UV Upconversion Research Articles

Blue to UV upconversion properties of Pr3+ doped ACaF3 (A = K, Rb, Cs) phosphors

Materials capable of converting visible light into the ultraviolet C (UVC) region are promising candidates for antimicrobial technology and photocatalytic applications. In this work, the effective UVC upconversion phosphors ACaF3:Pr3+ (A = K, Rb, Cs) were synthesized using solid state reactions. Upconverted emissions in the range from 230 to 315 nm were obtained with 444 nm laser excitation. The dependence of upconverted luminescence on pump power, the concentration of Pr3+ ions, and the decay profiles of upconverted luminescence provide insights into the primary mechanisms responsible for upconversion. Among the obtained fluoroperovskites, the rubidium composition showed the most intense luminescence. Additionally, ACaF3:1 %Pr3+ exhibits a manifold increase in upconversion emission compared to the previously studied reference material LiYF4:1 %Pr3+, indicating the potential use of fluoroperovskites for surface decontamination.

NIR-driven intense UV upconversion films for non-contact high-efficiency prevention of bacterial infections

Bacterial infections on wounds imposes a significant limitation to the wound healing. Although the conventional drug antibacterial dressing is employed for hindering bacterial infection, the inevitable microbial resistance and secondary damage severely limit the quality and speed of wound healing. Herein, the NIR-driven intense UV upconversion (UC) BaLu2F8:80%Yb3+/0.5%Tm3+ microcrystals are, for the first time, designed and fabricated into solid sterilization film to protect the wounds from infections. Equipped with excessive Yb3+ sensitizers, the emission of Yb3+/Tm3+ co-doped monoclinic BaLu2F8 matrix achieve a 175-fold enhancement at the UV band. The UV UC microcrystals was further fabricated into a NIR-to-UV sterilization film with a diameter of 1.5 cm and a thickness of 150 μm using solution casting method, which can efficiently destroy 97 % of E. coli with a NIR irradiation of 5 minutes. Due to the outstanding penetrability of NIR irradiation, the sterilization film under 4 layers gauze dressing can be activated to produce UV photons. The in-vivo mouse tests demonstrate the well-designed NIR-to-UV sterilization film can speed up the wound healing by high-efficient inhibiting E. coli infection under the irradiation of 980 nm NIR laser. The non-contact NIR-driven UV sterilization film require no more drugs and dressing exchange, thus entirely eliminating the effect of microbial resistance and secondary damage from conventional drug dressing. Our work provides a new alternative for constructing highly-efficiency sterilization dressing through the utilization of NIR-to-UV optical conversion materials.

Tuning the 5d State of Pr3+ in Oxyhalides for Efficient Deep Ultraviolet Upconversion

AbstractVisible‐to‐ultraviolet (UV) upconversion provides a fascinating strategy to achieve deep UV emission through readily accessible visible light. However, the intensity of deep UV emission obtained through visible‐to‐UV upconversion progress is still far from satisfactory, severely constraining its practical applications. Herein, a novel class of praseodymium ion (Pr3+)‐doped rare‐earth oxyhalides (YOCl, YOBr, and LuOBr) to achieve efficient upconverted deep UV emission in the spectral range of 250–350 nm is developed. The upconverted UV emission intensity of LuOBr:Pr3+ is determined to be 56.7 times stronger than that of the well‐established Lu7O6F9:Pr3+. When employed as a photon‐converter to activate photocatalytic water splitting reactions, upconverted deep UV emission enables H2 generation under visible light (λ > 420 nm) excitation from a xenon lamp. The efficient deep UV upconversion stems from tuning 4f15d1 state of Pr3+ by oxyhalide constituent which both facilitates the absorption of excitation photons in long‐lived intermediate 4f2 states and suppress the probability of nonradiative relaxation from 4f15d1 state. These findings not only provide new insights into a mechanistic understanding of the host effect on upconversion process but also make a breakthrough in developing efficient deep upconversion materials that will expand their further applications.

Natural and polyanionic heparin polysaccharide functionalized upconversion nanoparticles for highly sensitive and selective ratiometric detection of pesticide

Pesticide contamination is a global concern, threatening human health and food safety. Herein, we developed heparin (HEP) functionalized upconversion nanoparticles (UCNPs)-based ratiometric nanosensor for the sensitive detection of 2,6-dichloro-4-nitroaniline (DCN) pesticide via inner filter effect. The strategy for HEP functionalization of UCNPs is based on adjusting the surface potentials of UCNPs with polyanionic HEP through the electrostatic interaction. UCNPs (NaYbF4:Gd/Y/Tm@NaYbF4@NaYF4) was designed with core-shell-shell structure and extra sensitizer layer for efficient and strong upconversion luminescence (UCL) in the range of UV to NIR. After incorporation of DCN, the upconverted UV emission of UCNPs-HEP ratiometric nanosensor was considerably quenched with the NIR UCL at 800 nm remaining unchanged as internal standard. The UCNPs-HEP ratiometric nanosensor can achieve outstandingly selective and sensitive detection of DCN at the wide linear range of 5–300 μM with a detection limit of 0.41 μM. The remarkable applicability of the UCNPs-HEP ratiometric nanosensor was verified in apple, cucumber and grapes samples. The developed UCNPs-HEP ratiometric nanosensor with excellent biocompatibility and water dispersion capability, is promising for convenient, selective and sensitive sensing of DCN towards food and aqueous samples.

Spatially Controlled UV Light Generation at Depth using Upconversion Micelles.

UV light can trigger a plethora of useful photochemical reactions for diverse applications, including photocatalysis, photopolymerization, and drug delivery. These applications typically require penetration of high-energy photons deep into materials, yet delivering these photons beyond the surface is extremely challenging due to absorption and scattering effects. Triplet-triplet annihilation upconversion (TTA-UC) shows great promise to circumvent this issue by generating high-energy photons from incident lower-energy photons. However, molecules that facilitate TTA-UC usually have poor water solubility, limiting their deployment in aqueous environments. To address this challenge, a nanoencapsulation method is leveraged to fabricate water-compatible UC micelles, enabling on-demand UV photon generation deep into materials. Two iridium-based complexes are presented for use as TTA-UC sensitizers with increased solubilities that facilitate the formation of highly emissive UV-upconverting micelles. Furthermore, this encapsulation method is shown to be generalizable to nineteen UV-emitting UC systems, accessing a range of upconverted UV emission profiles with wavelengths as low as 350nm. As a proof-of-principle demonstration of precision photochemistry at depth, UV-emitting UC micelles are used to photolyze a fluorophore at a focal point nearly a centimeter beyond the surface, revealing opportunities for spatially controlled manipulation deep into UV-responsive materials.

MMP-2 and upconverted UV dual-mediated drug sequential delivery and on-site immobilization for enhanced multidrug-resistant cancer therapy

MMP-2 and upconverted UV dual-mediated drug sequential delivery and on-site immobilization for enhanced multidrug-resistant cancer therapy

Near-infrared light responsive intensified multiphoton ultraviolet upconversion in nanostructures towards efficient reactive oxygen species generation.

Near-infrared-to-ultraviolet (NIR-to-UV) multiphoton upconversion has recently received increasing attention owing to its promising frontier applications in the fields of biomedicine and nanophotonics. However, the realization of high-efficiency NIR-to-UV upconversion remains a dispiriting challenge due to weak excitation light harvesting and photo-conversion efficiency. Herein, we propose a mechanistic strategy to achieve intensified UV upconversion by manipulating the injected excitation energy flux. A simple LiYbF4:Tm@LiYF4 host-sensitized sublattice core-shell nanostructure was initially proposed to compete with the concentration quenching effect and increase energy transfer efficiency. Then, the organic dye ICG was further coated to introduce the antenna sensitization effect to highly increase the absorption ability of nanocrystals. After optimizing the ICG number loaded on the surface and separation distance, up to 167-fold UV upconversion emission enhancement was achieved under low-power excitation of 808 nm. More importantly, the efficient UV upconversion exhibits enhanced reactive oxygen species (ROS) generation activity by fabricating a TiO2-modified upconversion nanocomposite, revealing great application potential in frontier fields such as in vivo photodynamic therapy and bioimaging-guided therapeutics. Our results can provide versatile designs to achieve efficient UV upconversion, overcome conventional limitations, and offer exciting opportunities for potential applications in biomedical fields.

Gd3+ ion induced UV upconversion emission and temperature sensing in Tm3+/Yb3+:Y2O3 phosphor

Cubic phase Tm3+/Yb3+:Y2O3 and Tm3+/Yb3+/Gd3+:Y2O3 phosphors were prepared by low temperature combustion technique for upconversion emission in UV–visible range. The 980 nm excitation has generated UV emission at 314 nm in tridoped phosphor due to the energy transfer from Tm3+ to Gd3+ ion. Characteristic emission bands from Tm3+ are also observed in both the phosphors. Thermally coupled Stark sublevels 1G4(a) (476 nm) and 1G4(b) (488 nm) of Tm3+ ion were utilised for optical thermometry using fluorescent intensity ratio (FIR) method. The result shows that maximum absolute sensitivity in tridoped phosphor is observed to be 1.33 × 10−3 K−1 at 298 K. Moreover, temperature rise of phosphor at various pump power densities was also measured and it is estimated to achieve 407 K at the pump power density of 38.46 W/cm2.

Near-Infrared Light-Controlled and Real-Time Detection of Osteogenic Differentiation in Mesenchymal Stem Cells by Upconversion Nanoparticles for Osteoporosis Therapy.

Osteoporosis (OP) is one of the most common diseases in the elderly, and it is not effectively solved by current treatments. Mesenchymal stem cells (MSCs) have multiple differentiation potentials, which can induce osteogenic differentiation to treat OP; however, it is important to understand how to remotely control and detect osteogenic differentiation in vivo in real time. Here, we developed an upconversion nanoparticle (UCNP)-based photoresponsive nanoplatform for near-infrared (NIR) light-mediated control of intracellular icariin (ICA) release to regulate the osteogenic differentiation of MSCs for OP therapy. We simultaneously detected osteogenic differentiation in vivo in real time to evaluate the treatment effects. The Tm/Er-doped UCNPs were synthesized and coated with mesoporous silica (UCNP@mSiO2) first. Then, the photocaged linker 4-(hydroxymethyl)-3-nitrobenzoic acid (ONA) and the PEG linker (OH-PEG4-MAL) were linked to the surface of UCNP@mSiO2 to conjugate to the cap β-cyclodextrin (β-CD) and the Arg-Gly-Asp (RGD)-targeted peptide/matrix metalloproteinase 13 (MMP13)-sensitive peptide-BHQ (CGPLGVRGK-BHQ3) to form the UCNP nanoplatform (UCNP@mSiO2-peptide-BHQ-ONA-CD) for drug loading. Under 980 nm NIR light, the upconverted UV from the UCNPs triggered the cleavage of cap β-CD and the intracellular release of ICA to induce the osteogenic differentiation of MSCs for OP therapy. Meanwhile, MMP13, which was produced by osteogenic differentiation of MSCs, cleaved the MMP13-sensitive peptide to remove BHQ and recover the fluorescence of UCNPs, allowing real-time detection of osteogenic differentiation and the evaluation of the OP treatment effect. This photoresponsive UCNP nanoplatform has the potential to be used for the remote control and real-time detection of osteogenic differentiation of MSCs for OP therapy by NIR.

Viral Inactivation Using Visible to UV Upconversion Nanomaterials and Application in Self-Cleaning Anti-Viral Nanofilms on Personal Protective Equipment (PPE) to Mitigate Coronavirus Spread

COVID-19 has become one of the deadliest pandemics in human history and has taken a tremendous toll on human life in large part due to its ability to transmit through the air and from surface to surface. We developed a novel conformal nano-coating on PPE surfaces intended to capture and kill (inactivate) COVID-19 viruses on PPE surfaces. Disinfection and Sterilization has long been done using UV radiation. Taking inspiration from this conventional method, we came up with a product that can produce UV radiation locally and regeneratively, a visible to UV Upconversion Nanomaterial (UCNP). The idea here is to expose viruses to localized UV radiation (within the mutagenic range) to kill or deactivate them. In our work, we developed a Yttrium Orthosilicate-based UCNP. These nanoparticles were coated on PPE surfaces and cationic and anionic polymers using the layer by layer (LBL) coating method. An oligosaccharide species, chosen to possess strong bond affinity/complementarity to novel coronavirus S glycoprotein, was grafted to the polymer using functional groups/sites via click chemistry to add one more mechanism of virus inactivation. In our testing, two formulations, Y2SiO5(1% Pr, 1% Gd) and Y2SiO5 (1.2% Pr, 1.2% Gd, 7.2% Li) have reduced active coronavirus viral load 4*104 to 0 in an hour of exposure to white light.

Boosting the Energy Migration Upconversion through Inter-Shell Energy Transfer in Tb 3+ -Doped Sandwich Structured Nanocrystals

Boosting the Energy Migration Upconversion through Inter-Shell Energy Transfer in Tb ³⁺ -Doped Sandwich Structured Nanocrystals

Enhancing multiphoton upconversion emissions through confined energy migration in lanthanide-doped Cs2NaYF6 nanoplatelets.

Lanthanide (Ln3+)-doped upconversion (UC) nanocrystals have drawn tremendous attention because of their intriguing optical properties. Currently, it is highly desired but remains challenging to achieve efficient multiphoton UC emissions. Herein, we report the controlled synthesis of a new class of UC nanocrystals based on Cs2NaYF6:Yb/Tm nanoplatelets (NPs), which can effectively convert the 980 nm light to five-photon and four-photon UC emissions of Tm3+ without the fabrication of a complicated core/multishell structure required in traditional nanocrystals. Particularly, the as-prepared Cs2NaYF6:Yb/Tm NPs exhibit a maximal UV-to-NIR emission intensity ratio of 1.2, which is the highest among Tm3+-doped core-only UC nanocrystals. We reveal that the enhanced multiphoton UC emissions may benefit from the confined energy migration of Ln3+ dopants in the unique two-dimensional-like structure of Cs2NaYF6 NPs. As such, intense red and green UC emissions of Eu3+ and Tb3+ can further be generated via the cascade sensitization of Tm3+ and Gd3+ in Cs2NaYF6:Yb/Tm/Gd/Eu and Cs2NaYF6:Yb/Tm/Gd/Tb NPs, respectively. These results validate the superiority of Cs2NaYF6 for the future design of efficient UC nanocrystals towards versatile applications.

Near-infrared responsive upconversion glass-ceramic@BiOBr heterojunction for enhanced photodegradation performances of norfloxacin

An efficient luminous and electronic energy transmission BiOBr based near-infrared (NIR) responsive heterojunction photocatalyst was successfully fabricated through growing BiOBr nanosheets on the superficial layer of the SrF2–Bi2O3–B2O3/Yb3+,Tb3+ (SBBF) upconversion glass-ceramic (GC) via a facile in-situ etching GC method (FIEG). A high norfloxacin (NOR) degradation rate of 56% was obtained under 180 min NIR light irradiation for the NIR GC photocatalyst (SBBF/BiOBr-10), and it possesses much enhanced photocatalytic activity compared with that of pure BiOBr under UV–vis–NIR light irradiation. Wherein six intermediate products were identified in the NOR photodegradation process and the possible degradation pathways were proposed. B3+, Yb3+ and Tb3+ ions in GC can be doped into BiOBr layer during the FIEG process. The core–shell structure of the GC@BiOBr heterojunction photocatalyst is in favor of increasing charge transport and reducing the recombination rate of excited carriers, and it efficiently harvests NIR photons to emit UV and visible light upconversion emissions, which can be utilized during the photocatalysis process. The photocatalyst can be facilely regenerated via HBr etching again, moreover, the low-cost and less time requirement promote the possibility of large-scale fabrication of the efficient photocatalysts.

The construction of sublattice level energy cluster for promoting UV upconversion emission in tetragonal LiYF4

The preparation of high performance upconversion luminescence materials with stronger shortwave emissions is still a challenge. In this work, the feature of hexagon circles sublattice structure of tetragonal LiYF4 was revealed, and the sublattice level energy clusters of 4 Yb3+-1Tm3+ were constructed by the substitution of 70 mol% Yb3+ for Y3+ in tetragonal LiYF4 matrix. The sensitizing ions concentration quenching was inhibited by the hexagon circles sublattice structure, and the upconversion luminescence was dramatically enhanced, especially, the UV band emission was enhanced about 20 times and the intensity ratio of UV to blue emissions was improved about 10 folds under the excitation power density of 0.230 W/cm2. Photon numbers of upconversion emissions obviously decreased with the increasing of sublattice level energy clusters that the upconversion process of three photons was changed to two steps of two photons process. The upconversion luminescence mechanism of sublattice energy cluster construction was system investigated. The material with high performance of UV and blue UC luminescence can be a well candidate for the applications of photodynamic therapy and photocatalytic, etc. The work may be an inspiration for high efficient UC luminescence materials design and preparation.

Multicolor Solar Absorption as a Synergetic UV Upconversion Enhancement Mechanism in LiYF4:Yb3+,Tm3+ Nanocrystals

Motivated by the technologically important spectral conversion of sunlight for efficient photocatalysis, we present a detailed analysis of the multicolor excitation of LiYF4:Yb3+,Tm3+ nanocrystals leading to UV emission through upconversion. We demonstrate in particular that the combination of blue and IR light for generating upconversion UV emission is a linear mechanism that occurs at rather low density of excitation (a few mW/cm2). This upconversion efficiency is fully compatible with the broadband excitation from the sun, with comparable density similar to daylight excitation. It demonstrates that an appropriate design combining photocatalyst and a dedicated upconverter leads to a drastic improvement of the photocatalytic effect.

NIR-light-mediated spatially selective triggering of anti-tumor immunity via upconversion nanoparticle-based immunodevices

Immunomodulatory therapies are becoming a paradigm-shifting treatment modality for cancer. Despite promising clinical results, cancer immunotherapy is accompanied with off-tumor toxicity and autoimmune adverse effects. Thus, the development of smarter systems to regulate immune responses with superior spatiotemporal precision and enhanced safety is urgently needed. Here we report an activatable engineered immunodevice that enables remote control over the antitumor immunity in vitro and in vivo with near-infrared (NIR) light. The immunodevice is composed of a rationally designed UV light-activatable immunostimulatory agent and upconversion nanoparticle, which acts as a transducer to shift the light sensitivity of the device to the NIR window. The controlled immune regulation allows the generation of effective immune response within tumor without disturbing immunity elsewhere in the body, thereby maintaining the antitumor efficacy while mitigating systemic toxicity. The present work illustrates the potential of the remote-controlled immunodevice for triggering of immunoactivity at the right time and site.

Plasmonic Enhancement of NIR to UV Upconversion by a Nanoengineered Interface Consisting of NaYF4:Yb,Tm Nanoparticles and a Gold Nanotriangle Array for Optical Detection of Vitamin B12 in Serum.

A nanoengineered interface fabricated by self-assembly enables the online determination of vitamin B12 via a simple luminescence readout in serum without any pretreatment. The interplay of Tm3+-doped NaYF4 nanoparticles (UCNPs) and a gold nanotriangle array prepared by nanosphere lithography on a glass slide is responsible for an efficient NIR to UV upconversion. Hot spots of the gold assembly generate local electromagnetic-field enhancement, favoring the four-photon upconversion process at the low-power excitation of approximately 13 W·cm-2. An improvement by about 6 times of the intensity for the emission peaking at 345 nm is achieved. The nanoengineered interface has been applied in a proof-of-concept sensor for vitamin B12 in serum, which is known as a marker for the risk of cancer; Alzheimer disease; or, during pregnancy, neurological abnormalities in newborn babies. Vitamin B12 can be detected in serum down to 3.0 nmol·L-1 by a simple intensity-based optical readout, consuming only 200 μL of a sample, which qualifies as easy miniaturization for point-of-care diagnostics. Additionally, this label-free approach can be used for long-term monitoring because of the high photostability of the upconversion nanoparticles.

Integration of nanoscale light emitters: an efficient ultraviolet and blue random lasing from NaYF4:Yb/Tm hexagonal nanocrystals

Near infrared light-controlled release of payloads from ultraviolet-sensitive (UV-sensitive) polymer hydrogels or nanocarriers is one of the most promising strategies for biotherapy. Here, we propose the concept of light activation of NaYF4:20%Yb,2%Tm nanocrystals (NCs). NaYF4:20%Yb,2%Tm NCs are synthesized by a solvothermal method. Effective upconversion luminescence from NaYF4:20%Yb,2%Tm NCs excited by a continuous wave (CW) 980 nm laser is obtained. The NaYF4:20%Yb,2%Tm NCs are then used as a laser gain medium and sandwiched between Al and quartz reflectors to form laser microcavities. UV and blue upconverted random lasing is obtained from the laser microcavities. Hence, we verify explicitly that the NaYF4:Yb,Tm NCs support UV and blue upconversion random lasing via a 980 nm nanosecond laser excitation. Our work provides what we believe is a new concept for precision and localized cancer therapy by external light excitation.

Ultraviolet and visible up-conversion in sol-gel based SiO2-BaY0.78-xGdxYb0.2Tm0.02F5 nano-glass-ceramics

Sol-gel derived nano-glass-ceramics with composition 95SiO2-5BaY0.78-xGdxYb0.2Tm0.02F5, where x = 0, 0.2, 0.4, 0.6 and 0.78, were obtained after adequate thermal treatments of precursor glasses. X-ray diffraction, transmission electron microscope and energy dispersive X-ray spectroscopy, confirmed the precipitation and distribution of nanocrystals, with sizes around 10–13 nm, in an amorphous silica network. Under excitation at 980 nm, along with blue, red and NIR characteristic up-conversion emissions of Tm3+ ions, intense UV up-conversion emissions coming from 1I6 and 1D2 levels of Tm3+ ions were also observed in all the studied samples. Additionally, when substituting Y3+ by Gd3+ ions, UV up-conversion emissions coming from Gd3+ ions, along with a reduction of the UV up-conversion emissions of Tm3+ ions, were observed, involving an energy transfer process from Yb3+/Tm3+ systems to Gd3+ ions. UC mechanisms and energy transfer processes were confirmed by transient emission and pump power measurements. Moreover, power dependence analysis revealed saturation effects in all up-conversion emissions, even at low pump power. Results suggest that these highly efficient up-conversion nano-glass-ceramics present potential applications as UV-blue solid state laser materials and solid state lighting.

Near-infrared light-controlled regulation of intracellular calcium to modulate macrophage polarization

Macrophages are multifunctional immune cells with diverse physiological functions such as fighting against infection, influencing progression of pathologies, maintaining homeostasis, and regenerating tissues. Macrophages can be induced to adopt distinct polarized phenotypes, such as classically activated pro-inflammatory (M1) phenotypes or alternatively activated anti-inflammatory and pro-healing (M2), to execute diverse and dynamic immune functions. However, unbalanced polarizations of macrophage can lead to various pathologies, such as atherosclerosis, obesity, tumor, and asthma. Thus, the capability to remotely control macrophage phenotypes is important to the success of treating many pathological conditions involving macrophages. In this study, we developed an upconversion nanoparticle (UCNP)-based photoresponsive nanocarrier for near-infrared (NIR) light-mediated control of intracellular calcium levels to regulate macrophage polarization. UCNP was coated with mesoporous silica (UCNP@mSiO2), into which loaded calcium regulators that can either supply or deplete calcium ions. UCNP@mSiO2 was chemically modified through serial coupling of photocleavable linker and Arg-Gly-Asp (RGD) peptide-bearing molecular cap via cyclodextrin-adamantine host-guest complexation. The RGD-bearing cap functioned as the photolabile gating structure to control the release of calcium regulators and facilitated the cellular uptake of UCNP@mSiO2 nanocarrier. The upconverted UV light emission from the UCNP@mSiO2 under NIR light excitation triggered the cleavage of cap and intracellular release of calcium regulators, thereby allowing temporal regulation on the intracellular calcium levels. Application of NIR light through skin tissue promoted M1 or M2 polarization of macrophages, by elevating or depleting intracellular calcium levels, respectively. To the best of our knowledge, this is the first demonstration of NIR light-mediated remote control on macrophage polarization. This photoresponsive nanocarrier offers the potential to remotely manipulate in vivo immune functions, such as inflammation or tissue regeneration, via NIR light-controlled macrophage polarization.