Temperature-Induced Reversible Photoluminescence Switching and Ultraviolet-Pumped Light-Emitting Diode Applications of a Perovskite (C6H10N2)2MnCl6·2H2O Crystal.

Zero-dimensional (0D) organic-inorganic hybrid halides present many fascinating photophysical properties for promising optoelectronic applications such as light-emitting diodes (LEDs), X-ray imaging, photodetectors, and anticounterfeiting. Herein, a centimeter-sized single crystal (C6H10N2)2MnCl6·2H2O with a 0D perovskite structure was obtained via a solvent evaporation method. A bright red emission at 618 nm with a larger Stokes shift of more than 300 nm and a long fluorescence lifetime of 6.21 ms were measured. Notably, a reversible PL switching from red emission to nonluminescence has been presented in the cycles of heating-cooling processes from RT to 100 °C. Furthermore, the temperature-induced luminescence shows a quick recovery after 20 conversion cycles, exhibiting excellent stability and temperature sensing. According to the structural and theoretical analyses, the temperature-induced luminescence is primarily due to hydrogen-bonding interactions between (MnCl6)4- and H2O molecules. Particularly, a temperature anticounterfeiting application has been designed based on its reversible temperature-dependent PL switching. Importantly, the ultraviolet-pumped LEDs fabricated by (C6H10N2)2MnCl6·2H2O single crystals are perfectly achieved. Anyway, this work clearly demonstrates that 0D Mn-based perovskite with temperature-dependent PL switching greatly extends its potential applications in electro-optical display, temperature sensing, and anticounterfeiting devices.

Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s2 Lone Pairs and Trimethylammonium Cations.

Organic-inorganic hybrid metal halides have unique optical and electronic properties, which are advantageous in the study of nonlinear optical materials. To investigate the effect of stereoactive lone pair electrons and the induction of organic cations on the structure of hybrid antimony(III) halides on nonlinear optics, we synthesize two noncentrosymmetric hybrid antimony(III)-based halide single crystals (TMA)3Sb2X9 (TMA = NH(CH3)3+, X = Cl, Br) by a room-temperature slow evaporation method, and their single-crystal structures, phase transition, X-ray photoelectron spectroscopy, and energy-band structure calculations are studied. More importantly, second-harmonic generation results of (TMA)3Sb2X9 (X = Cl, Br) are about 0.7 and 0.8 × KH2PO4(KDP), respectively. Interestingly, (TMA)3Sb2Cl9 single crystals undergo a reversible structural transition from Pc (No. 7) at room temperature to P21/c (No. 14) at 400 K, while the (TMA)3Sb2Br9 single crystals belong to the noncentrosymmetric space group R3c (No. 161), which clarifies the previous results. This work not only deepens the understanding of the role in lone pair electrons and organic cations in the structural induction in antimony-based halide perovskite materials but also provides guidance for subsequent nonlinear optical explorations.

Ultra-Broad-Band-Excitable Cu-Based Halide (C4H10N)4Cu4I8 with High Stability for LED Applications.

Currently, organic-inorganic hybrid cuprous-based halides are receiving substantial attention for their eco-friendliness, distinctive structures, and outstanding photophysical properties. Nevertheless, most of the reported cuprous-based halides demand deep ultraviolet excitation with a narrow excitation range that can meet the commercial requirement. Herein, zero-dimensional (0D) cuprous-based halide (C4H10N)4Cu4I8 single crystals (SCs) were synthesized, with an ultrabroad band excitation ranging 260-450 nm and a greenish-yellow emission band peaking at 560 nm. Excitingly, (C4H10N)4Cu4I8 also features a large Stokes shift of 300 nm, a high photoluminescence quantum yield (PLQY) of up to 84.66%, and a long lifetime of 137 µs. Furthermore, density functional theory calculations were performed to explore the relationship between structure and photophysical properties, and the photoluminescence performance of (C4H10N)4Cu4I8 originates from the electron interactions in [Cu2I4]2- clusters. Taking advantage of broad band excitation and excellent photoluminescent performances, a high luminescence characteristic UV-pumped light-emitting diode (LED) device with remarkable color stability was fabricated by employing the as-synthesized (C4H10N)4Cu4I8 SCs, which present the promising applications of low-dimensional cuprous-based halides in solid-state lighting.

Outstanding Circularly Polarized TADF in Chiral Cu(I) Emitters: From Design to Application in CP-TADF OLEDs.

Low-cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high-tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral-at-metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(-)-menthol-derived 1,10-phenanthroline ligand (L*). These complexes exhibit a yellow CP-TADF with a record-high quantum yield (close to 100%) and high dissymmetry factor (|glum| ~ 1×10-2). Remarkably, the above compounds also show a negative thermal-quenching (NTQ) of luminescence in the 300-77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP-TADF OLEDs displaying mirror-imaged CPL bands with high |gEL| factors of 1.5×10-2  and the maximum EQE of 6.15%. Equally important, using the (+)-[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP-TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low-cost and robust CP-TADF emitters.

High-precision wavelength measurement using a virtual Fizeau cavity.

Fizeau wavelength measurement plays an important role in the fields of laser technology, optical communication, and optical metrology. The accuracy of the traditional multistage Fizeau wavemeter is limited owing to the degradation of the stripe symmetry and finesse caused by variations in the cavity length. Herein, we propose a virtual Fizeau cavity (VFC) based on the principle of phase difference to address this issue. The principle analysis and simulation of this measurement system are presented, along with experiments that verified the feasibility and performance of the VFC method. The wavelength measurement accuracy of this system is superior to 60 MHz in the 350-1100 nm wavelength range. The design concept of "virtual-real combined" cavities first proposed in this paper to our knowledge introduces possibilities for the development of high-accuracy Fizeau wavelength measurements.

Thermal/Water-Induced Phase Transformation and Photoluminescence of Hybrid Manganese(II)-Based Chloride Single Crystals.

Mn(II)-based hybrid halides have attracted great attention from the optoelectronic fields due to their nontoxicity, special luminescent properties, and structural diversity. Here, two novel organic-inorganic hybrid Mn(II)-based halide single crystals (1-mpip)MnCl4·3H2O and (1-mpip)2MnCl6 (1-mpip = 1-methylpiperazinium, C5H14N2+) were grown by a slow evaporation method in ambient atmosphere. Interestingly, (1-mpip)2MnCl6 single crystals exhibit the green emission with a PL peak at 522 nm and photoluminescence quantum yields (PLQYs) of ≈5.4%, whereas (1-mpip)MnCl4·3H2O single crystals exhibit no emission characteristics. More importantly, there exists a thermal-induced phase transformation from (1-mpip)MnCl4·3H2O to emissive (1-mpip)2MnCl6 at 372 K. Moreover, a reversible luminescent conversion between (1-mpip)MnCl4·3H2O and (1-mpip)2MnCl6 was simply achieved when heated to 383 K and placed in a humid environment or sprayed with water. This work not only deepens the understanding of the thermal-induced phase transformation and humidity-sensitive luminescent conversion of hybrid Mn(II)-based halides, but also provides a guidance for thermal and humidity sensing and anticounterfeiting applications of these hybrid materials.

Salivary microbiome and metabolome analysis of severe early childhood caries.

BACKGROUND: Severe early childhood caries (SECC) is an inflammatory disease with complex pathology. Although changes in the oral microbiota and metabolic profile of patients with SECC have been identified, the salivary metabolites and the relationship between oral bacteria and biochemical metabolism remains unclear. We aimed to analyse alterations in the salivary microbiome and metabolome of children with SECC as well as their correlations. Accordingly, we aimed to explore potential salivary biomarkers in order to gain further insight into the pathophysiology of dental caries. METHODS: We collected 120 saliva samples from 30 children with SECC and 30 children without caries. The microbial community was identified through 16S ribosomal RNA (rRNA) gene high-throughput sequencing. Additionally, we conducted non-targeted metabolomic analysis through ultra-high-performance liquid chromatography combined with quadrupole time-of-flight mass spectrometry to determine the relative metabolite levels and their correlation with the clinical caries status. RESULTS: There was a significant between-group difference in 8 phyla and 32 genera in the microbiome. Further, metabolomic and enrichment analyses revealed significantly altered 32 salivary metabolites in children with dental caries, which involved pathways such as amino acid metabolism, pyrimidine metabolism, purine metabolism, ATP-binding cassette transporters, and cyclic adenosine monophosphate signalling pathway. Moreover, four in vivo differential metabolites (2-benzylmalate, epinephrine, 2-formaminobenzoylacetate, and 3-Indoleacrylic acid) might be jointly applied as biomarkers (area under the curve = 0.734). Furthermore, the caries status was correlated with microorganisms and metabolites. Additionally, Spearman's correlation analysis of differential microorganisms and metabolites revealed that Veillonella, Staphylococcus, Neisseria, and Porphyromonas were closely associated with differential metabolites. CONCLUSION: This study identified different microbial communities and metabolic profiles in saliva, which may be closely related to caries status. Our findings could inform future strategies for personalized caries prevention, detection, and treatment.

Carbon Nitride with Rationally Designed π-Conjugated Structure for Bright Blue-Violet Light-Emitting Diodes.

Carbon nitride consisting of the broken π-conjugated structure (bc-CN) is designed as the emitting layer in a blue-violet light emitting diode (LED). The bc-CN is prepared by a metal-oxide (MgO) template-assisted method, in which the low reaction temperature and nano MgO jointly control the degree of polymerization to form cyano groups and broken π-conjugation in the bc-CN nanosheets (bc-CN NS) which emit intense blue-violet photoluminescence at 412 nm. The broken π-conjugated heptazine-ring structure in the bc-CN NS mitigates non-radiation energy loss and promotes the d*-LP transition. As a result, a high quantum efficiency of 73.1% is achieved. The excellent dispersing ability of the bc-CN NS enables solution-based fabrication of the light emitting diode (LED). The LED exhibits intense electroluminescence of 236 cd m-2 at 412 nm with an external quantum efficiency of 0.46%. The broken π-conjugation modulates the optical properties of the polymerized carbon nitride semiconductor giving rise to intense blue-violet electroluminescence, which is very desirable for printable and wide-color-gamut display devices.

One-step electrodeposition preparation of polyaniline/f-MWCNTs as electrochemical sensors for detection of 10-hydroxycamptothecine.

In our work, one-step electro-deposition method was adopted to produce polyaniline (PANI) and functional multiwalled carbon nanotubes (f-MWCNTs) films on glass carbon electrodes, and the modified electrodes were applied as an electrochemical sensor for determination of 10-hydroxycamptothecine (10-HCPT). The f-MWCNTs were handled by ultrasound processing in concentrated oxidizing acid solution, which can obtain a wonderful dissolution in water and attach new functional groups, such as -COOH and -OH. Then, aniline monomer could polymerize on the surface easily. The surface characterization was investigated using various techniques including scanning electron microscope, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, and electro-catalytic properties were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Under optimal conditions, the resulting of PANI/f-MWCNTs sensor showed a wide linear range (3 × 10-9 to 7 × 10-7 mol L-1 ) and a low detection limit (1 × 10-9 mol L-1 ), which is attributing to its large special surface area and good conductivity. Moreover, the modified electrodes are convenient to fabricate, which can be used to detect 10-HCPT in urine samples successfully.

A sandwich-configuration electrochemiluminescence immunoassay based on Cu2O@OMC-Ru nanocrystals and OMC-MoS2 nanocomposites for determination of alpha-fetoprotein.

A sandwich-format electrochemiluminescence (ECL) immunosensor has been developed for alpha-fetoprotein (AFP) detection based on the use of ordered mesoporous carbon-molybdenum disulfide (OMC-MoS2) as a sensor platform and cuprous oxide @ ordered mesoporous carbon-Ru(bpy)32+ (Cu2O@OMC-Ru) composites as signal tags. OMC alongside MoS2 plays a synergistic role in improving the electrochemical performance of the electrode in the electron transfer process. The uniform cubic-shaped Cu2O@OMC-Ru nanocrystals display excellent luminous efficiency, with a signal amplification strategy of OMC-MoS2 synergistic enhancement and Cu2O@OMC which is capable of immobilizing more Ru(bpy)32+ serving as a tracing tag to label antibodies. A detectable ECL emission at a Cu2O@OMC-Ru nanocrystals modified electrode is initiated at an applied voltage of +1.15 V (scanning range: 0-1.2 V), in the presence of the tripropylamine (TPA) as coreactant. With the increase in AFP concentration, the loading of Cu2O@OMC-Ru at the electrode increases. Afterward, the ECL detection of AFP shows a wide linear range from 0.1 pg/mL to 10 ng/mL with a correlation coefficient of 0.9964 and a detection limit of 0.011 pg/mL (S/N = 3) under the optimal experimental conditions. The recoveries were in the range 91.2-97.1% with RSD varying from 4.8 to 8.5%. Overall, the novel immunosensor has been successfully applied to the analysis of human serum samples, indicating a great potential for application in clinical diagnostics.

Analysis of material concentration in step-index fibers with alumina cores produced by means of the powder-in-tube technique.

Step-index fibers (SIFs) with alumina cores were fabricated employing the powder-in-tube technique. The fabricated SIFs have alumina concentrations of up to 32 mol%, which is the highest value reported so far for fibers with core diameters smaller than 25 µm. The mixing mechanisms between alumina and silica during fiber drawing were revealed by energy dispersive X-ray analysis of the neck-down area of the preform. The results of the measurements and simulations indicate that besides diffusion, fluid dynamics between softened silica and alumina powder also play an important role in the resulting alumina and silica concentrations in the fiber. The influence of different drawing parameters on the alumina and silica concentrations of the fibers is also presented.

MnO2/rGO/CNTs Framework as a Sulfur Host for High-Performance Li-S Batteries.

Lithium-sulfur batteries are very promising next-generation energy storage batteries due to their high theoretical specific capacity. However, the shuttle effect of lithium-sulfur batteries is one of the important bottlenecks that limits its rapid development. Herein, physical and chemical dual adsorption of lithium polysulfides are achieved by designing a novel framework structure consisting of MnO2, reduced graphene oxide (rGO), and carbon nanotubes (CNTs). The framework-structure composite of MnO2/rGO/CNTs is prepared by a simple hydrothermal method. The framework exhibits a uniform and abundant mesoporous structure (concentrating in ~12 nm). MnO2 is an α phase structure and the α-MnO2 also has a significant effect on the adsorption of lithium polysulfides. The rGO and CNTs provide a good physical adsorption interaction and good electronic conductivity for the dissolved polysulfides. As a result, the MnO2/rGO/CNTs/S cathode delivered a high initial capacity of 1201 mAh g-1 at 0.2 C. The average capacities were 916 mAh g-1, 736 mAh g-1, and 547 mAh g-1 at the current densities of 0.5 C, 1 C, and 2 C, respectively. In addition, when tested at 0.5 C, the MnO2/rGO/CNTs/S exhibited a high initial capacity of 1010 mAh g-1 and achieved 780 mAh g-1 after 200 cycles, with a low capacity decay rate of 0.11% per cycle. This framework-structure composite provides a simple way to improve the electrochemical performance of Li-S batteries.

Fast measurement of the laser beam quality factor based on phase retrieval with a liquid lens.

In this paper, a new method for measuring the beam quality (M2) of lasers based on phase retrieval with a liquid lens is proposed. With intensity profiles obtained under different focal lengths in a certain position, a variable-focus iterative retrieval algorithm is established for the reconstruction of the complex amplitude. Then M2 can be calculated with the angular spectrum theory. Feasibility of the proposed method is demonstrated with single- and multimode lasers through both simulations and experiments. Compared with the traditional liquid lens method, the M2 of lasers can be measured faster with the proposed method.

Suppressing the influence of charge-coupled device vertical blooming on the measurement of laser beam quality factor (M2) of a near-infrared laser.

In this paper, a new method, which is based on reconstructing the original intensity distribution of a laser with images captured by a charge-coupled device (CCD) in two orthogonal directions, is proposed for suppressing the influence of CCD vertical blooming on the measurement of the laser beam quality factor (M2). A simplified theoretical model for the distribution of CCD blooming is also proposed. With the proposed method and model, the influence of CCD vertical blooming on the measurement of M2 is simulated. The experimental results demonstrate that the new method can be an effective means to measure the M2 of a near-infrared laser with a silicon CCD camera. The proposed method can be applied to a beam quality analyzer in order to suppress the influence of blooming on the measurement of M2.

Heat suppression of the fiber coating on a cladding light stripper in high-power fiber laser.

We present a theoretical model for the thermal effect of the fiber coating on a high-power cladding light stripper, which is fabricated by chemical etching. For the input and output of the fiber coating, a novel segmented corrosion method and increasing attenuation method are proposed for heat suppression, respectively. The relationship between the attenuation and temperature rise of the fiber coating at the output is experimentally demonstrated. The temperature distribution of the fiber coating at the input as well as the return light power caused by scattering are measured for the etched fiber with different surface roughness values. The results suggest that the rise in temperature is primarily caused by the scattering light propagating into the coating. Finally, an attenuation of 27 dB is achieved. At a room temperature of 23°C and input pump power of 438 W, the highest temperature of the input fiber coating decreases from 39.5°C to 27.9°C by segmented corrosion, and the temperature rise of the output fiber coating is close to 0.

Determination of the laser beam quality factor (M2) by stitching quadriwave lateral shearing interferograms with different exposures.

A complete complex amplitude reconstruction method for the determination of the laser beam quality factor M2 based on the multiple exposure of a quadriwave lateral shearing interferometer (QWLSI) is presented. The theoretical analysis and simulation of the influence of the information in the small signal area on the calculation of the M2 factor is provided. The experimental results demonstrate that the new method can be an accurate means to measure the M2 factor. The proposed method can avoid the influence of phase inaccuracy in the small signal area of the interferogram, during the measurement of the M2 factor.

Characterization of novel MSX1 variants causally associated with non-syndromic oligodontia in Chinese families.

BACKGROUND: MSX1 (OMIM #142983) is crucial to normal dental development, and variants in MSX1 are associated with dental anomalies. The objective of this study was to characterize the pathogenicity of novel MSX1 variants in Chinese families with non-syndromic oligodontia (NSO). METHODS: Genomic DNA was extracted from individuals representing 35 families with non-syndromic oligodontia and was analyzed by Sanger sequencing and whole-exome sequencing. Pathogenic variants were screened via analyses involving PolyPhen-2, Sorting-Intolerant from Tolerant, and MutationTaster, and conservative analysis of variants. Patterns of MSX1-related NSO were analyzed. MSX1 structural changes suggested functional consequences in vitro. RESULTS: Three previously unreported MSX1 heterozygous variants were identified: one insertion variant (c.576_577insTAG; p.Gln193*) and two missense variants (c. 871T>C; p.Tyr291His and c. 644A>C; p.Gln215Pro). Immunofluorescence analysis revealed abnormal subcellular localization of the p.Gln193* MSX1 variant. In addition, we found that these MSX1 variants likely lead to the loss of second premolars. CONCLUSION: Three novel MSX1 variants were identified in Chinese Han families with NSO, expanding the MSX1 variant spectrum and presenting a genetic origin for the pathogenesis detected in patients and their families.

Tuning the structure of N-methyldiethanolamine-based deep eutectic solvents for efficient and reversible SO2 capture.

Three cheap DESs comprising of N-methyldiethanolamine (MDEA) and imidazole (Im), 1,2,4-triazole, and tetrazole were investigated for capturing SO2 at low concentrations. Surprisingly, with the addition of Im, the SO2 absorption capacity and desorption efficiency were improved. Spectroscopic analysis and quantum chemical calculations confirmed that MDEA-Im effectively and reversibly captured SO2 through the hydrogen bond network and synergistic action between MDEA and Im.

Efficient Single-Phase Tunable Dual-Color Luminescence with High Quantum Yield Greater than 100% for Information Encryption and LED Applications.

In modern society, the investigation of highly efficient photoluminescent bulk materials with excitation-induced tunable multicolor luminescence and multiexciton generation (MEG) is of great significance to information security and the application of optoelectronic devices. In this study, two bulk Cu-based halide crystals of (C4H10NO)4Cu2Br5·Br and (C4H10NO)4Cu2I5·I·H2O, respectively, with one-dimensional structures were grown by a solvent evaporation method. Unexpectedly, (C4H10NO)4Cu2I5·I·H2O displayed excitation-induced tunable dual-color luminescence; one band is a brilliant green-yellow emission centered at 547 nm with a high photoluminescence quantum yield (PLQY) of up to 169.67%, and the other is a red emission at 695 nm with a PLQY of 75.76%. Just as importantly, (C4H10NO)4Cu2Br5·Br exhibits a strong broadband green-yellow emission at 561 nm under broad band excitation ranging from 252 to 350 nm, a long PL decay lifetime of 106.9 µs, and an ultrahigh PLQY of 198.22%. These materials represent the first two examples of 1D bulk crystals and Cu(I)-based halides that have a PLQY exceeding 100%. Combining the unusual luminescence characteristics with theoretical calculations reveals that MEG contributes to the green-yellow emission with ultrahigh PLQY > 100%, and that the red emission can be ascribed to [Cu2I5]3- cluster-centered emission. Additionally, an information encryption method was designed based on the Morse Code. The high luminescence characteristics of LED devices fabricated using the (C4H10NO)4Cu2Br5·Br and (C4H10NO)4Cu2I5·I·H2O crystals appear to lead to promising applications in solid-state lighting. This work extends the catalog of high-performance luminescent materials and also promotes application prospects of low-dimensional copper-based halides in optoelectronics.

A novel PAX9 variant in a Chinese family with non-syndromic oligodontia and genotype-phenotype analysis of PAX9variants.

OBJECTIVES: This study aimed to identifyPAX9variants in non-syndromic tooth agenesis families of China, as well as to analyze the genotype⁃phenotype of non-syndromic tooth agenesis caused by PAX9variants, which can provide a basis for the genetic diagnosis of tooth agenesis. METHODS: We collected the data of 44 patients with non-syndromic oligodontia who underwent treatment at Stomatological Hospital of Hebei Medical University between 2018 and 2023. Whole-exome sequencing was performed on the peripheral blood of the proband and its core family members, and the variants were verified by Sanger sequencing. Pathogenicity analysis and function prediction of the variants were performed using bioinformatics tools. The correlation between the genotype of PAX9 variant and its corresponding phenotype was examined by reviewing 55 publications retrieved from PubMed. The studies involved 232 tooth agenesis patients with PAX9 variants. RESULTS: A novel PAX9 c.447delG (p.Pro150Argfs*62) and a reported PAX9 c.406C>T (p.Gln136*) were identified in two Chinese families. Through bioinformatics analysis and three-dimensional structural modeling, we postulated that the frameshift variant was pathogenic. The outcome was the premature cessation of PAX9 protein, which caused severe structural and functional deficiencies. Summarizing the PAX9 genotype-phenotype relationship revealed that patients carrying the PAX9 variant commonly led to loss of the second molars. CONCLUSIONS: We identified the novel PAX9 c.447delG (p.Pro150Argfs*62) in a Chinese family of non-syndromic oligodontia, expanding the known variant spectrum of PAX9. The most susceptible tooth position for PAX9 variants of tooth agenesis was the second molars and the deciduous molars during the deciduous dentition.