Near-infrared Emission Research Articles

Synthesis and functionalities of FeSn12 superatom prepared by single atom introduction with a dendrimer template.

Superatoms are promising as new building block materials that can be designed by precise controlling of the constituent atoms. Stannaspherene (Sn12 2-) is a rigid cage-like cluster with icosahedral symmetry, for which one-atom encapsulation was theoretically expected and detected in the gas phase. Here, a single-atom introduction method into stannaspherene using a dendrimer template with polyvinylpyrrolidone (PVP) protection is demonstrated. This advanced solution-phase synthesis allows not only the selective doping of one atom into the cluster cage, but also enable further detail characterization of optical and magnetic properties that were not possible in the gas-phase synthesis. In other words, this liquid-phase synthesis method has enabled the adaptation of detailed analytical methods. In this study, FeSn12 was synthesized and characterized, revealing that a single Fe atom introduction in the Sn12 2- cage result in the appearance of near-infrared emission and enhancement in the magnetism.

Long-wavelength absorbing and mitochondria or lysosome organelle-targeting photosensitizers with flexible or rigid terminus for fluorescence imaging and high-performance photodynamic therapy

In this study, two chlorin photosensitizers (PSs) having long-wavelength absorbing (λmax 707 and 709 nm) and mitochondria or lysosome organelle-targeting abilities have been developed for use in photodynamic therapy (PDT). We simply modified two PSs, PS1 (N-propyl unit as a flexible terminus) and PS2 (N-propargyl unit as a rigid terminus), which displayed near-infrared absorption and fluorescence emission and high 1O2 quantum yield (0.720 and 0.593), indicating a suitable PS for PDT, resulting in high-performance photodynamic activity with low IC50 values (0.31–0.36 μM against A549 and HeLa cells). Importantly, PS1 and PS2 exhibited excellent mitochondrial or lysosomal organelle-targeting ability with high Pearson's correlation coefficient values (∼0.9). The excellent PDT effect of PS1 and PS2 was confirmed by fluorescence images of intracellular reactive oxygen species generation as well as live/dead staining images. Therefore, these two PSs have great potential as fluorescence imaging materials and PDT reagents.

Chiral Aggregation-Induced Emission Carbon Dot-Based Multicolor and Near-Infrared Circularly Polarized Delayed Fluorescence via a Light-Harvesting System.

Circularly polarized luminescence (CPL) materials are the research frontier of chiral luminescence. As a kind of luminescent carbon material, carbon dots (CDs) are expected to become excellent candidates for the construction of CPL materials. However, the construction of CD-based circularly polarized afterglow emission, especially multicolor and near-infrared emission, remains a great challenge due to aggregation-caused quenching and the instability of triplet excitons. In this work, we synthesized chiral CDs with aggregation-induced emission using dithiosalicylic acid and l/d-arginine as precursors through a one-step solvothermal method. Notably, the CDs exhibit green delayed fluorescence (DF) in poly(vinyl alcohol) films. Furthermore, multicolor and near-infrared circularly polarized delayed fluorescence is successfully realized via engineering a chiral light-harvesting system in which the CDs with green DF emission act as energy donors and fluorescent dyes with emission colors ranging from yellow to the near infrared serve as energy acceptors.

Grafting Carbon Dots on Persistent Luminescence Phosphors to Generate Remarkably Improved NIR Afterglow for Microenvironment Fluorescence Detection

AbstractRecently, combining long afterglow materials with organic fluorescent dyes, particularly carbon dots (CDs) to produce heterojunction and improve its luminescence and persistence properties became an important research direction. However, the precise role of these internal defects in the energy transfer process of CD@inorganic matrix composite fluorescent materials has not been thoroughly discussed. Establishing matching trap level to promote the energy transfer between the trap level and CDs level not only helps to enhance the afterglow performance, but also can explain the heterogeneous structure interaction between organic–inorganic fluorescent materials. Herein, ZLAGC@CDs luminescent composite is successfully synthesized via coating CDs on Zn1‐x(Li/Al)xGa2xO4:0.005Cr3+ (ZLAGC, x = 0–1), which exhibits a unique double emission at ≈430 nm (the defect luminescence of CDs) and 718 nm (the 2E→4A2 transition of Cr3+). After coating, the energy transfer from the defect level of CDs to the excited state of Cr3+ enhanced the NIR emission. The electron transfer between the defect level of CDs and the split deeper trap level of ZLAGC also improved the visible and near‐infrared (NIR) afterglow. The fluorescence and afterglow signals of ZLAGC@CDs are highly sensitive to solution pH under acidic conditions, indicating that the prepared fluorescent composite has potential application in acid microenvironment fluorescence detection.

Novel estrogen receptor β/histone deacetylase dual-targeted near-infrared fluorescent probes as theranostic agents for imaging and treatment of prostate cancer

Estrogen receptor (ER) β and histone deacetylases (HDACs), when overexpressed, are associated closely with the occurrence and development of prostate cancer and are, therefore, considered important targets and biomarkers used in the clinical treatment of prostate cancer. The present study involved the design and synthesis of the first ERβ and HDAC dual-target near-infrared fluorescent probe with both imaging capacity and antitumor activity for prostate cancer. Both P1 and P2 probes exhibited excellent ERβ selectivity, with P1 being almost exclusively selective for ERβ compared to ERα. In addition, P1 exhibited good optical properties, such as strong near-infrared emission, large Stokes shift, and better anti-interference ability, along with excellent imaging ability for living cells. P1 also exhibited potent inhibitory activity against HDAC6 and DU-145 cells, with IC50 values of 52 nM and 0.96 μM, respectively. Further, P1 was applied successfully for the in vivo imaging of prostate cancer in a mouse model, and significant in vivo antitumor efficacy was achieved. The developed dual-target NIR fluorescent probe is expected to serve as an effective tool in the research on prostate cancer, leading to novel insights for the theranostic study of diseases related to ERβ and HDACs.

Turn-on Near-Infrared Phosphorescent Recognition of Anion Based on Self-Assembly of Cyclometalated Platinum Complexes That Induce Oncosis and Monitor Living Cells.

The design of bio-responsive functional molecular materials that can undergo self-assembly to form nanostructures within cells in response to cellular endogenous stimuli and the clarification of their prospective reaction mechanisms are of paramount significance. This work aims to elucidate the spatiotemporal generation of subcellular nanostructures and their influence on cellular functionality. Three sets of cyclometalated platinum complexes have been designed and synthesized as near-infrared phosphorescent turn-on probes for specific anions based on dynamic self-assembly in aqueous solution. The augmentation of the quantity of aromatic rings in the NN bidentate ligand of the complex modifies both the intensity of the intermolecular Pt-Pt interaction and the capacity to generate self-assembled nanowires with near-infrared emission. Besides, we explored the impact of the CN ligand's substituent effect on anion recognition, which revealed that complexes with electron-absorbing F atom substitution exhibit superior selectivity for Br-. These complexes display vivid green turn-on luminescence upon interaction with cellular biomolecules, enabling dynamic monitoring of their subcellular distribution and their interaction on diverse conditions. Furthermore, our complexes were observed to induce oncosis in cancer cells, underscoring the potential of our work in facilitating in vitro diagnosis and developing effective theranostic agents for cancer therapy.

Tunable near-infrared light emission from layered TiS3 nanoribbons

Tunable near-infrared light emission from layered TiS3 nanoribbons

A New Theranostic Platform Against Gram-Positive Bacteria Based on Near-Infrared-Emissive Aggregation-Induced Emission Nanoparticles.

Infections induced by Gram-positive bacteria pose a great threat to public health. Antibiotic therapy, as the first chosen strategy against Gram-positive bacteria, is inevitably associated with antibiotic resistance selection. Novel therapeutic strategies for the discrimination and inactivation of Gram-positive bacteria are thus needed. Here, a specific type of aggregation-induced emission luminogen (AIEgen) with near-infrared fluorescence emission as a novel antibiotic-free therapeutic strategy against Gram-positive bacteria is proposed. With the combination of a positively charged group into a highly twisted architecture, self-assembled AIEgens (AIE nanoparticles (NPs)) at a relatively low concentration (5µm) exhibited specific binding and photothermal effect against living Gram-positive bacteria both in vitro and in vivo. Moreover, toxicity assays demonstrated excellent biocompatibility of AIE NPs at this concentration. All these properties make the AIE NPs as a novel generation of theranostic platform for combating Gram-positive bacteria and highlight their promising potential for in vivo tracing of such bacteria.

Cucurbit[8]uril-based non-covalent heterodimer realized NIR cell imaging through topological transformation from nanowire to nanorod

In recent years, multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials, cell imaging and other fields. Herein, several kinds of macrocycles including cucurbiturils, calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine (G), wherein cucurbit[8]uril (CB[8]) and G can form nanowires at a stoichiometric ratio of n:n through host-guest encapsulation to form a non-covalent heterodimer. Significantly, the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 nm. When the supramolecular polymer is further assembled with amphiphilic calix[4]arene (SC4A8), the fluorescence emission of G⊂CB[8] further increases to 1.4 times, accompanied by the morphological transformation from linear structure to nanorod structure. Subsequently, a very small amount of dye Cy5 is added to the assembly solution as an energy receptor, and the negatively charged G⊂CB[8]@SC4A8 system is regarded as an energy donor. The efficient energy transfer process enables near-infrared (NIR) emission at 675 nm with 71% energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:1. Finally, the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.

Directly Identifying Multiple Cr3+ Emitting Centers for Broad Near‐Infrared Emission in an Efficient and Near‐Zero Thermal Quenching Garnet‐Type Phosphor

AbstractCr3+ doped garnet‐type (A3B2C3O12) near‐infrared (NIR) phosphors is a desirable research hotspot due to their prospective night vision, bioimaging, and plant growth utilizations. Meanwhile, the origin of multisite broad emission is yet a controversial topic. To resolve the trouble, verifying accurately the multiple Cr3+ occupancy sites is a key. Furthermore, it is an urgent need for improving the external quantum efficiency and luminescent thermostability. Herein, in Y3Sc2Al3O12 (YSAO), advanced electron microscopy technique is employed to directly confirm that the obtained broadband NIR emission originates from Cr3+ in [ScO6] octahedral and [YO8] dodecahedral sites. The optimal YSAO:5%Cr3+ sample exhibits high quantum efficiency (IQE/EQE = 74/31%) and near‐zero thermal quenching (97%@423 K and 92%@473 K). The theoretical calculations and experimental proofs reveal that YSAO possesses high structural rigidity and wide bandgap, which is responsible for the extremely thermostable luminescence. The high‐power YSAO:5%Cr3+‐converted NIR LED device shows promising multifunctional applications. This work not only provides an efficient NIR broadband phosphor with near‐zero thermal quenching, but also provides an effective determination method for the multiple emitting centers of phosphor materials.

A Self-Sustaining Near-Infrared Afterglow Chemiluminophore for High-Contrast Activatable Imaging.

Afterglow imaging holds great promise for ultrasensitive bioimaging due to its elimination of autofluorescence. Self-sustaining afterglow molecules (SAMs), which enable all-in-one photon sensitization, chemical defect formation and afterglow generation, possess a simplified, reproducible, and efficient superiority over commonly used multi-component systems. However, there is a lack of SAMs, particularly those with much brighter near-infrared (NIR) emission and structural flexibility for building high-contrast activatable imaging probes. To address these issues, this study for the first time reports a methylene blue derivative-based self-sustaining afterglow agent (SAN-M) with brighter NIR afterglow chemiluminescence peaking at 710 nm. By leveraging the structural flexibility and tunability, an activatable nanoprobe (SAN-MO) is customized for simultaneously activatable fluoro-photoacoustic and afterglow imaging of peroxynitrite (ONOO- ), notably with a superior activation ratio of 4523 in the afterglow mode, which is at least an order of magnitude higher than other reported activatable afterglow systems. By virtue of the elimination of autofluorescence and ultrahigh activation contrast, SAN-MO enables early monitoring of the LPS-induced acute inflammatory response within 30 min upon LPS stimulation and precise image-guided resection of tiny metastatic tumors, which is unattainable for fluorescence imaging.

Excited state properties of 5-fluoro-4-thiouridine derivative†.

The excited state properties of thionated 5-fluorouridine (2',3',5'-tri-O-acetyl-5-fluoro-4-thiouridine; ta5F4TUrd), synthesized with Lawesson's reagent, have been intensively investigated with nanosecond transient absorption spectroscopy, time-resolved thermal lensing, near-infrared emission, and quantum chemical calculation. The intrinsic triplet lifetime of ta5F4TUrd was determined to be μs in acetonitrile, and the formation quantum yield of the excited triplet state was as large as . The quenching rate constants of the triplet ta5F4TUrd by the dissolved oxygen molecule and by the self-quenching process were found to be nearly equal to the diffusion-controlled rate of acetonitrile. The quantum yield of the singlet molecular oxygen produced through energy transfer between the triplet ta5F4TUrd and the dissolved oxygen, , was successfully determined to be under the oxygen-saturated condition. From the oxygen concentration dependence of the value, the fraction of triplet ta5F4TUrd quenched by dissolved oxygen which gives rise to the 1 O2 * formation, , was successfully obtained to be , which was the largest among the thionucleobases and the thionucleosides reported so far. This could be due to the lower energy and/or the ππ* character of the triplet state.

Ketocyanine-Based Fluorescent Probe Revealing the Polarity Heterogeneity of Lipid Droplets and Enabling Accurate Diagnosis of Hepatocellular Carcinoma.

Hepatocellular carcinoma (HCC) has gradually become a pronoun for terrifying death owing to its high mortality rate. With the progression of HCC, lipid droplets (LDs) in HCC cells exhibit specific variations such as increased LDs number and decreased polarity, which can serve as the diagnostic target. However, developing an effective method to achieve HCC diagnosis and reveal LDs polarity heterogeneity is still a crucial challenge. Herein, the first high-performance LDs-targeting probe (1) is reported based on ketocyanine strategy with ultrasensitive polarity-responding ability and near-infrared emission. Probe 1 shows excellent sensitivity to polarity parameter Δf (0.027-0.290) with 808-fold fluorescence enhancement and the emission wavelength red-shifts 91nm. In HCC cells, probe 1 shows a 2.5- to 5.9-fold fluorescence enhancement compared with normal and other cancer cells which exceeds clinical threshold of 2.0, indicating probe 1 can distinguish HCC cells. The LDs polarity heterogeneity is revealed and it displays a sequence, HCC cells < other cancer cells < normal cells, which may provide useful insight to engineer LDs-targeting probes for HCC cell discrimination. Finally, probe 1 realizes accurate HCC diagnosis on the cellular, organ, and in vivo levels, providing a satisfying tool for clinical HCC diagnosis and surgical navigation.

Enhancing Purely Organic Room Temperature Phosphorescence via Supramolecular Self-Assembly.

Long-lived and highly efficient room temperature phosphorescence (RTP) materials are in high demand for practical applications in lighting and display, security signboards, and anti-counterfeiting. Achieving RTP in aqueous solutions, near-infrared (NIR) phosphorescence emission, and NIR-excited RTP are crucial for applications in bio-imaging, but these goals pose significant challenges. Supramolecular self-assembly provides an effective strategy to address the above problems. This review focuses on the recent advances in the enhancement of RTP via supramolecular self-assembly, covering four key aspects: small molecular self-assembly, cocrystals, the self-assembly of macrocyclic hosts and guests, and multi-stage supramolecular self-assembly. This review not only highlights progress in these areas but also underscores the prominent challenges associated with developing supramolecular RTP materials. The resulting strategies for the development of high-performance supramolecular RTP materials are discussed, aiming to satisfy the practical applications of RTP materials in biomedical science.

Pr3+ ions, another alternative near-infrared luminescence emitter though energy transfer from Eu2+ for NIR pc-LEDs

Near-infrared (NIR) light-emitting diodes (LED) have garnered significant research attention worldwide. This research presents a novel near-infrared phosphor doped with Pr3+ ions, exhibiting a broad NIR emission ranging from 800 to 1100 nm. Under 450 nm excitation, Li3Cs2Ba2B3P6O24:Pr3+ material generates near-infrared emission bands peaking at 882 and 1038 nm. However, this material exhibits relatively lower luminous intensity. Through Eu2+ co-doping, the NIR emission intensity of Li3Cs2Ba2B3P6O24:Pr3+ is significantly enhanced due to energy transfer. Photoluminescence spectra and luminescence decay curves support the efficient energy transfer (ET) between Eu2+ and Pr3+, resulting in remarkable NIR luminescence. The study evaluates the temperature stability and practical application of Li3Cs2Ba2B3P6O24:Eu2+, Pr3+ in near-infrared LED applications. Consequently, Pr3+ ions emerge as an alternative near-infrared luminescence emitter though energy transfer from Eu2+, offering new insights into developing NIR light sources for broadband NIR pc-LED applications.

Collapsars as Sites of r-process Nucleosynthesis: Systematic Photometric Near-infrared Follow-up of Type Ic-BL Supernovae

One of the open questions following the discovery of GW170817 is whether neutron star (NS) mergers are the only astrophysical sites capable of producing r-process elements. Simulations have shown that 0.01–0.1 M ⊙ of r-process material could be generated in the outflows originating from the accretion disk surrounding the rapidly rotating black hole that forms as a remnant to both NS mergers and collapsing massive stars associated with long-duration gamma-ray bursts (collapsars). The hallmark signature of r-process nucleosynthesis in the binary NS merger GW170817 was its long-lasting near-infrared (NIR) emission, thus motivating a systematic photometric study of the light curves of broad-lined stripped-envelope (Ic-BL) supernovae (SNe) associated with collapsars. We present the first systematic study of 25 SNe Ic-BL—including 18 observed with the Zwicky Transient Facility and 7 from the literature—in the optical/NIR bands to determine what quantity of r-process material, if any, is synthesized in these explosions. Using semi-analytic models designed to account for r-process production in SNe Ic-BL, we perform light curve fitting to derive constraints on the r-process mass for these SNe. We also perform independent light curve fits to models without the r-process. We find that the r-process-free models are a better fit to the light curves of the objects in our sample. Thus, we find no compelling evidence of r-process enrichment in any of our objects. Further high-cadence infrared photometric studies and nebular spectroscopic analysis would be sensitive to smaller quantities of r-process ejecta mass or indicate whether all collapsars are completely devoid of r-process nucleosynthesis.

Lanthanide Doping into All-Inorganic Heterometallic Halide Layered Double Perovskite Nanocrystals for Multimodal Visible and Near-Infrared Emission.

The introduction of lanthanide ions (Ln3+) into all-inorganic lead-free halide perovskites has captured significant attention in optoelectronic applications. However, doping Ln3+ ions into heterometallic halide layered double perovskite (LDP) nanocrystals (NCs) and their associated doping mechanisms remain unexplored. Herein, we report the first colloidal synthesis of Ln3+ (Yb3+, Er3+)-doped LDP NCs utilizing a modified hot-injection method. The resulting NCs exhibit efficient near-infrared (NIR) photoluminescence in both NIR-I and NIR-II regions, achieved through energy transfer down-conversion mechanisms. Density functional theory calculations reveal that Ln3+ dopants preferentially occupy the Sb3+ cation positions, resulting in a disruption of local site symmetry of the LDP lattices. By leveraging sensitizations of intermediate energy levels, we delved into a series of Ln3+-doped Cs4M(II)Sb2Cl12 (M(II): Cd2+ or Mn2+) LDP NCs via co-doping strategies. Remarkably, we observe a brightening effect of the predark states of Er3+ dopant in the Er3+-doped Cs4M(II)Sb2Cl12 LDP NCs owing to the Mn component acting as an intermediate energy bridge. This study not only advances our understanding of energy transfer mechanisms in doped NCs but also propels all-inorganic LDP NCs for a wider range of optoelectronic applications.

Blueshift and Photoluminescence Enhancement in Broadband Near‐Infrared Emitting Phosphor NaSr2(Al/Ga)Ge5O14: Cr3+ Dependence on the Sc/In Substitution

AbstractCr3+‐activated near‐infrared (NIR) phosphors have gained extensive attention for use in NIR phosphor‐converted light‐emitting diodes (pc‐LEDs), which are required for smart NIR spectroscopy techniques. Nevertheless, obtaining broadband NIR‐emitting phosphors with outstanding thermal stabilities and photoluminescence (PL) efficiencies remains a significant challenge. Herein, considering NaSr2XGe5O14 (X = Al, Ga, Sc, and In) as hosts, which possess a large band gap and multiple sites for the substitution of Cr3+ ions. NaSr2XGe5O14:Cr3+ phosphors are successfully prepared using a solid‐state reaction technology. Upon blue light excitation, the phosphors cover a broad NIR emission band in 650–1100 nm region. Notably, an abnormal blueshift and PL enhancement are observed following the substitution of Al/Ga with Sc/In. In particular, the PL internal quantum efficiency is improved from 34.5% (NaSr2GaGe5O14: Cr3+) to 87.5% (NaSr2ScGe5O14: Cr3+). Moreover, the manufactured NIR pc‐LED exhibited an exceptional photoelectric efficiency of 17.7% with an NIR output power of 10.2 mW at 20 mA, and its potential application in nondestructive detection is demonstrated.

Organoboron-Conjugated Homopolymers with Bright Narrowband Near-Infrared Emission

Organoboron-Conjugated Homopolymers with Bright Narrowband Near-Infrared Emission

Emerging Fe3+ Doped Broad NIR‐Emitting Phosphor Ca2.5Hf2.5(Ga, Al)3O12: Fe3+ for LWUV Pumped NIR LED

AbstractFe3+ is a promising dopant for designing near‐infrared (NIR) phosphors due to its broadband emitting, non‐toxic, and inexpensive properties. However, the 4E (4D) and 4E + 4A1 (4G) levels of Fe3+ ions are independent of the crystal‐field parameter, and the spectral regulation has become a huge challenge. Herein, a broadband NIR‐emitting phosphor Ca2.5Hf2.5(Ga, Al)3O12: Fe3+ is successfully developed toward long‐wave ultraviolet (LWUV) light‐pumped NIR phosphor‐converted LED (pc‐LED). Significantly, the excited transition reverse of Ca2.5Hf2.5Ga3O12: Fe3+ can be realized by simply adjusting Fe3+ concentration, which results in the largely enhanced excitation around 410 nm and matches well with the commercial LWUV LED. Moreover, Ca2.5Hf2.5Ga3O12: Fe3+ can exhibit a broadband NIR emission centered at 770 nm with optimized doping content at 0.01 mol%, which are demonstrated to ascribe to Fe3+ occupying both octahedral Hf 4+ and tetrahedral Ga3+ sites. Further, a simple cation modulation strategy is proposed to successfully break the lattice symmetry around Fe3+ ions and largely enhance the NIR‐emission intensity to 200% as much as before. Finally, a NIR pc‐LED is fabricated by employing Ca2.5Hf2.5Ga3O12: Fe3+, Al3+ coating on a 410 nm LED chip, which shows great potential in non‐destructive inspection applications.