Double Perovskite Single Crystals with High Laser Irradiation Stability for Solid-State Laser Lighting and Anti-counterfeiting.

Laser lighting devices, comprising an ultraviolet (UV) laser chip and a phosphor material, have emerged as a highly efficient approach for generating high-brightness light sources. However, the high power density of laser excitation may exacerbate thermal quenching in conventional polycrystalline or amorphous phosphors, leading to luminous saturation and the eventual failure of the device. Here, for the first time, we raise a single-crystal (SCs) material for laser lighting considering the absence of grain boundaries that scatter electrons and phonons, achieving high thermal conductivity (0.81 W m-1 K-1) and heat-resistance (575 °C). The SCs products exhibit a high photoluminescence quantum yield (89%) as well as excellent stability toward high-power lasers (>12.41 kW/cm2), superior to all previously reported amorphous or polycrystalline matrices. Finally, the laser lighting device was fabricated by assembling the SC with a UV laser chip (50 mW), and the device can maintain its performance even after continuous operation for 4 h. Double perovskite single crystals doped with Yb3+/Er3+ demonstrated multimodal luminescence with the irradiation of 355 and 980 nm lasers, respectively. This characteristic holds significant promise for applications in spectrally tunable laser lighting and multimodal anticounterfeiting.

Stereo-Hindrance Engineering of A Cation toward <110>-Oriented 2D Perovskite with Minimized Tilting and High-Performance X-Ray Detection.

2D <100>-oriented Dion-Jacobson or Ruddlesden-Popper perovskites are widely recognized as promising candidates for optoelectronic applications. However, the large interlayer spacing significantly hinders the carrier transport. <110>-oriented 2D perovskites naturally exhibit reduced interlayer spacings, but the tilting of metal halide octahedra is typically serious and leads to poor charge transport. Herein, a <110>-oriented 2D perovskite EPZPbBr4 (EPZ = 1-ethylpiperazine) with minimized tilting is designed through A-site stereo-hindrance engineering. The piperazine functional group enters the space enclosed by the three [PbBr6]4- octahedra, pushing Pb─Br─Pb closer to a straight line (maximum Pb─Br─Pb angle ≈180°), suppressing the tilting as well as electron-phonon coupling. Meanwhile, the ethyl group is located between layers and contributes an extremely reduced effective interlayer distance (2.22 Å), further facilitating the carrier transport. As a result, EPZPbBr4 simultaneously demonstrates high µτ product (1.8 × 10-3 cm2 V-1) and large resistivity (2.17 × 1010 Ω cm). The assembled X-ray detector achieves low dark current of 1.02 × 10-10 A cm-2 and high sensitivity of 1240 µC Gy-1 cm-2 under the same bias voltage. The realized specific detectivity (ratio of sensitivity to noise current density, 1.23 × 108 µC Gy-1 cm-1 A-1/2) is the highest among all reported perovskite X-ray detectors.

Covalent drugs based on small molecules and peptides for disease theranostics.

Biomacromolecules, such as proteins, nucleic acids and polysaccharides, are widely distributed in the human body, and some of them have been recognized as the targets of drugs for disease theranostics. Drugs typically act on targets in two ways: non-covalent bond and covalent bond. Non-covalent bond-based drugs have some disadvantages, such as structural instability and environmental sensitivity. Covalent interactions between drugs and targets have a longer action time, higher affinity and controllability than non-covalent interactions of conventional drugs. With the development of artificial intelligence, covalent drugs have received more attention and have been developed rapidly in pharmaceutical research in recent years. From the perspective of covalent drugs, this review summarizes the design methods and the effects of covalent drugs. Finally, we discuss the application of covalent peptide drugs and expect to provide a new reference for cancer treatment.

Infrared Evanescent Wave Sensing Based on a Ge10As30Se40Te20 Fiber for Alcohol Detection.

Infrared evanescent wave sensing based on chalcogenide fiber is an emerging technology for qualitative and quantitative analysis of most organic compounds. Here, a tapered fiber sensor made from Ge10As30Se40Te20 glass fiber was reported. The fundamental modes and intensity of evanescent waves in fibers with different diameters were simulated with COMSOL. The 30 mm length tapered fiber sensors with different waist diameters, 110, 63, and 31 µm, were fabricated for ethanol detection. The sensor with a waist diameter of 31 µm has the highest sensitivity of 0.73 a.u./% and a limit of detection (LoD) of 0.195 vol.% for ethanol. Finally, this sensor has been used to analyze alcohols, including Chinese baijiu (Chinese distilled spirits), red wine, Shaoxing wine (Chinese rice wine), Rio cocktail, and Tsingtao beer. It is shown that the ethanol concentration is consistent with the nominal alcoholicity. Moreover, other components such as CO2 and maltose can be detected in Tsingtao beer, demonstrating the feasibility of its application in detecting food additives.

Growth mechanism of metal halide perovskite single crystals in solution.

Metal halide perovskite (MHP) single crystals (SCs) have been demonstrated to have significant potential in photodetectors and photovoltaic devices due to their exceptional optoelectronic properties. The most promising approach for large-scale fabrication of high-quality MHP SCs is the synthesis of MHP SCs in solution. To explain the mechanism and guide the crystal growth process, the classical nucleation-growth theory was established. However, it mainly focuses on zone melting systems and does not account for the interaction between perovskite and solvent. In this review, we specifically focus on the difference in the growth mechanism between MHP SCs in solution and traditional SCs synthesized by the melting method, which includes a discussion of the dissolution, nucleation, and growth processes. We then summarize recent advances in the preparation of MHP SCs based on the special growth mechanism of the perovskite system. The purpose of this review is to provide comprehensive information to offer targeted theoretical guidance as well as unified understanding for the preparation of high-quality MHP SCs in solution.

Cell membrane-specific self-assembly of peptide nanomedicine induces tumor immunogenic death to enhance cancer therapy.

Immunogenic cell death (ICD), as an unusual cell death pattern, mediates cancer cells to release a series of damage-associated molecular patterns (DAMPs), and is widely used in the field of cancer immunotherapy. Injuring the cell membrane can serve as a novel ICD initiation strategy. In this study, a peptide nanomedicine (PNpC) is designed using the fragment CM11 of cecropin, which is effective in disrupting cell membranes because of its α-helical structure. PNpC self-assembles in situ in the presence of high levels of alkaline phosphatase (ALP) on the tumor cell membrane, transforming from nanoparticles to nanofibers, which reduces the cellular internalization of the nanomedicine and increases the interaction between CM11 and tumor cell membranes. Both in vitro and in vivo results indicate that PNpC plays a significant role in killing tumor cells by triggering ICD. The ICD induced by the destruction of the cancer cell membrane is accompanied by the release of DAMPs, which promotes the maturation of DCs and facilitates the presentation of tumor-associated antigens (TAA), resulting in the infiltration of CD8+ T cells. We believe that PNpC can trigger ICD while killing cancer cells, providing a new reference for cancer immunotherapy.

High Refractive Index GRIN Lens for IR Optics.

Infrared gradient refractive index (GRIN) material lenses have attracted much attention due to their continuously varying refractive index as a function of spatial coordinates in the medium. Herein, a glass accumulation thermal diffusion method was used to fabricate a high refractive index GRIN lens. Six Ge17.2As17.2SexTe(65-x) (x = 10.5-16) glasses with good thermal stability and high refractive index (n@10 µm > 3.1) were selected for thermal diffusion. The refractive index span (∆n) of 0.12 was achieved in this GRIN lens. After thermal diffusion, the lens still had good transmittance (45%) in the range of 8-12 µm. Thermal imaging confirmed that this lens can be molded into the designed shape. The refractive index profile was indirectly characterized by the structure and composition changes. The structure and composition variation became linear with the increase in temperature from 260 °C to 270 °C for 12 h, indicating that the refractive index changed linearly along the axis. The GRIN lens with a high refractive index could find applications in infrared optical systems and infrared lenses for thermal imaging.

High Verdet Constant Glass for Magnetic Field Sensors.

Due to the high transparency, high Verdet constant, as well as easy processing properties, rare-earth ion-doped glasses have demonstrated great potential in magneto-optical (MO) applications. However, the variation in the valence state of rare-earth ions (Tb3+ to Tb4+) resulted in the decreased effective concentration of the paramagnetic ions and thus degraded MO performance. Here, a strategy was proposed to inhibit the oxidation of Tb3+ into Tb4+ as well as improve the thermal stability by tuning the optical basicity of glass networks. Moreover, the depolymerization of the glass network was modulated to accommodate more Tb ions. Thus, a record high effective concentration (14.19 × 1021/cm3) of Tb ions in glass was achieved, generating a high Verdet constant of 113 rad/(T·m) at 650 nm. Lastly, the first application of MO glass for magnetic field sensors was demonstrated, achieving a sensitivity of 0.139 rad/T. We hope our work provides guidance for the fabrication of MO glass with high performance and thermal stability and could push MO glass one step further for magnetic sensing applications.

Visualization of X-rays with an Ultralow Detection Limit via Zero-Dimensional Perovskite Scintillators.

X-rays play an extremely significant role in medical diagnosis, safety testing, scientific research, and other practical applications. However, as the main sources of radioactive pollution, the hazard of X-rays to human health and the environment has been a major concern. Herein, the explored perovskite scintillator of Cs2Zr1-xPbxCl6 in this work exhibits an ultrahigh radioluminescence intensity owing to the enhanced X-ray absorption for the introduction of Pb2+ ions. The Cs2Zr1-xPbxCl6 crystals are demonstrated as efficient scintillators with a self-trapped exciton emission and extremely high steady-state light yield (∼101,944 photons meV-1). This fascinating scintillator provides a convenient visual tool for X-ray detection even for an indoor lighting environment, reaching a low detection limit of ∼14.2 nGy·s-1, which is about 1/387 of the typical medical imaging dose (5.5 µGy·s-1). Moreover, X-ray imaging with a high resolution of 16.6 lp·mm-1 is achieved with the as-explored Cs2Zr1-xPbxCl6 scintillator film. Herein, the Cs2Zr1-xPbxCl6 scintillator provides a feasible strategy for X-ray monitoring in the field of biomedicine, high-energy physics, national security, and other applications.

Flexible and robust low-loss selenium-based multimaterial infrared fibers towards CO2 laser ablation.

A small-scale delivery medium for CO2 laser energy with stable performance, flexibility, and high-strength is crucial in extreme laser processing environments, especially for minimally invasive surgery in high-humidity, twisty and narrow channels. Here, flexible and robust multimaterial infrared fibers made of selenium-based chalcogenide glasses and thermoplastic polymer were developed with a low loss of 7.18 dB/m at 10.6 µm. The resulting fibers were capable of stably delivering single-mode CO2 laser with 0.42 W average power. Moreover, to achieve precise control over the fibers in the practical clinical environment, customized co-polymers of polyphenylene sulfone resin and polyvinylidene fluoride were used as the fiber built-in jackets. Consequently, the fibers exhibited hydrophobicity, thermostability, high tensile strength, and low bending stiffness. The results demonstrated that the fibers can be used to deliver CO2 laser energy for fabric cutting and bio-tissues ablation, making them attractive for CO2 laser material processing and minimally invasive laser surgery.

Optimizing Evanescent Efficiency of Chalcogenide Tapered Fiber.

Evanescent wave absorption-based mid-infrared chalcogenide fiber sensors have prominent advantages in multicomponent liquid and gas detection. In this work, a new approach of tapered-fiber geometry optimization was proposed, and the evanescent efficiency was also theoretically calculated to evaluate sensing performance. The influence of fiber geometry (waist radius (Rw), taper length (Lt), waist deformation) on the mode distribution, light transmittance (T), evanescent proportion (TO) and evanescent efficiency (τ) is discussed. Remarkably, the calculated results show that the evanescent efficiency can be over 10% via optimizing the waist radius and taper length. Generally, a better sensing performance based on tapered fiber can be achieved if the proportion of the LP11-like mode becomes higher or Rw becomes smaller. Furthermore, the radius of the waist boundary (RL) was introduced to analyze the waist deformation. Mode proportion is almost unchanged as the RL increases, while τ is halved. In addition, the larger the micro taper is, the easier the taper process is. Herein, a longer waist can be obtained, resulting in larger sensing area which increases sensitivity greatly.

Facile Melting-Crystallization Synthesis of Cs2NaxAg1-xInCl6: Bi Double Perovskites for White Light-Emitting Diodes.

Lead-free double perovskites (DPs) have outstanding luminescent properties, which make them excellent candidates for wide use in optoelectronics. Herein, a solvent-free melting-crystallization technique, which can produce kilogram-scale DP microcrystals (DP-MCs) in one batch, is invented to synthesize the Cs2NaxAg1-xInCl6: Bi (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) DP-MCs. The structure and composition analysis confirmed the products are pure Cs2NaxAg1-xInCl6 DP-MCs. Affected by Jahn-Teller distortion of AgCl6 octahedra, self-trapped excitons appear in the excited state, resulting in the broadband emission (400-850 nm) of Cs2Ag1-xNaxInCl6: Bi DP-MCs. The enhancement of the photoluminescence quantum yield can be realized by introducing Na+ to break the parity-forbidden transition in the Cs2AgInCl6 DP. Optimized Cs2Na0.4Ag0.6InCl6: Bi DP-MC phosphors combined with commercial blue and green phosphors were coated on ultraviolet chips (365 nm) to fabricate white light-emitting diodes (WLEDs) from warm white (2930 K) to cold white (6957 K). An ultrahigh color rendering index of 97.1 and a CCT of 5548 K as well as Commission Internationale de l'Eclairage color coordinates of (0.331, 0.339) have been demonstrated. This kilogram-scale synthesis technique could stimulate the industrial development of WLEDs for general lighting based on DP-MC phosphors.

An Ultrasound-Induced Self-Clearance Hydrogel for Male Reversible Contraception.

Nearly half of pregnancies worldwide are unintended mainly due to failure of contraception, resulting in negative effects on women's health. Male contraception techniques, primarily condoms and vasectomy, play a crucial role in birth control, but cannot be both highly effective and reversible at the same time. Herein, an ultrasound (US)-induced self-clearance hydrogel capable of real-time monitoring is utilized for in situ injection into the vas deferens, enabling effective contraception and noninvasive recanalization whenever needed. The hydrogel is composed of (i) sodium alginate (SA) conjugated with reactive oxygen species (ROS)-cleavable thioketal (SA-tK), (ii) titanium dioxide (TiO2), which can generate a specific level of ROS after US treatment, and (iii) calcium chloride (CaCl2), which triggers the formation of the hydrogel. For contraception, the above mixture agents are one-time injected into the vas deferens, which can transform from liquid to hydrogel within 160 s, thereby significantly physically blocking the vas deferens and inhibiting movability of sperm. When fertility is needed, a noninvasive remedial ultrasound can make TiO2 generate ROS, which cleaves SA-tK to destroy the network of the hydrogel. Owing to the recanalization, the refertility rate is restored to 100%. Meanwhile, diagnostic ultrasound (D-US, 22 MHz) can monitor the occlusion and recanalization process in real-time. In summary, the proposed hydrogel contraception can be a reliable, safe, and reversible male contraceptive strategy that addresses an unmet need for men to control their fertility.

Effect of Se on Structure and Electrical Properties of Ge-As-Te Glass.

The Ge-As-Te glass has a wide infrared transmission window range of 3-18 µm, but its crystallization tendency is severe due to the metallicity of the Te atom, which limits its development in the mid- and far-infrared fields. In this work, the Se element was introduced to stabilize the Ge-As-Te glass. Some glasses with ΔT ≥ 150 °C have excellent thermal stability, indicating these glasses can be prepared in large sizes for industrialization. The Ge-As-Se-Te (GAST) glasses still have a wide infrared transmission window (3-18 µm) and a high linear refractive index (3.2-3.6), indicating that the GAST glass is an ideal material for infrared optics. Raman spectra show that the main structural units for GAST glass are [GeTe4] tetrahedra, [AsTe3] pyramids, and [GeTe4Se4-x] tetrahedra, and with the decrease of Te content (≤50 mol%), As-As and Ge-Ge homopolar bonds appear in the glass due to the non-stoichiometric ratio. The conductivity σ of the studied GAST glasses decreases with the decrease of the Te content. The highest σ value of 1.55 × 10-5 S/cm is obtained in the glass with a high Te content. The activation energy Ea of the glass increases with the decrease of the Te content, indicating that the glass with a high Te content is more sensitive to temperature. This work provides a foundation for widening the application of GAST glass materials in the field of infrared optics.

Accelerating solid diffusion and suppressing phase transition in LiV3O8via calcium doping at lithium sites.

The phase transition of LiV3O8 from an α phase to a ß phase during the discharge/charge process leads to drastic structural change and rapid capacity decay, and the consequent sluggish Li+ solid-state diffusion results in a serious concentration polarization. Herein, Ca-doped LiV3O8 was rationally designed and synthesized to address these issues. The electrochemical behaviors of Ca-doped and undoped LiV3O8, together with their structural evolution and changes in the ion solid diffusion paths, are studied in detail. Calculations at the atomic scale have revealed that Ca doping effectively suppresses the undesired α-ß phase transition and stabilizes the structure of LiV3O8 during cycling. Moreover, the calcium dopant preferentially situated at lithium sites in LiV3O8 serves as a pillar to increase the interlayer distance and extend the electrochemically active (001) plane, and thus facilitates anisotropic Li+ diffusion. More importantly, the variable-cell Nudged-Elastic-Band (VCNEB) calculations indicate that the phase transformation was hindered by kinetic factors, not by thermodynamics. The dominant factors for the electrochemical performance of LiV3O8 were clarified, and valuable insights for LiV3O8 commercialization in lithium-ion batteries were provided.

A ratiometric fluorescent probe for determination of the anthrax biomarker 2,6-pyridinedicarboxylic acid based on a terbium(III)- functionalized UIO-67 metal-organic framework.

Terbium(III)-functionalized zirconium-based MOFs (Tb3+@UIO-67) were synthesized by doping Tb3+ into UIO-67 using a post-synthetic modification. The Tb3+@UIO-67 (solid or aqueous dispersion) shows only blue fluorescence (emission peaks at 420 nm) under an ultraviolet lamp (254 nm). Upon addition of 2,6-pyridinedicarboxylic acid (DPA; an anthrax biomarker), the color of the Tb3+@UIO-67 aqueous dispersion under an ultraviolet lamp changes from blue to green. This is mainly because DPA has a good sensitization effect on Tb3+. DPA can be determined by measurement of the ratio of the fluorescence intensities at 544 nm and 420 nm (excitation at 278 nm). The method allows DPA to be detected in the 0.3 to 6 µM concentration range, with a detection limit of 36 nM. Graphical abstract Schematic representation of a ratiometric fluorescent probe synthesized by doping terbium ions into a zirconium-based MOF (UIO-67) for determination of an anthrax biomarker.

Changes of gut microbiota during silybin-mediated treatment of high-fat diet-induced non-alcoholic fatty liver disease in mice.

AIM: Gut microbiota are involved in the pathogenesis of non-alcoholic fatty liver disease (NAFLD). Silybin (Sil), a naturally occurring hepatoprotective agent, is widely used for treating NAFLD. Whether Sil affects gut microbiota during its actions in treating NAFLD is unknown. We aimed to examine the effect of Sil on intestinal flora dysbiosis induced by a high-fat diet (HFD). METHODS: After 10 weeks of feeding normal chow diet or HFD, mice were given a daily gavage for 8 weeks. Cecal contents were harvested for study of short-chain fatty acids, bile acids, and gut microbiota alteration. RESULTS: Sil showed protective effects against dietary-induced obesity and liver steatosis; accordingly, gut microbiota composition changed. At the phylum level, compared with the HFD group, mice in the Sil-treated group had significantly lower levels of Firmicutes, and the ratio of Firmicutes-to-Bacteroidetes was lower (P < 0.05). At the genus level, the Sil-treated group have significantly lower levels of Lachnoclostridium, Lachnospiraceae_UCG-006, and Mollicutes_RF9, which were reported to be potentially related to diet-induced obesity, and increased levels of Blautia (P < 0.05), Akkermansia (P < 0.05), and Bacteroides (P < 0.05), which are known to have a beneficial effect on improving NAFLD. Sil also showed an inhibitory effect on well-known beneficial bacteria, such as Alloprevotella and Lactobacillus. Furthermore, the production of acetate, propionate, and butyrate increased, whereas the generation of formate and conversion of cytotoxic secondary metabolites (lithocholic acid and deoxy-cholic acid) decreased in mice treated with Sil. CONCLUSIONS: Sil might have beneficial effects on ameliorating NAFLD and mediating HFD-induced change of gut microbiota composition, followed by major changes in secondary metabolites, such as short-chain fatty acids and bile acids.

In situ and ex-situ physical scenario of the femtosecond laser-induced periodic surface structures.

Laser-induced periodic surface structures (LIPSS) are a universal phenomenon that can allow tailoring nanoelectronics and nanophotonics devices. However, there is an issue about the formation mechanism of LIPSS, and the current research mainly focuses on the formation process of the individual structures, such as the low spatial frequency LIPSS (LSFL), sub-wavelength structures, and laser-induced periodic annular surface structures (LIPASS). A whole process formation picture of the series of these periodic structures is still missing. In this study, a pump-probing setup is applied to ensure the real-time and in situ monitoring of surface modification under different pulse numbers. LSFL firstly appears on the surface after two laser shots, and then, laser-induced orthogonal periodic structures (LIOPS) become the dominant morphology after five laser shots, which result from the local field enhancement of the surface ripples. As the laser shots increase, the LSFL split leads to the formation of nanopillars, and the formation of the nanopillars under the surface LSFL (after ten laser shots) is due to the transition between the LSFL and HSFL with an orientation parallel to the laser polarization. A dip surrounded by annular periodic fringes after 50 laser shots is observed, which is due to the interference of the incident laser field and the reflected laser field on the crater surface. Finally, a direct writing technique for fabrication of nano-gratings is also reported.

Discovery of Dioxino[2,3-f]quinazoline derivative VEGFR-2 inhibitors exerting significant antipro-liferative activity in HUVECs and mice.

Twelve 2,3-dihydro-[1,4]-dioxino[2,3-f]quinazoline derivatives were designed and evaluated as vascular endothelial growth factor receptor 2 (VEGFR-2) inhibitors. The most half-maximal inhibitory concentration (IC50) values of them were less than 10 nM. Among these compounds, 13d displayed highly effective inhibitory activity against VEGFR-2 (IC50 = 2.4 nM) and excellent antiproliferative activities against human umbilical vein endothelial cells (HUVECs) (IC50 = 1.2 nM). When anti-tumor animal experiments were carried out in mice, the tumor almost disappeared (TGI = 133.0%) after six days of administration of 13d. Therefore, 13d was a potential and effective anticancer agent. The binding conformations were respectively compared between VEGFR-2 with 13d and leading compound lenvatinib, and shows that they have similar binding modes.

In-Situ and Ex-Situ Characterization of Femtosecond Laser-Induced Ablation on As2S3 Chalcogenide Glasses and Advanced Grating Structures Fabrication.

Femtosecond laser pulse of 800 nm wavelength and 150 fs temporal width ablation of As2S3 chalcogenide glasses is investigated by pump-probing technology. At lower laser fluence (8.26 mJ/cm²), the surface temperature dropping to the melting point is fast (about 43 ps), which results in a clean hole on the surface. As the laser fluence increases, it takes a longer time for lattice temperature to cool to the melting point at high fluence (about 200 ps for 18.58 mJ/cm², about 400 ps for 30.98 mJ/cm²). The longer time of the surface heating temperature induces the melting pool in the center, and accelerates material diffusing and gathering surrounding the crater, resulting in the peripheral rim structure and droplet-like structure around the rim. In addition, the fabricated long periodic As2S3 glasses diffraction gratings can preserve with high diffraction efficiency by laser direct writing technology.