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1.
Luminescence ; 39(5): e4750, 2024 May.
Article in English | MEDLINE | ID: mdl-38733198

ABSTRACT

Ultra-high thermally stable Ca2MgWO6:xSm3+ (x = 0.5, 0.75, 1, 1.25, and 1.5 mol%) double perovskite phosphors were synthesized through solid-state reaction method. Product formation was confirmed by comparing the X-ray diffraction (XRD) patterns of the phosphors with the standard reference file. The structural, morphological, thermal, and optical properties of the prepared phosphor were examined in detail using XRD, Fourier transform infrared spectra, scanning electron microscopy, diffused reflectance spectra, thermogravimetric analysis (TGA), photoluminescence emission, and temperature-dependent PLE (TDPL). It was seen that the phosphor exhibited emission in the reddish region for the near-ultraviolet excitation with moderate Colour Rendering Index values and high colour purity. The optimized phosphor (x = 1.25 mol%) was found to possess a direct optical band gap of 3.31 eV. TGA studies showed the astonishing thermal stability of the optimized phosphor. Additionally, near-zero thermal quenching was seen in TDPL due to elevated phonon-assisted radiative transition. Furthermore, the anti-Stokes and Stokes emission peaks were found to be sensitive toward the temperature change and followed a Boltzmann-type distribution. All these marked properties will make the prepared phosphors a suitable candidate for multifield applications and a fascinating material for further development.


Subject(s)
Luminescence , Luminescent Agents , Samarium , Temperature , Tungsten Compounds , Tungsten Compounds/chemistry , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Samarium/chemistry , Luminescent Measurements , X-Ray Diffraction , Calcium Compounds/chemistry , Oxides/chemistry , Thermogravimetry
2.
Luminescence ; 39(5): e4762, 2024 May.
Article in English | MEDLINE | ID: mdl-38698695

ABSTRACT

Broadband near-infrared (NIR) spectroscopy has gained significant attention due to its versatile application in various fields. In the realm of NIR phosphors, Fe3+ ion is an excellent activator known for its nontoxic and harmless nature. In this study, we prepared an Fe3+-activated SrGa12O19 (SGO) NIR phosphor and analyzed its phase and luminescence properties. Upon excitation at 326 nm, the SGO:Fe3+ phosphor exhibited a broadband emission in the range 700-1000 nm, peaking at 816 nm. The optical band gap of SGO:Fe3+ was evaluated. To enhance the long-lasting phosphorescence, an oxygen vacancy-rich SGO:Fe3+ (VO-SGO:Fe3+) sample was prepared for activation. Interestingly, the increase in the oxygen-vacancy concentration indeed contributed to the activation of persistent luminescence of Fe3+ ions. The VO-SGO:Fe3+ sample has a long duration and high charge storage capacity, allowing it to perform efficiently in various applications. This work provides the foundation for further design of Cr3+-free PersL phosphors with efficient NIR PersL.


Subject(s)
Luminescence , Luminescent Agents , Oxygen , Oxygen/chemistry , Luminescent Agents/chemistry , Strontium/chemistry , Luminescent Measurements , Ferric Compounds/chemistry , Gallium/chemistry , Iron/chemistry , Spectroscopy, Near-Infrared
3.
J Am Chem Soc ; 146(19): 13406-13416, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38698549

ABSTRACT

Bioluminescent indicators are power tools for studying dynamic biological processes. In this study, we present the generation of novel bioluminescent indicators by modifying the luciferin molecule with an analyte-binding moiety. Specifically, we have successfully developed the first bioluminescent indicator for potassium ions (K+), which are critical electrolytes in biological systems. Our approach involved the design and synthesis of a K+-binding luciferin named potassiorin. Additionally, we engineered a luciferase enzyme called BRIPO (bioluminescent red indicator for potassium) to work synergistically with potassiorin, resulting in optimized K+-dependent bioluminescence responses. Through extensive validation in cell lines, primary neurons, and live mice, we demonstrated the efficacy of this new tool for detecting K+. Our research demonstrates an innovative concept of incorporating sensory moieties into luciferins to modulate luciferase activity. This approach has great potential for developing a wide range of bioluminescent indicators, advancing bioluminescence imaging (BLI), and enabling the study of various analytes in biological systems.


Subject(s)
Luciferases , Luminescent Measurements , Potassium , Potassium/metabolism , Potassium/chemistry , Animals , Luminescent Measurements/methods , Mice , Luciferases/chemistry , Luciferases/metabolism , Humans , Protein Engineering , Luminescent Agents/chemistry , Firefly Luciferin/chemistry , Firefly Luciferin/metabolism
4.
Plant Physiol Biochem ; 211: 108672, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38718531

ABSTRACT

Luminescent materials can adjust the spectrum of light energy utilization by plants. However, current research on the effects of luminescent materials on aquatic plants and periphytic biofilms is limited. This study investigated the effects of the luminescent materials 4-(di-p-tolylamino) benzaldehyde-A (DTB-A) and 4-(di-p-tolylamino) benzaldehyde-M (DTB-M) on the submerged macrophyte Vallisneria natans (V. natans) and periphytic biofilm. Result demonstrated that low concentrations of DTB (0.1 µM) significantly promoted the growth and photosynthetic rate of V. natans. In terms of enzyme activity, exposure to a higher concentration of DTB (10 µM) increased the activities of peroxidase (POD), superoxide dismutase (SOD) and catalase (CAT). A combination of DTB-A and DTB-M treatment significantly changed the V. natans morphology and physiological characteristics, reducing the thickness of the cell wall and subsequently, promoting protein accumulation in leaves. There was no difference in the removal of ammonia or phosphate by V. natans at the 0.1 µM concentration, and the removal of ammonia and phosphate by V. natans decreased significantly as the concentration of luminescent material increased. A total of 3563 OTUs were identified in the biofilm community. The microbial community was dominated by Pseudomonas and Fusobacteria. Furthermore, results showed that an obvious decrease in diversity in the DTB-A and DTB-M mixed treatment group. In addition, the migratory aggregation of DTB molecules in plants was observed by fluorescence imaging. Overall, these findings extend our understanding of the mechanism of effect of luminescent materials on submerged macrophytes and their periphytic microorganisms.


Subject(s)
Biofilms , Hydrocharitaceae , Biofilms/drug effects , Biofilms/growth & development , Hydrocharitaceae/metabolism , Hydrocharitaceae/microbiology , Benzaldehydes/metabolism , Benzaldehydes/pharmacology , Photosynthesis/drug effects , Luminescence , Catalase/metabolism , Peroxidase/metabolism , Plant Leaves/metabolism , Superoxide Dismutase/metabolism , Luminescent Agents/metabolism
5.
Inorg Chem ; 63(22): 10443-10451, 2024 Jun 03.
Article in English | MEDLINE | ID: mdl-38774973

ABSTRACT

Long-term in situ plasma membrane-targeted imaging is highly significant for investigating specific biological processes and functions, especially for the imaging and tracking of apoptosis processes of cells. However, currently developed membrane probes are rarely utilized to monitor the in situ damage of the plasma membrane. Herein, a transition-metal complex phosphorescent indicator, Ru-Chol, effectively paired with cholesterol, exhibits excellent properties on staining the plasma membrane, with excellent antipermeability, good photostability, large Stokes shift, and long luminescence lifetime. In addition, Ru-Chol not only has the potential to differentiate cancerous cells from normal cells but also tracks in real time the entire progression of cisplatin-induced plasma membrane damage and cell apoptosis. Therefore, Ru-Chol can serve as an efficient tool for the monitoring of morphological and physiological changes in the plasma membrane, providing assistance for drug screening and early diagnosis and treatment of diseases, such as immunodeficiency, diabetes, cirrhosis, and tumors.


Subject(s)
Cell Membrane , Cholesterol , Coordination Complexes , Ruthenium , Humans , Ruthenium/chemistry , Cholesterol/chemistry , Cholesterol/analysis , Cell Membrane/chemistry , Cell Membrane/metabolism , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Coordination Complexes/pharmacology , Apoptosis/drug effects , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Cisplatin/pharmacology , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Molecular Structure
6.
Colloids Surf B Biointerfaces ; 239: 113975, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38762934

ABSTRACT

Early and accurate cancer diagnosis is crucial for improving patient survival rates. Luminescent nanoparticles have emerged as a promising tool in fluorescence bioimaging for cancer diagnosis. To enhance diagnostic accuracy, ligands promoting endocytosis into cancer cells are commonly incorporated onto nanoparticle surfaces. Folic acid (FA) is one such ligand, known to specifically bind to folate receptors (FR) overexpressed in various cancer cells such as cervical and ovarian carcinoma. Therefore, surface modification of luminescent nanoparticles with FA can enhance both luminescence efficiency and diagnostic accuracy. In this study, luminescent europium-doped hydroxyapatite (EuHAp) nanocrystals were prepared via hydrothermal method and subsequently modified with (3-Aminopropyl)triethoxysilane (APTES) followed by FA to target FR-positive human cervical adenocarcinoma cell line (HeLa) cells. The sequential grafting of APTES and then FA formed a robust covalent linkage between the nanocrystals and FA. Rod-shaped FA-modified EuHAp nanocrystals, approximately 100 nm in size, exhibited emission peaks at 589, 615, and 650 nm upon excitation at 397 nm. Despite a reduction in photoluminescence intensity following FA modification, fluorescence microscopy revealed a remarkable 120-fold increase in intensity compared to unmodified EuHAp, attributed to the enhanced uptake of FA-modified EuHAp. Additionally, confocal microscope observations confirmed the specificity and the internalization of FA-modified EuHAp nanocrystals in HeLa cells. In conclusion, the modification of EuHAp nanocrystals with FA presents a promising strategy to enhance the diagnostic potential of cancer bioimaging probes.


Subject(s)
Durapatite , Europium , Folic Acid , Nanoparticles , Humans , Folic Acid/chemistry , Europium/chemistry , Nanoparticles/chemistry , HeLa Cells , Durapatite/chemistry , Luminescence , Microscopy, Fluorescence , Propylamines/chemistry , Particle Size , Luminescent Agents/chemistry
7.
Anal Chem ; 96(22): 9236-9243, 2024 Jun 04.
Article in English | MEDLINE | ID: mdl-38767294

ABSTRACT

The early detection of nonalcoholic fatty liver disease (NAFLD) through bioluminescent probes is of great significance. However, there remains a challenge to apply them in nontransgenic natural animals due to the lack of exogenous luciferase. To address this issue, we herein report a new strategy for in situ monitoring of endogenous hydrogen sulfide (H2S) in the liver of NAFLD mice by leveraging a H2S-responsive bioluminescent probe (H-Luc) combined with firefly luciferase (fLuc) mRNA delivery. The probe H-Luc was created by installing a H2S recognition moiety, 2,4-dinitrophenol, onto the luciferase substrate (d-luciferin), which is allowed to release cage-free d-luciferin in the presence of H2S via a nucleophilic aromatic substitution reaction. In the meantime, the intracellular luciferase was introduced by lipid nanoparticle (LNP)-mediated fLuc mRNA delivery, rendering it suitable for bioluminescence (BL) imaging in vitro and in vivo. Based on this luciferase-luciferin system, the endogenous H2S could be sensitively and selectively detected in living cells, showing a low limit of detection (LOD) value of 0.72 µM. More importantly, after systematic administration of fLuc mRNA-loaded LNPs in vivo, H-Luc was able to successfully monitor the endogenous H2S levels in the NAFLD mouse model for the first time, displaying a 28-fold higher bioluminescence intensity than that in the liver of normal mice. We believe that this strategy may shed new light on the diagnosis of inflammatory liver disease, further elucidating the roles of H2S.


Subject(s)
Hydrogen Sulfide , Luciferases, Firefly , Luminescent Measurements , Non-alcoholic Fatty Liver Disease , RNA, Messenger , Animals , Non-alcoholic Fatty Liver Disease/metabolism , Hydrogen Sulfide/metabolism , Hydrogen Sulfide/analysis , Luciferases, Firefly/genetics , Luciferases, Firefly/metabolism , Mice , RNA, Messenger/metabolism , RNA, Messenger/administration & dosage , Humans , Luminescent Agents/chemistry , Nanoparticles/chemistry , Mice, Inbred C57BL
8.
Luminescence ; 39(5): e4779, 2024 May.
Article in English | MEDLINE | ID: mdl-38769873

ABSTRACT

Carbon dots have attracted widespread attention due to their excellent optical properties and so on and are therefore used in various fields such as anti-counterfeiting. There are many reports on carbon dot-based room-temperature phosphorescent materials, but there are still fewer reports on carbon dot-based room-temperature phosphorescent materials with time-dependent color-changing properties. In this work, a time-dependent color-changing carbon dot-based room-temperature phosphorescent material with the ability to change from green to blue was successfully prepared by a simple one-pot heating method using hydroxyurea as the only raw material. In this process, hydroxyurea is used as both a carbon and nitrogen source, and in the process of material formation, hydroxyurea also partially forms cyanuric acid as a matrix to make the carbon dots uniformly dispersed in it. By blending the ratio of the dual emission centers of the carbon dots themselves, the final effect of time-dependent color-changing is achieved by taking advantage of the intensity changes and color differences of each emission center. The present work provides new ideas for the preparation of time-dependent color-changing carbon dot-based room-temperature phosphorescent materials.


Subject(s)
Carbon , Color , Quantum Dots , Temperature , Carbon/chemistry , Quantum Dots/chemistry , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Time Factors
9.
Luminescence ; 39(5): e4751, 2024 May.
Article in English | MEDLINE | ID: mdl-38666358

ABSTRACT

This study describes the luminous properties of Pb5(PO4)3Br doped with RE3+ (RE = Dy3+, Eu3+ and Tb3+) synthesised using the solid-state method. The synthesised phosphor was characterised using Fourier-transform infrared, X-ray diffraction, scanning electron microscopy and photoluminescence measurements. Dy3+-doped Pb5(PO4)3Br phosphor exhibited blue and yellow emissions at 480 and 573 nm, respectively, on excitation at 388 nm. Eu3+-doped Pb5(PO4)3Br phosphor exhibited orange and red emissions at 591 and 614 nm, respectively, on excitation at λex = 396 nm. Pb5(PO4)3Br:Tb3+ phosphor exhibited the strongest green emission at 547 nm on excitation at λex = 380 nm. Additionally, the effect of the concentration of rare-earth ions on the emission intensity of Pb5(PO4)3Br:RE3+ (RE3+ = Dy3+, Eu3+ and Tb3+) phosphors was investigated.


Subject(s)
Europium , Luminescence , Luminescent Agents , Europium/chemistry , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Terbium/chemistry , Phosphates/chemistry , Luminescent Measurements , X-Ray Diffraction , Lead/chemistry
10.
Talanta ; 274: 126000, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38608630

ABSTRACT

Luminescent ß-diketonate-europium(III) complexes have been found a wide range of applications in time-gated luminescence (TGL) bioassays, but their poor water solubility is a main problem that limits their effective uses. In this work we propose a simple and general strategy to enhance the water solubility of luminescent ß-diketonate-europium(III) complexes that permits facile synthesis and purification. By introducing the fluorinated carboxylic acid group into the structures of ß-diketone ligands, two highly water-soluble and luminescent Eu3+ complexes, PBBHD-Eu3+ and CPBBHD-Eu3+, were designed and synthesized. An excellent solubility exceeding 20 mg/mL for PBBHD-Eu3+ was found in a pure aqueous buffer, while it also displayed strong and long-lived luminescence (quantum yield φ = 26%, lifetime τ = 0.49 ms). After the carboxyl groups of PBBHD-Eu3+ were activated, the PBBHD-Eu3+-labeled streptavidin-bovine serum albumin (SA-BSA) conjugate was prepared, and successfully used for the immunoassay of human α-fetoprotein (AFP) and the imaging of an environmental pathogen Giardia lamblia under TGL mode, which demonstrated the practicability of PBBHD-Eu3+ for highly sensitive TGL bioassays. The carboxyl groups of PBBHD can also be easily derivatized with other reactive chemical groups, which enables PBBHD-Eu3+ to meet diverse requirements of biolabeling technique, to provide new opportunities for developing functional europium(III) complex biolabels serving for TGL bioassays.


Subject(s)
Europium , Solubility , Water , Europium/chemistry , Water/chemistry , Humans , Luminescent Measurements/methods , Serum Albumin, Bovine/chemistry , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Giardia lamblia/drug effects , Luminescence , Animals , Biological Assay/methods , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Streptavidin/chemistry , Time Factors , Cattle , Keto Acids/chemistry
11.
Inorg Chem ; 63(18): 8320-8328, 2024 May 06.
Article in English | MEDLINE | ID: mdl-38660721

ABSTRACT

Histidine plays an essential role in most biological systems. Changes in the homeostasis of histidine and histidine-rich proteins are connected to several diseases. Herein, we report a water-soluble Cu(II) coordination polymer, labeled CuCP, for the fluorimetric detection of histidine and histidine-rich proteins and peptides. Single-crystal structure determination of CuCP revealed a two-dimensional wavy network structure in which a carboxylate group connects the individual Cu(II) dimer unit in a syn-anti conformation. The weakly luminescent and water-soluble CuCP shows turn-on blue emission in the presence of histidine and histidine-rich peptides and proteins. The polymer can also stain histidine-rich proteins via gel electrophoresis. The limits of quantifications for histidine, glycine-histidine, serine-histidine, human serum albumin (HSA), bovine serum albumin, pepsin, trypsin, and lysozyme were found to be 300, 160, 600, 300, 600, 800, 120, and 290 nM, respectively. Utilizing the fluorescence turn-on property of CuCP, we measured HSA quantitatively in the urine samples. We also validated the present urinary HSA measurement assay with existing analytical techniques. Job's plot, 1H NMR, high-resolution mass spectrometry (HRMS), electron paramagnetic resonance (EPR), fluorescence, and UV-vis studies confirmed the ligand displacement from CuCP in the presence of histidine.


Subject(s)
Copper , Histidine , Peptides , Proteins , Water , Copper/chemistry , Copper/analysis , Histidine/chemistry , Histidine/analysis , Histidine/urine , Humans , Water/chemistry , Peptides/chemistry , Proteins/chemistry , Proteins/analysis , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Solubility , Polymers/chemistry , Cattle , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Animals
12.
Anal Chem ; 96(18): 6978-6985, 2024 May 07.
Article in English | MEDLINE | ID: mdl-38652863

ABSTRACT

Drug-induced liver injury (DILI) is a common liver disease with a high rate of morbidity, and its pathogenesis is closely associated with the overproduction of highly reactive hypochlorite (ClO-) in the liver. However, bioluminescence imaging of endogenous hypochlorite in nontransgenic natural mice remains challenging. Herein, to address this issue, we report a strategy for imaging ClO- in living cells and DILI mice by harnessing a bioluminescent probe formylhydrazine luciferin (ClO-Luc) combined with firefly luciferase (fLuc) mRNA-loaded lipid nanoparticles (LNPs). LNPs could efficiently deliver fLuc mRNA into living cells and in vivo, expressing abundant luciferase in the cytoplasm in situ. In the presence of ClO-, probe ClO-Luc locked by formylhydrazine could release cage-free d-luciferin through oxidation and follow-up hydrolysis reactions, further allowing for bioluminescence imaging. Moreover, based on the luciferase-luciferin system, it was able to sensitively and selectively detect ClO- in vitro with a limit of detection of 0.59 µM and successfully monitor the endogenous hypochlorite generation in the DILI mouse model for the first time. We postulate that this work provides a new method to elucidate the roles of ClO- in related diseases via bioluminescence imaging.


Subject(s)
Chemical and Drug Induced Liver Injury , Hypochlorous Acid , Liposomes , Luciferases, Firefly , Luminescent Measurements , Nanoparticles , RNA, Messenger , Animals , Hypochlorous Acid/metabolism , Mice , Nanoparticles/chemistry , Luciferases, Firefly/genetics , Luciferases, Firefly/metabolism , Chemical and Drug Induced Liver Injury/metabolism , Chemical and Drug Induced Liver Injury/diagnostic imaging , RNA, Messenger/metabolism , RNA, Messenger/genetics , Luminescent Agents/chemistry , Humans , Lipids/chemistry , Optical Imaging
13.
Biosens Bioelectron ; 256: 116236, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38608494

ABSTRACT

Au nano-clusters (Au NCs) were promising electrochemiluminescence (ECL) nano-materials. However, the small size of Au NCs presented a challenge in terms of their immobilization during the construction of an ECL biosensing platform. This limitation significantly hindered the wider application of Au NCs in the ECL field. In this work, we successfully used the reducibility of Ti3C2 to fabricate in situ a self-enhanced nano-probe Ti3C2-TiO2-Au NCs. The strategy of in situ generation not only improved the immobilization of Au NCs on the probe but also eliminated the requirement of adding reducing agents during preparation. In addition, in situ generated TiO2 could serve as a co-reaction accelerator, shortening the electron transfer distance between S2O82- and Au NCs, thereby improving the utilization of intermediates and enhancing the ECL response of Au NCs. The constructed ECL sensing platform could achieve sensitive detection of polynucleotide kinase (PNK). At the same time, the 5'-end phosphate group of DNA phosphorylation could chelate with a large amount of Ti on the surface of Ti3C2, thereby achieving the goal of specific detection of PNK. The sensor based on self-enhanced ECL probes had a broad dynamic range spanning for PNK detection from 10.0 to 1.0 × 107 µU mL-1, with a limit of detection of 1.6 µU mL-1. Moreover, the ECL sensor showed satisfactory detection performance in HeLa cell lysate and serum. This study not only provided insights for addressing the issue of ECL luminescence efficiency in Au NCs but also presented novel concepts for ECL self-enhancement strategies.


Subject(s)
Biosensing Techniques , Gold , Limit of Detection , Luminescent Measurements , Polynucleotide 5'-Hydroxyl-Kinase , Titanium , Titanium/chemistry , Biosensing Techniques/methods , Humans , Luminescent Measurements/methods , Gold/chemistry , Polynucleotide 5'-Hydroxyl-Kinase/analysis , Electrochemical Techniques/methods , Metal Nanoparticles/chemistry , Luminescent Agents/chemistry
14.
Luminescence ; 39(3): e4705, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38445417

ABSTRACT

In this work, we present the synthesis of a green-emitting series of BaGd2 ZnO5 :xHo3+ (0.5-3 mol%) phosphors using a high-temperature solid-state reaction method. Phase purity and crystal structure information were evaluated through X-ray powder diffraction patterns. Optical properties were examined through diffuse reflectance spectra, revealing that the prepared phosphor exhibited a band gap of 4.65 eV. The effect of Ho3+ doping on the morphology and ion distribution on the surface was assessed using scanning electron microscopy and time-of-flight secondary ion mass spectrometry techniques, respectively. The excitation spectra of the synthesized phosphor exhibited a charge transfer band and strong absorption transitions. The emission spectra displayed typical holmium emission characteristics, featuring a strong green emission band associated with f-f transitions from 5 F4 + 2 S2 → 5 I8 . Decay dynamics of the synthesized phosphor exhibited a single-exponential decay pattern, with lifetimes ranging from 0.103 to 0.053 ms. The intrinsic radiative lifetime, calculated through Auzel's fitting was determined to be 0.14 ms. Using the emission spectra, colorimetric behaviour was analyzed, revealing that the Commission Internationale de l'éclairage (CIE) coordinates exclusively lay within the green region at (0.285, 0.705), with an impressive colour purity of 99.6%. Given these marked properties, the synthesized phosphor exhibits great potential for a wide range of green-emitting applications, including displays, white light-emitting diodes, and security signage.


Subject(s)
Luminescent Agents , Zinc Oxide , Colorimetry , Lighting , Microscopy, Electron, Scanning
15.
Angew Chem Int Ed Engl ; 63(21): e202319780, 2024 May 21.
Article in English | MEDLINE | ID: mdl-38523406

ABSTRACT

Tumor-associated macrophages (TAMs) play a role in both pro- and anti-tumor functions; and the targeted polarization from M2 to M1 TAMs has become an effective therapy option. Although detection of M1 TAMs is imperative to assess cancer immunotherapeutic efficacy, existing optical probes suffer from shallow tissue penetration depth and poor specificity toward M1 TAMs. Herein, we report a tandem-locked NIR chemiluminescent (CL) probe for specific detection of M1 TAMs. Through a combined molecular engineering approach via both atomic alternation and introduction of electron-withdrawing groups, near-infrared (NIR) chemiluminophores are screened out to possess record-long emission (over 800 nm), record-high CL quantum yield (2.7 % einstein/mol), and prolonged half-life (7.7 h). Based on an ideal chemiluminophore, the tandem-locked probe (DPDGN) is developed to only activate CL signal in the presence of both tumour (γ-glutamyl transpeptidase) and M1 macrophage biomarkers (nitric oxide). Such a tandem-lock design ensures its high specificity towards M1 macrophages in the tumor microenvironment over those in normal tissues or peripheral blood. Thus, DPDGN permits noninvasive imaging and tracking of M1 TAM in the tumor of living mice during R837 treatment, showing a good correlation with ex vivo methods. This study not only reports a new molecular approach towards highly efficient chemiluminophores but also reveals the first tandem-locked CL probes for enhanced imaging specificity.


Subject(s)
Tumor-Associated Macrophages , Animals , Mice , Optical Imaging , Humans , Luminescent Agents/chemistry , Luminescent Measurements
16.
Chembiochem ; 25(9): e202400094, 2024 May 02.
Article in English | MEDLINE | ID: mdl-38488304

ABSTRACT

Phosphorescent iridium(III) complexes are widely recognized for their unique properties in the excited triplet state, making them crucial for various applications including biological sensing and imaging. Most of these complexes display single phosphorescence emission from the lowest-lying triplet state after undergoing highly efficient intersystem crossing (ISC) and ultrafast internal conversion (IC) processes. However, in cases where these excited-state processes are restricted, the less common phenomenon of dual emission has been observed. This dual emission phenomenon presents an opportunity for developing biological probes and imaging agents with multiple emission bands of different wavelengths. Compared to intensity-based biosensing, where the existence and concentration of an analyte are indicated by the brightness of the probe, the emission profile response involves modifications in emission color. This enables quantification by utilizing the intensity ratio of different wavelengths, which is self-calibrating and unaffected by the probe concentration and excitation laser power. Moreover, dual-emissive probes have the potential to demonstrate distinct responses to multiple analytes at separate wavelengths, providing orthogonal detection capabilities. In this concept, we focus on iridium(III) complexes displaying fluorescence-phosphorescence or phosphorescence-phosphorescence dual emission, along with their applications as biological probes for sensing and imaging.


Subject(s)
Coordination Complexes , Iridium , Iridium/chemistry , Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Humans , Biosensing Techniques/methods , Optical Imaging , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Animals , Luminescent Measurements , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis
17.
Luminescence ; 39(3): e4718, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38501347

ABSTRACT

The structural, surface morphological, optical absorption and emission features of Y2 O3 :Ce (0%-5%) were studied. The samples had a body-centred cubic crystal structure. The undoped sample had a crystallite size of 29.03 nm, and it varied after doping with Ce. The grain size of the samples varied from 23.00 to 50.78 nm. All the samples exhibited a strong absorption band at 206 nm due to F-centre absorption and absorption involving the delocalised bands. In addition, the doped samples exhibited a secondary band at ~250 nm due to 4f → 5d transitions of Ce3+ ions. The optical bandgap of the undoped sample was found to be ~5.37 eV, and it decreased to 5.20 eV with an increase in Ce concentration to 5%. The undoped sample under 350-nm excitation exhibited a broad photoluminescence (PL) emission band with the maxima at 406 nm and a secondary band at 463 nm. In contrast, multiple PL peaks were centred at ~397, 436, 466, 488 and 563 nm in all the doped samples. The average lifetime of the emission band at 406 nm was 1.05 ns and that of the emission band at ~466 nm was 1.63 ns. The material has potential for solid-state lighting applications.


Subject(s)
Azocines , Benzhydryl Compounds , Lighting , Luminescent Agents
18.
Macromol Rapid Commun ; 45(11): e2400045, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38365211

ABSTRACT

Non-traditional intrinsic luminescent (NTIL) polymer is an emerging field, and its color-tunable modification is highly desirable but still rarely investigated. Here, a click chemistry approach for the color-tunable modifications of NTIL polymers by introducing clickable polymerization-induced emission luminogen (PIEgen), is demonstrated. Through Cu-catalyzed azide-alkyne cycloaddition click chemistry, a series of PIEgens is successful prepared, which is further polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Interestingly, after clickable modification, these monomers are nonemissive in both solution and aggregation states; while, the corresponding polymers exhibit intriguing aggregation-induced emission (AIE) characteristics, confirming their PIEgen characteristics. By varying alkynyl substitutions, color-tunable NTIL polymers are achieved with emission wavelength varying from 448 to 498 nm, revealing a series of PIEgens and verifying the importance of modification of NTIL polymers. Further luminescence energy transfer application is carried out as well. This work therefore designs a series of clickable PIEgens and opens a new avenue for the modification of NTIL polymers via click chemistry, which may cause inspirations to the research fields including luminescent polymer, NTIL, click chemistry, AIE and modification.


Subject(s)
Click Chemistry , Color , Luminescence , Polymerization , Polymers , Polymers/chemistry , Polymers/chemical synthesis , Molecular Structure , Catalysis , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Azides/chemistry , Alkynes/chemistry
19.
Luminescence ; 39(1): e4555, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37461122

ABSTRACT

A green phosphor Sr2 ZnGe2 O7 :Mn2+ with a melilite structure was prepared using a high-temperature solid-state reaction. When the 535 nm emission was monitored, the excitation spectrum of the Sr2 ZnGe2 O7 :Mn2+ was found to contain two excitation bands in the ultraviolet (UV) region. When excited by UV light, the sample shows bright green emission at 535 nm, which corresponds to the distinctive transition of Mn2+ (4 T1 →6 A1 ). Moreover, the quantum efficiency of Sr2 ZnGe2 O7 :Mn2+ could reach 67.6%. Finally, a high-performance white-light-emitting diode (WLED) with a low correlated colour temperature of 4632 K and a high colour rendering index (CRI) of 92.3 were packaged by coating commercial blue and red phosphors with an optimized Sr2 ZnGe2 O7 :Mn2+ sample on a 310 nm UV chip. This indicated that Sr2 ZnGe2 O7 :Mn2+ has the potential application as a green component in the WLED lighting field.


Subject(s)
Luminescent Agents , Luminescent Agents/chemistry , Green Light , Luminescence , Ultraviolet Rays
20.
Luminescence ; 39(1): e4591, 2024 Jan.
Article in English | MEDLINE | ID: mdl-37675627

ABSTRACT

Cerium has been widely used as a dopant in luminescent materials due to its unique electronic configurations. It is generally anticipated that the luminescence properties of rare-earth-doped materials are closely related to the local environment of activators, especially for Ce3+ . In addition, it is convenient to modulate its emission wavelength by adjusting the composition and structure. In this study, we systematically analyzed the microstructure of the Ce-doped CaYAlO4 system at atomic resolution. The quantitive results indicated that the structure distortion greatly influenced the valence state of the Ce dopant, which is critical to its luminescence efficiency. In addition, valence variations also exist from surface to inner structure due to the big distortion area around the surface. Our results unravel the interplay of local structure and valence transitions in Ce-doped aluminate phosphors, which has the potential to be applied in other luminescent materials.


Subject(s)
Cerium , Luminescent Agents , Metals, Rare Earth , Luminescence , Luminescent Agents/chemistry , Metals, Rare Earth/chemistry , Cerium/chemistry
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