Mn2+ and Sb3+ Codoped Cs2ZnCl4 Metal Halide with Excitation-Wavelength-Dependent Emission for Fluorescence Anticounterfeiting.

In recent years, there has been a growing demand for luminescence anticounterfeiting materials that possess the properties of environmentally friendly, single-component, and multimode fluorescence. Among the materials explored, the low dimensional metal halides have gained wide attention because of unique characteristics including low toxicity, simple synthesis, good stability, and so on. Here, we synthesized Mn2+ and Sb3+ codoped Cs2ZnCl4 single crystals by a facile hydrothermal method. Under 365 nm excitation, the codoped compound exhibits dual-band emissions at 530 and 730 nm. However, under 316 nm excitation, the compound only shows one emission band from 500 to 850 nm peaking at 730 nm, while under 460 nm excitation, the emission from 500 to 650 nm with an emission peak at 530 nm can be observed. Based on the study of the photoluminescence mechanism, the green and red emissions originate from the Mn2+ located in the tetrahedron and self-trapped exciton emission of [SbCl4]- clusters, respectively. Due to the zero-dimensional structure of the Cs2ZnCl4 host, there is minimal energy transfer between these dopants. Consequently, the luminous ratios of the two emissions can be independently regulated. Except by tuning the dopant concentrations, the Cs2ZnCl4:Mn2+, Sb3+ demonstrates excitation-wavelength-dependent properties, which could emit more than two colors with the change of excitation wavelength. As a result, multimode anticounterfeiting based on Cs2ZnCl4:Mn2+, Sb3+ crystals has been designed, which aligns with the requirements of environmentally friendly, single-component, and multimode fluorescence properties.

Bright Triplet Self-Trapped Excitons to Dopant Energy Transfer in Halide Double-Perovskite Nanocrystals.

For inorganic semiconductor nanostructure, excitons in the triplet states are known as the "dark exciton" with poor emitting properties, because of the spin-forbidden transition. Herein, we report a design principle to boost triplet excitons photoluminescence (PL) in all-inorganic lead-free double-perovskite nanocrystals (NCs). Our experimental data reveal that singlet self-trapped excitons (STEs) experience fast intersystem crossing (80 ps) to triplet states. These triplet STEs give bright green color emission with unity PL quantum yield (PLQY). Furthermore, efficient energy transfer from triplet STEs to dopants (Mn2+) can be achieved, which leads to white-light emitting with 87% PLQY in both colloidal and solid thin film NCs. These findings illustrate a fundamental principle to design efficient white-light emitting inorganic phosphors, propelling the development of illumination-related applications.

Wavelength-tunable narrow-linewidth gaseous Raman laser.

Gaseous Raman lasers cover a range of wavelengths but lack wavelength tunability. Here, a 1cm-1 linewidth 532 nm laser was used as a pump laser, and with a narrow-linewidth seed laser injection, a narrow-linewidth first Stokes (S1) Raman laser was achieved. By tuning the wavelength of the seed laser, a tuning range of S1 up to 1cm-1 was obtained. The wavelengths of the first anti-Stokes and second Stokes lasers could also be tuned. A theoretical model was developed, and spectral profiles of Raman lasers from experiments and simulations agreed well; further simulation predicted that the linewidth of S1 could be compressed to as narrow as 0.01cm-1 under optimal conditions. A universal method of fine-tunable Raman lasers is presented that can be utilized in several important applications.

Improving the Stability of UV-Cured Materials by the Radical Scavenger Loaded into Halloysite Nanotubes.

We prepared a new size-stable UV-cured material by loading a radical scavenger, 4-methoxyphenol (MEHQ), into halloysite nanotubes (HNTs) to improve the size-stability of UV-cured products. Loading the MEHQ into halloysite nanotubes was intended to protect the curing reaction from the typical inhibitive influence of a radical scavenger. After the curing process, heating treatment was performed on the cured products to accelerate the release of MEHQ from the halloysite lumen. The Brunauer-Emmett-Teller tests and transmission electron micrographs showed that MEHQ was successfully loaded into the halloysite lumen. The photopolymerization kinetic curves of composites revealed that adding the MEHQ-loaded halloysite nanotubes (HNTs-M) into UV-cured materials enabled faster photopolymerization rate than adding a simple mixture of HNTs and MEHQ. With MEHQ loaded in HNTs, the inhibition influence of MEHQ could be reduced. The results of the size-stability test showed that composites with HNTs-M underwent lower deformation during daily use than neat cured materials. In particular, the volume shrinkage of the composites with 8 wt% HNTs-M in daily use was decreased by 51.3%. The results of the release experiment showed that the release rate of MEHQ could be increased through heating treatment. This method may be used to improve the size-stability of UV-curable materials in the future.

Investigation on the mechanisms of scorpion venom in hepatocellular carcinoma model mice via untargeted metabolomics profiling.

Metabolic reprogramming is frequently accompanied by hepatocellular carcinoma (HCC) progression. Disrupted metabolites act as potential biomarkers and drug therapeutic targets for HCC. Peptide extract of scorpion venom (PESV) induces cytotoxic anti-proliferative effects and apoptosis in tumors. However, the action mechanisms of PESV remain unknown. This study aimed to explore the serum metabolic profiles of tumor-bearing mouse model. We generated an orthotopic HCC xenograft mouse model by implanting H22 cells into the left hepatic lobe of male C57BL/6 mice. After surgery, the mice were assigned to two groups randomly: PESV (PESV-treated 40 mg/kg daily, i.g.; n = 6) and control (treated with the solvent equally for 14 d, n = 6) groups. Based on an untargeted metabolomics approach using ultra-high-performance liquid chromatography/quadrupole time-of-flight mass spectrometry, differential metabolites were screened via univariate and multivariate data analyses. A total of 48 differential metabolites in negative ion mode and 63 in positive ion mode were identified in the serum samples. Furthermore, metabolic pathway analysis revealed that aminoacyl-tRNA biosynthesis, amino acid pathway, glutathione metabolism, protein transports, protein digestion and absorption, and cAMP signaling pathways play vital roles in PESV-induced inhibition of tumors. These findings highlight the distinct changes in the metabolic profiles of HCC-bearing mice after PESV treatment, suggesting the potential of the identified metabolic molecules as therapeutic targets for HCC.

Chemical transformation mechanism for blue-to-green emitting CsPbBr3 nanocrystals.

Recently, metal-halide perovskites have rapidly emerged as efficient light emitters with near-unity quantum yield and size-dependent optical and electronic properties, which have attracted considerable attention from researchers. However, the ultrafast nucleation rate of ionic perovskite counterparts severely limits the in-depth exploration of the growth mechanism of colloidal nanocrystals (NCs). Herein, we used an inorganic ligand nitrosonium tetrafluoroborate (NOBF4) to trigger a slow post-synthesis transformation process, converting non-luminescent Cs4PbBr6 NCs into bright green luminescent CsPbBr3 NCs to elucidate the concrete transformation mechanism via four stages: (i) the dissociation of pristine NCs, (ii) the formation of Pb-Br intermediates, (iii) low-dimensional nanoplatelets (NPLs) and (iv) cubic CsPbBr3 NCs, corresponding to the blue-to-green emission process. The desorption and reorganization of organic ligands induced by NO+ and the involvement of BF4- in the ligand exchange process played pivotal roles in this dissolution-recrystallization of NCs. Moreover, controlled shape evolution from anisotropic NPLs to NCs was investigated through variations in the amount of NOBF4. This further validates that additives exert a decisive role in the symmetry and growth of nanostructured perovskite crystals during phase transition based on the ligand-exchange mechanism. This finding serves as a source of inspiration for the synthesis of highly luminescent CsPbBr3 NCs, providing valuable insights into the chemical mechanism in post-synthesis transformation.

Thermodynamic behavior of correlated electron-hole fluids in van der Waals heterostructures.

Coupled two-dimensional electron-hole bilayers provide a unique platform to study strongly correlated Bose-Fermi mixtures in condensed matter. Electrons and holes in spatially separated layers can bind to form interlayer excitons, composite Bosons expected to support high-temperature exciton condensates. The interlayer excitons can also interact strongly with excess charge carriers when electron and hole densities are unequal. Here, we use optical spectroscopy to quantitatively probe the local thermodynamic properties of strongly correlated electron-hole fluids in MoSe2/hBN/WSe2 heterostructures. We observe a discontinuity in the electron and hole chemical potentials at matched electron and hole densities, a definitive signature of an excitonic insulator ground state. The excitonic insulator is stable up to a Mott density of ~0.8 × 1012 cm-2 and has a thermal ionization temperature of ~70 K. The density dependence of the electron, hole, and exciton chemical potentials reveals strong correlation effects across the phase diagram. Compared with a non-interacting uniform charge distribution, the correlation effects lead to significant attractive exciton-exciton and exciton-charge interactions in the electron-hole fluid. Our work highlights the unique quantum behavior that can emerge in strongly correlated electron-hole systems.

Self-trapped exciton engineering for white-light emission in colloidal lead-free double perovskite nanocrystals.

Intrinsic broadband photoluminescence (PL) of self-trapped excitons (STEs) are systematically studied in lead-free double perovskite nanocrystals (NCs). It is clarified that bandgap (direct/indirect) has important influence on the PL properties of STEs: indirect bandgap NCs exhibit strong exciton-phonon coupling which results in non-radiative STEs, while direct bandgap NCs exhibit moderate exciton-phonon coupling, inducing bright STE PL. Furthermore, by alloying K+ and Li+ ions in Cs2AgInCl6 NCs, the NCs exhibit broadband white-light emission. Charge-carrier dynamics study indicates that the efficient white-light emission originates from the further suppressed non-radiative processes of the STEs in the direct bandgap structure. This work may deepen the understanding of STEs and guide the design of high-performance lead-free perovskites.