Ultrathin BiOCl-OV/CoAl-LDH S-scheme heterojunction for efficient photocatalytic peroxymonosulfate activation to boost Co (IV)=O generation.

Sustainable and rapid production of high-valent cobalt-oxo (Co(IV)=O) species for efficiently removing organic pollutants is challenging in permoxymonosulfate (PMS) based advanced-oxidation-processes (AOPs) due to the limitation of the high 3d-orbital electronic occupancy of Co and slow conversion from Co(III) to Co(II). Herein, S-scheme BiOCl-OV/CoAl-LDH heterojunction were constructed by ultrathin BiOCl with the oxygen-vacancy (OV) self-assembled with ultrathin CoAl-LDH. OV promoted the formation of charge transfer channel (Bi-O-Co bonds) at the interface of the heterojunction and reduced electron occupation of the Co 3d-orbital to facilitate the generation of Co(IV)=O in the BiOCl-OV/CoAl-LDH/PMS/Visible-light system. S-scheme heterojunction accelerated the photogenerated electrons to allow rapid conversion of Co(III) to Co(II), promoting the fast two-electron transfer from Co(II) to Co(IV)=O. Consequently, the developed BiOCl-OV/CoAl-LDH/PMS/Visible-light system showed excellent degradation efficiency for most of organic pollutions, and exhibited very high removal capability for the actual industrial wastewater. This study provides a new insight into the evolution of Co(IV)=O and the coordinative mechanism for photocatalysis and PMS activation.

Circularly Polarized Luminescence Induced by Hydrogen-Bonding Networks in a One-Dimensional Hybrid Manganese(II) Chloride.

Chiral hybrid metal halides hold great potential as circularly polarized luminescence light sources. Herein, we have obtained two enantiomeric pairs of one-dimensional hybrid chiral manganese(II) chloride single crystals, R/S-(3-methyl piperidine)MnCl3 (R/S-1) and R/S-(3-hydroxy piperidine)MnCl3 (R/S-2), crystallizing in the non-centrosymmetric space group P212121. In comparison to R/S-1, R/S-2 single crystals not only show red emission with near-unity photoluminescence quantum yield (PLQY) and high resistance to thermal quenching but also exhibit circularly polarized luminescence with an asymmetry factor (glum) of 2.5×10-3, which can be attributed to the enhanced crystal rigidity resulting from the hydrogen bonding networks between R/S-(3-hydroxy piperidine) cations and [MnCl6]4- chains. The circularly polarized luminescence activities originate from the asymmetric [MnCl6]4- luminophores induced by N-H⋅⋅⋅Cl hydrogen bonding with R/S-(3-hydroxy piperidine). Moreover, these samples demonstrate great application potential in circularly polarized light-emitting diodes and X-ray scintillators. This work shows a highly efficient photoluminescent Mn-based halide and offers a strategy for designing multifunctional chiral metal halides.

First report of Rhizopus stolonifer causing flower rot of yellow passion fruit (Passiflora edulis f. flavicarpa Deg.) in China.

The genus Passiflora, commonly known as passion fruit, originated in South America, is an economically important horticulture crop and widely distributed in the tropics and subtropics. Yellow passion fruit (Passiflora edulis f. flavicarpa) and purple passion fruit (Passiflora edulis f. edulis) are the two most planted species (Santos-Jiménez et al., 2022), which have been largely cultivated in southern China. The average annual production reaches 600,000 tons, of which yellow fruit accounts for more than 70% (Zhou et al., 2022). In 2022 to 2023, a disease caused flower rot severely in passion fruit plantations. The incidence rate was generally 10% in purple passion fruit, with an incidence up to 60% in yellow passion fruit 'Qinmi No. 9'. Flower rot occurs mainly in the rainy season, especially during periods of prolonged rain. Infected flowers had black patches that were water-soaked on the interior of the flower bud. The patches covered the entire flower bud, and fluffy mycelium and sporangia developed, which caused the flower bud rotten and abscised easily. Five symptomatic flowers from Wuhua, Guangdong (23°23'N, 115°18'E) and 8 symptomatic flowers from Shangsi, Guangxi (21°15'N, 107°98'E) of 'Qinmi No. 9' were collected during flowering period in 2022 and 2023. Diseased flower pieces were surface-sterilized with 70% ethanol for 2 to 3 min, rinsed with sterile distilled water 3 times, and placed on PDA medium at 25℃ in darkness. Four and 6 fungal isolates with similar morphology were isolated from the infected samples of Wuhua and Shangsi, respectively. Two isolates, PRFJ01 from Wuhua and PRGX02 from Shangsi, were randomly selected for further study. Purified fungal colonies at the age of 3 days accompany with diffuse cottony mycelia, turned white to gray later. The mycelia were hyaline and aseptate. Sporangiophores with 0.56 (0.22~1.10) mm in length and 6.1 (3.18~10.87) µm in width (n=100) were erect, light brown, and had rhizoids and stolons at their bases. Sporangia with 48.0 (23.45~92.85) µm in diameter (n=100) were dark-colored, near spherical and having dark ovoid sporangiospores with 3.56 (2.34~6.39) µm × 2.82 (1.73~4.70) µm (n=100). The morphology of the fungus were identical to Rhizopus stolonifer (Ehrenb.) Vuill (Haque et al. 2023). The two isolates were molecularly identified using genomic regions of 28S large ribosomal subunit (LSU) with NL1 and LR3 primers (Cruz-Lachica et al., 2018). The phylogenetic trees revealed the sequences of PRFJ01 (OR801560.1) and PRGX02 (OR801561.1) were 100% and 99% identical to R. stolonifer (MK705761.1 and KC412868.1), respectively. Pathogenicity tests were conducted on healthy flowers and leaves of 5-month-old grafted 'Qinmi No. 9' plants. Mycelial plugs with 5-mm diameter were placed on the flowers and leaves. Three plants were performed for each of the isolates, and the test was repeated twice. The inoculated plants were moisturized with plastic bags. Healthy flowers and leaves inoculated with sterile PDA plugs were used as control. Typical symptoms were observed on inoculated plants after 2 days. The dark grey mycelia and sporangia covered the entire flower after 4 days inoculation. The flower bud became putrid and the flower stalk split off. Lesions on leaves expanded accompany with numerous aerial mycelium. However, the controls were symptomless. R. stolonifer was reisolated from inoculated tissues. Previously, flower rot on passion fruit caused by R. stolonifer has only been recorded in Brazil (Ploetz, 2003). To our knowledge, this is the first report of R. stolonifer causing flower rot on passion fruit in China.

Metal Halide Perovskite Nanocrystals for Near-Infrared Circularly Polarized Luminescence with High Photoluminescence Quantum Yield via Chiral Ligand Exchange.

Using ligand exchange on FAPbI3 perovskite nanocrystals (PNCs) surface with chiral tridentate l-cysteine (l-cys) ligand, we successfully prepared chiral FAPbI3 PNCs that show circularly polarized luminescence (CPL) (dissymmetry factor; glum = 2.1 × 10-3) in the near-infrared (NIR) region from 700 to 850 nm and a photoluminescence quantum yield (PLQY) of 81%. The chiral characteristics of FAPbI3 PNCs are ascribed to induction by chiral l/d-cys, and the high PLQY is attributed to the passivation of the PNCs defects with l-cys. Also, effective passivation of defects on the surface of FAPbI3 PNCs by l-cys results in excellent stability toward atmospheric water and oxygen. The conductivity of the l-cys treated FAPbI3 NC films is improved, which is attributed to the partial substitution of l-cys for the insulating long oleyl ligand. The CPL of the l-cys ligand treated FAPbI3 PNCs film retains a glum of -2.7 × 10-4. This study demonstrates a facile yet effective approach to generating chiral PNCs with CPL for NIR photonics applications.

Durability of neutralization against Omicron subvariants after vaccination and breakthrough infection.

Booster immunizations and breakthrough infections can elicit severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) Omicron subvariant neutralizing activity. However, the durability of the neutralization response is unknown. We characterize the sensitivity of BA.1, BA.2, BA.2.75, BA.4/BA.5, BF.7, BQ.1.1, and XBB against neutralizing antibodies from vaccination, hybrid immunity, and breakthrough infections 4-6 months after vaccination and infection. We show that a two-dose CoronaVac or a third-dose ZF2001 booster elicits limited neutralization against Omicron subvariants 6 months after vaccination. Hybrid immunity as well as Delta, BA.1, and BA.2 breakthrough infections induce long-term persistence of the antibody response, and over 70% of sera neutralize BA.1, BA.2, BA.4/BA.5, and BF.7. However, BQ.1.1 and XBB, followed by BA.2.75, are more resistant to neutralization, with neutralizing titer reductions of ∼9- to 41-fold, ∼16- to 63-fold, and ∼4- to 25-fold, respectively. These data highlight additional vaccination in CoronaVac- or ZF2001-vaccinated individuals and provide insight into the durability of neutralization against Omicron subvariants.

Synthesis and Properties of Stable Amino Metal Halide Molecular Clusters in the Solid State.

Nanosized molecular clusters (MCs) composed of PbBr2 and neutral ligand butylamine (BTYA) with unique optical properties in solution and solid states have been synthesized using ligand-assisted reprecipitation and spin-coating, separately. The studies of their optical properties using ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) show the first electronic absorption and PL band of the MCs at 401 and 411 nm, respectively, for the solution and solid state samples that exhibit good stability under ambient conditions. Low-temperature PL spectra below 30 K show vibronic peaks indicative of a single size or a very narrow size distribution of the MCs. On the basis of Raman, X-ray diffraction, and transmission electron microscopy measurements, a layered structural model is proposed for the MCs with a BTYA ligand capping on the surface of the corner-shared tilted [PbBr6]4- octahedral framework. The stable and retained structure of MCs in the solid state is promising for photonics applications.

Competing Energy Transfer in Two-Dimensional Mn2+-Doped BDACdBr4 Hybrid Layered Perovskites with Near-Unity Photoluminescence Quantum Yield.

Two-dimensional (2D) hybrid layered perovskites (HLPs) have attracted extensive attention due to their excellent optoelectronic properties. Herein, we successfully prepared high-quality Mn-doped BDACdBr4 (BDA = NH2(CH2)4NH2, butylene diammonium) HLP single crystals (SCs). The incorporation of Mn2+ ions modulates the electronic band structure of BDACdBr4 perovskites and tailors the energy transfer process of excited states. A near-unity photoluminescence (PL) quantum yield of 96% from the Mn2+ emission at 608 nm is achieved. Excitation wavelength-dependent spectroscopic characterizations help to clarify the energy transfer mechanism of Mn-doped BDACdBr4, in which competing PL from the 3Eg → 1A1g transition of Cd2+ and the 4T1(G) → 6A1(S) transition of Mn2+ dopants is observed. Temperature-dependent PL spectroscopic characterizations indicate that the efficient energy transfer from BDACdBr4 perovskite host to Mn2+ dopants requires thermal activation to overcome a potential barrier. This work provides new insight into the photophysics and optical properties of 2D HLPs, especially the influence of Mn2+ doping on competing energy transfer in hybrid luminescent materials.

Competing Energy Transfer-Modulated Dual Emission in Mn2+-Doped Cs2NaTbCl6 Rare-Earth Double Perovskites.

A2BIBIIIX6 double perovskites are promising materials due to their outstanding photoelectronic properties and excellent stability in the environment. Herein, we synthesized Mn2+:Cs2NaTbCl6 with dual emission through a solvothermal method for the first time. Mn2+:Cs2NaTbCl6 double perovskites exhibit excellent environmental stability and high photoluminescence quantum yields (PLQYs). The Cs2NaTbCl6 was successfully doped with Mn2+ in two modes: at Mn-feeding concentrations below 1%, Mn2+ first tend to insert into the interstitial void, but if the Mn-feeding concentration exceeds 1%, Mn2+ will further substitute Na+ site of the Cs2NaTbCl6 lattice and thus both two doping modes coexist. After Mn2+ doping, efficient energy transfer from the 5D4 level of Tb3+ ions to the 4T1 level of Mn2+ ions occurs, resulting in tunable dual emission from the Tb3+5D4 → 7FJ=6,5,4,3 transition and Mn2+4T1 → 6A1 transition. Further, LED based on the Mn2+:Cs2NaTbCl6 double perovskites exhibits excellent performance and stability. This work demonstrates a strategy to achieve novel lanthanide-based double perovskites with potential applications in photonics.

Modulating optical properties and interfacial electron transfer of CsPbBr3 perovskite nanocrystals via indium ion and chlorine ion co-doping.

In this work, we demonstrated an in situ approach for doping CsPbBr3 nanocrystals (NCs) with In3+ and Cl- with a ligand-assisted precipitation method at room temperature. The In3+ and Cl- co-doped NCs are characterized by the powder x-ray diffraction patterns, ultraviolet-visible, photoluminescence (PL) spectroscopy, time-resolved PL (TRPL), ultraviolet photoelectron spectroscopy, x-ray photoelectron spectroscopy, and transmission electron microscopy. Based on PL and TRPL results, the non-radiative nature of In3+-doping induced localized impurity states is revealed. Furthermore, the impact of In3+ and Cl- doping on charge transfer (CT) from the NCs to molecular acceptors was investigated and the results indicate that the CT at the interface of NCs can be tuned and promoted by In3+ and Cl- co-doping. This enhanced CT is attributed to the enlarged energy difference between relevant states of the molecular acceptor and the NCs by In3+ and Cl- upon co-doping. This work provides insight into how to control interfacial CT in perovskite NCs, which is important for optoelectronic applications.

Protein deubiquitylase USP3 stabilizes Aurora A to promote proliferation and metastasis of esophageal squamous cell carcinoma.

Aurora A kinase is a cell cycle regulator that is dysregulated in several different malignancies. Nevertheless, its regulatory mechanisms are still not fully understood. Here, we report that ubiquitin specific peptidase 3 (USP3) promotes proliferation and metastasis of esophageal squamous cell carcinoma (ESCC) cells by mediating deubiquitination of Aurora A. Analysis of human clinical samples indicated that USP3 and Aurora A are highly expressed in ESCC. Cellular experiments confirmed that high expression of USP3 and Aurora A in ESCC cells promoted malignant cell proliferation and invasion. In this mechanism, USP3 leads to suppression of Aurora A ubiquitination, resulting less proteasome degradation. We constructed the deubiquitinated mimetic K143R of Aurora A and found that K143R significantly promoted the proliferation and invasion of ESCC cells and was not regulated by the deubiquitination of USP3. Moreover, Aurora A K143R potentiated the kinase activity of Aurora A in ESCC cells. Thus, our findings demonstrate that the tumorigenic feature of ESCC is in part mediated by USP3-facilitated deubiquitination of Aurora A.

Enhanced Photoluminescence of All-Inorganic Manganese Halide Perovskite-Analogue Nanocrystals by Lead Ion Incorporation.

Herein, we develop an effective approach for incorporating lead (Pb) ions into manganese (Mn) halide perovskite-analogue nanocrystals (PA NCs) of CsMn(Cl/Br)3·2H2O via room-temperature supersaturation recrystallization. Pb2+-incorporated Mn-PA NCs exhibit strong orange emission upon UV light illumination, a peak centered at 600 nm assigned to Mn2+ transition (4T1g → 6A1g) with a photoluminescence quantum yield (PLQY) of 41.8% compared to the pristine Mn-PA NCs with very weak PL (PLQY = 0.10%). The significant enhancement of PLQY is attributed to the formation of [Mn(Cl/Br)4(OH)2]4--[Pb(Cl/Br)4(OH)2]4--[Mn(Cl/Br)4(OH)2]4- chain network structure, in which Pb2+ effectively dilutes the Mn2+ concentration to reduce magnetic coupling between Mn2+ pairs to relax the spin and parity selection rules. In addition, excited energy can effectively transfer from the [Pb(Cl/Br)4(OH)2]4- unit to Mn2+ luminescence centers owing to the low activation energy. Pb2+-incorporated PA NCs also exhibit excellent stability. The combined strong PL and high stability make Pb2+-incorporated Mn-based PA NCs an excellent candidate for potential optronic applications.

[Cd Pollution and Safe Planting Zoning in Paddy Soils: A Case Study in a District of Chongqing].

Rice has a strong ability to accumulate Cd in soil, and it is of great significance to study Cd pollution and safe planting zoning in paddy soils. In this work, 300 sets of paddy soil-rice samples were simultaneously collected in 22 towns in a District of Chongqing, and soil pH, soil total and available Cd contents, and brown rice Cd contents were determined. Soil Cd pollution was assessed using the geoaccumulation index, bioconcentration factor, and the single-factor pollution index. Based on the Cd pollution indices of soil and brown rice, safe planting zoning for rice was determined. The results showed that the paddy soils were generally acidic, and total Cd contents ranged from 0.09 mg·kg-1 to 1.60 mg·kg-1, with 35.0% of sites exceeding the risk screening value. The Cd contents of the brown rice ranged from 0.002 mg·kg-1 to 0.808 mg·kg-1 and exceeded the food safety limit in 13.7% of cases. Pearson correlation analysis showed that the Cd content of brown rice was significantly positively correlated with soil total and available Cd (P<0.01). The pollution evaluation indicated that significant Cd accumulation occurred in the paddy soils, with some areas showing light-to-moderate pollution levels. The enrichment coefficients of rice to soil Cd ranged from 0.004 to 1.72. Overall, the paddy soils in the studied area were considered generally safe with respect to Cd pollution, with low-risk areas distributed in the south, west, and east, whereas some medium-high risk areas were detected in eight towns.

Charge State of Au25(SG)18 Nanoclusters Induced by Interaction with a Metal Organic Framework Support and Its Effect on Catalytic Performance.

We investigated the charge transfer between Au25(SG)18 nanoclusters and metal-organic framework (MOF) supports including Mil-101-Cr, Mil-125-Ti, and ZIF-8 by an X-ray photoemission technique and discussed the influence of resulted charge states of supported Au25(SG)18 nanoclusters on the 4-nitrophenol reduction reaction. Charge transfer from Au25(SG)18 to Mil-101-Cr induces positive charge Auδ+ (0 < δ < 1) while charge transfer from ZIF-8 to Au25(SG)18 generates negative charge Auδ- due to different metal-support interactions. Au25(SG)18 on Mil-125 shows metallic Au0, similar to unsupported Au25(SG)18, due to negligible charge transfer. The resulted charge state of Auδ- inhibits the formation of adsorbed hydride (H-) species because of electrostatic repulsion, while Auδ+ impairs the reductive ability of adsorbed hydride (H-) species due to strong affinity between them. In comparison, metallic Au0 in Au25(SG)18/Mil-125 and unsupported Au25(SG)18 presents the optimum catalytic activity. The current work provides guidelines to design effective metal nanoclusters in heterogeneous catalysis through metal-support interaction exerted by metal-oxo/nitric clusters within MOFs.

Design and preparation of three-dimensional hetero-electrocatalysts of NiCo-layered double hydroxide nanosheets incorporated with silver nanoclusters for enhanced oxygen evolution reactions.

Layered double hydroxides (LDHs) are one of the most effective electrocatalysts. However, it is still necessary to improve the lower conductivity and limited active sites of LDHs to enhance their catalytic performance. Targeted generation of vacancies on the catalyst's surface by the incorporation of metal nanoparticles has been explored as a promising strategy to synthesize highly efficient electrocatalysts. Herein, we designed and prepared novel three-dimensional (3D) hetero-electrocatalysts of NiCo-layered double hydroxide nanosheets incorporated with silver nanoclusters on a Ni foam (labeled as Ag@NiCo-LDH/NF) by a one-pot hydrothermal method. We also conducted experimental and theoretical investigations to demonstrate the high electrocatalytic performance of the Ag@NiCo-LDH/NF hetero-electrocatalysts for OERs and the underlying mechanism. The resulting hetero-electrocatalysts show a low overpotential of 262 mV at a current density of 10 mA cm-2, and even exhibit low overpotentials of 300 mV at a high current density of 50 mA cm-2 and 324 mV at 100 mA cm-2, and a small Tafel slope of 41 mV dec-1 as well as excellent durability for 80 h for OERs in 1.0 M KOH. The excellent performance is attributed to the synergistic effects between Ag nanoclusters and LDHs. The population engineering effect of silver not only helps to modulate the intrinsic properties of active sites but also induces the generation of abundant oxygen vacancies on the surface; finally, it facilitates the rate-determining step of OERs (ΔG3 (O* → OOH*) = 1.31 eV) to gain high performance. The one-pot silver incorporating strategy and the resulting high performance pave new ways for the further development of highly efficient electrocatalysts for OERs.

Recent advances in ultrathin two-dimensional materials and biomedical applications for reactive oxygen species generation and scavenging.

Graphene and graphene-like two-dimensional (2D) nanomaterials, such as black phosphorus (BP), transition metal carbides/carbonitrides (MXene) and transition metal dichalcogenides (TMD), have been extensively studied in recent years due to their unique physical and chemical properties. With atomic-scale thickness, these 2D materials and their derivatives can react with ROS and even scavenge ROS in the dark. With excellent biocompatibility and biosafety, they show great application potential in the antioxidant field and ROS detection for diagnosis. They can also generate ROS under light and be applied in antibacterial, photodynamic therapy (PDT), and other biomedical fields. Understanding the degradation mechanism of 2D nanomaterials by ROS generated under ambient conditions is crucial to developing air stable devices and expanding their application ranges. In this review, we summarize recent advances in 2D materials with a focus on the relationship between their intrinsic structure and the ROS scavenging or generating ability. We have also highlighted important guidelines for the design and synthesis of highly efficient ROS scavenging or generating 2D materials along with their biomedical applications.