR radiation, whereas the use of auxiliary light-absorbing materials or shells is optional for photothermal therapy. For this purpose, a computational model of tissue heating based on the energy balance equations was developed and verified with the experimentally obtained thermal-graphic maps of a mouse in response to the 975-nm laser irradiation. Labeling of biotissue with UCNPs was found to increase the local temperature up to 2°C compared to that of the non-labeled area under the laser intensity lower than 1 W/cm2. The cellular response to the UCNP-initiated hyperthermia at subcritical ablation temperatures (lower than 42°C) was demonstrated by measuring the heat shock protein overexpression. This indicates that the absorption cross section of Yb3+ in UCNPs is relatively large, and microscopic temperature of nanoparticles exceeds the integral tissue temperature. In summary, a new approach based on the use of UCNP without any additional NIR absorbers was used to demonstrate a simple approach in the development of photoluminescent probes for simultaneous bioimaging and local hyperthermia.

Detection systems with deferred registration of luminescence signals are promising for performing complex tasks of imaging of biological objects due to their simplicity and low cost. In the present work, β‑NaYF 4 :Tm 3+ Yb 3+ /NaYF 4 nanocrystals with anti-Stokes photoluminescence have been used in deferred registration systems. It has been shown that there is a significant time delay between the exciting laser pulse and luminescence signal, which makes it possible to use this class of nanoparticles in the creation of wide-field imaging systems with deferred registration. The possibility of using nanoparticles for detecting a photoluminescence signal in the second transparency window of biotissue has been demonstrated. This system can be based on the resonance excitation and detection of the photoluminescence signal of Yb 3 + ions.

We propose a method for obtaining a fluorescence tomographic image for visualization and diagnosis of tissues of a living organism. The method is based on the excitation of the luminescence of multicolor upconverting nanoparticles localized in the depth of the biological tissue or a phantom imitating it by IR light. By recording the changes in the shape of the spectrum of the intensity of luminescence radiation from luminescent nanoparticles on the surface of the tissue, it is possible to obtain information about the depth of their occurrence. To implement this approach, upconverting nanoparticles were synthesized on the base of β-NaYF 4 crystal matrix doped with rare-earth elements Yb 3+ , Er 3+ , and Tm 3+ . The luminescence spectra of the produced nanoparticles upon excitation at a wavelength of 980 nm contain three narrow bands with maxima at wavelengths 540, 655, and 800 nm.

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 frozen in a polymer matrix. We also developed a strategy of grafting from 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.

AbstractWe propose a method for obtaining a fluorescence tomographic image for visualization and diagnosis of tissues of a living organism. The method is based on the excitation of the luminescence of multicolor upconverting nanoparticles localized in the depth of the biological tissue or a phantom imitating it by IR light. By recording the changes in the shape of the spectrum of the intensity of luminescence radiation from luminescent nanoparticles on the surface of the tissue, it is possible to obtain information about the depth of their occurrence. To implement this approach, upconverting nanoparticles were synthesized on the base of β-NaYF_4 crystal matrix doped with rare-earth elements Yb^3+, Er^3+, and Tm^3+. The luminescence spectra of the produced nanoparticles upon excitation at a wavelength of 980 nm contain three narrow bands with maxima at wavelengths 540, 655, and 800 nm.

AbstractDetection systems with deferred registration of luminescence signals are promising for performing complex tasks of imaging of biological objects due to their simplicity and low cost. In the present work, β‑NaYF_4:Tm^3+Yb^3+/NaYF_4 nanocrystals with anti-Stokes photoluminescence have been used in deferred registration systems. It has been shown that there is a significant time delay between the exciting laser pulse and luminescence signal, which makes it possible to use this class of nanoparticles in the creation of wide-field imaging systems with deferred registration. The possibility of using nanoparticles for detecting a photoluminescence signal in the second transparency window of biotissue has been demonstrated. This system can be based on the resonance excitation and detection of the photoluminescence signal of Yb^3 + ions.

Lanthanide-based upconversion nanoparticles attach great attention in theranostics due to their unique physicochemical and optical properties. It is innovative platform possessing peculiar properties for luminescent imaging, temperature mapping, sensing, and therapy. In present work we demonstrate advantages of new luminescent agents based on upconversion nanoparticles and hydrophylic biocompatible polymer.

Three-dimensional (3D) rapid prototyping technology based on near-infrared light-induced polymerization of photocurable compositions containing upconversion nanomaterials has been explored. For this aim, the rationally-designed core/shell upconversion nanoparticles NaYF 4 :Yb 3+ ,Tm 3+ /NaYF 4 , with the distinct ultraviolet-emitting lines and unprecedentedly high near-infrared to ultraviolet conversion efficiency of η_UC^(UV)=2% have been used. The upconverted ultraviolet photons were capable to efficiently activate photoinitiators contained in light-sensitive resins under moderate intensities of NIR excitation below 10 W cm −2 and induce generation of radicals and photopolymerization in situ . Near infrared-activated polymerization process, both at the millimeter and sub-micron scales, was investigated. Polymeric macro- and microstructures were fabricated by means of near infrared laser scanning photolithography in the volume of liquid photocurable compositions with focused laser light at 975 nm wavelength. Examination of the polymerization process in the vicinity of the nanoparticles shows strong differences in the rate of polymer shell growth on flat and edge nanoparticle sides. This phenomenon mainly defines the resolution of the demonstrated near infrared - ultraviolet 3D printing technology at the micrometer scale level.

In recent years, the overwhelming majority of the upconversion nanoparticles (UCNPs) prominent applications have originated from their unique luminescent properties. Due to original properties of inorganic UCNPs they attract the interest in numerous fields. We discussed a number of UCNP assisted techniques, such as biomedical imaging, therapy agents, anti-counterfeit labels and 3D printing, showing highly versatile and translatable UCNP photoluminescent nanotechnology for the applications in industry and biomedicine.

Recently introduced upconversion nanoparticles (UCNPs) have pushed the depth of photodynamic therapy (PDT) treatment to the centimetre range by converting deeply-penetrating near-infrared (NIR) radiation to visible radiation for photoexcitation of PDT drugs. Here we demonstrate that the direct exposure of the cancer tissue to phototoxic ultraviolet radiation generated by NIR-photoexcited UCNPs enabled successful PDT. To this aim, core/shell UCNPs of the formula NaYF4:Yb3+Tm3+/NaYF4 featuring an enhanced band in the ultraviolet UV-A and UV-B spectral bands were rationally designed and synthesised. Coupling UCNPs to the recombinant modules of the Designed Ankyrin Repeat Protein (DARPin) fused to a fluorescent protein mCherry allowed the target delivery of DARPin-mCherry/UCNP to human breast adenocarcinoma SK-BR-3 cells overexpressing HER2/neu receptors, as confirmed by fluorescence microscopy. DARPin-mCherry/UCNPs were demonstrated to be phototoxic to SK-BR-3 cells under 975 nm laser irradiation at a dose of 900 J cm-2 due to the UV photoexcitation of endogenous photosensitizers and concomitant generation of reactive oxygen species. The Lewis lung cancer mouse model was employed to demonstrate the feasibility of PDT using UCNP-mediated UV excitation of endogenous photosensitizers in the tumor tissue at a NIR dose of 1200 J cm-2. This study paves the way for exploring and harnessing UV photoexcitation processes in deep tissues in vivo.

Prospects for using upconversion nanoparticles as markers for tumor optical imaging are discussed. Using a model of epidermoid Lewis lung carcinoma engrafted in mice, luminescent signals from nanoparticles delivered into the tumor tissue are registered in vivo.

Biocompatible PEG-containing UCNPs were designed for in vivo passive targeting of tumor associated with UCNP efficient accumulation and tumor contrast visualization.