Dimethylamine Copper(I) Halide Single Crystals: Structure, Physical Properties, and Scintillation Performance.

Hybrid copper(I) halides have garnered a significant amount of attention as potential substitutes in luminescence and scintillation applications. Herein, we report the discovery and crystal growth of new zero-dimensional compounds, (C2H8N)3Cu2I5 and (C2H8N)4Cu2Br6. The bromide and iodide have a triclinic structure with space group P1̅ and an orthorhombic structure with space group Pnma, respectively. (C2H8N)3Cu2I5 exhibits cyan emission peaking at 504 nm with a photoluminescence quantum yield (PLQY) of 34.79%, while (C2H8N)4Cu2Br6 shows yellowish-green emission peaking at 537 nm with a PLQY of 38.45%. The temperature-dependent photoluminescence data of both compounds were fitted to theoretical models, revealing that nonradiative intermediate states significantly affect thermal quenching and antiquenching. Electron-phonon interactions, the origin of emission line width broadening and peak shifting, were also investigated via fittings. The scintillation properties of (C2H8N)3Cu2I5 were evaluated, and an X-ray imaging device was successfully fabricated using (C2H8N)3Cu2I5. This work demonstrates the potentiality of copper halides in lighting and X-ray imaging applications.

High-stability double perovskite scintillator for flexible X-ray imaging.

Metal halide perovskites, as a new class of attractive and potential scintillators, are highly promising in X-ray imaging. However, their application is limited by the sensitivity to moisture and irradiation. To address this issue, we reported a 2D layered double perovskite material Cs4Cd1-xMnxBi2Cl12 that exhibits high stability both under ambient condition and under X-ray irradiation. Cs4Cd1-xMnxBi2Cl12 demonstrates superior scintillation performance, including excellent X-ray response linearity and a high light yield (∼34,450 photons/MeV). More importantly, the X-ray excited emission intensity maintains 92% and 94% of its original value after stored at ambient condition for over two years and after X-ray irradiation with a total dose of 11.4 Gy, respectively. By mixing with PDMS (polydimethylsiloxane), we have successfully produced a high-quality flexible film that can be bent freely while maintaining its excellent scintillation properties. The scintillating screen exhibits outstanding imaging ability with a spatial resolution of up to 16.7 line pairs per millimeter (lp/mm), also, the superiority of this scintillation screen in flexible X-ray imaging is demonstrated. These results indicate the huge potential of this high-stability double perovskite scintillator in X-ray imaging.

Albumin-to-D-dimer ratios: A novel prognostic factor for evaluating first-line chemotherapy efficacy in advanced lung adenocarcinoma patients.

The prognosis of advanced lung adenocarcinoma (LUAD) remains unfavorable, with chemotherapy constituting a primary treatment modality. Discerning the efficacy of chemotherapy for advanced LUAD is imperative. Prior investigations have demonstrated the prognostic value of albumin and D-dimer individually for malignancies; however, the predictive capacity of albumin-to-D-dimer ratios (ADR) for advanced LUAD subjected to first-line platinum-based chemotherapy remains unexplored. A cohort of 313 patients with advanced LUAD was retrospectively examined in this study, spanning from January 2017 to January 2021. ADR threshold values were ascertained via receiver operating characteristic analysis, followed by the evaluation of the association between pretreatment ADR and clinicopathological characteristics, disease control rate (DCR), and overall response rate (ORR) pertinent to first-line chemotherapy. Prognostic factors for progression-free survival (PFS) were determined employing Cox univariate and multivariate analyses. Subsequently, survival data were illustrated utilizing the Kaplan-Meier method and scrutinized through the log-rank test across the entire and subgroup populations. ADR demonstrated a superior area under the curve (AUC) value relative to albumin and D-dimer individually and exhibited enhanced prognostic predictive capability compared to albumin-to-fibrinogen ratios (AFR) for advanced LUAD (AUC: 0.805 vs. 0.640, DeLong test: p<0.001). ADR yielded a cut-off value of 16.608. A greater proportion of non-smokers was observed within the high-ADR group (ADR>16.608) compared to the low-ADR group (ADR≤16.608). Patients in the high-ADR group displayed elevated BMI and Na+ levels and reduced neutrophil count, monocyte count, globulin, and alkaline phosphatase (all p<0.05). Notably, the high-ADR group exhibited heightened DCR (96.7% vs. 89.2%, p=0.008) and ORR rates (70.1% vs. 51.0%, p=0.001) relative to the low-ADR group. Multivariate analysis outcomes indicated that high ADR constituted an independent risk factor for PFS (hazard ratio: 0.24, p<0.001). Furthermore, patients in the high-ADR cohort displayed a significantly prolonged median PFS (254 vs. 142 days, p<0.0001) compared to their low-ADR counterparts. In subpopulations exhibiting favorable implications for PFS, as determined by multivariate analysis, high-ADR patients consistently demonstrated extended PFS durations relative to the low-ADR group (all p<0.0001). Collectively, our findings suggest that ADR constitutes a novel and promising prognostic indicator for advanced LUAD patients, surpassing the accuracy of albumin and D-dimer individually and AFR. ADR thus serves as a potent instrument for assessing treatment effects and PFS in advanced LUAD patients undergoing first-line chemotherapy.

Colloidal Synthesis of Hollow Double Perovskite Nanocrystals and Their Applications in X-ray Imaging.

Rare earth-based halide double perovskites are regarded as an emerging class of X-ray scintillation materials. However, the majority of related scintillator applications are still focused on single crystal and powder systems; the application of nanocrystal (NC) scintillators is rarely reported. Here, we present the synthesis of high-purity Cs2NaTbCl6 NCs by an improved hot-injection method. Interestingly, hollow Cs2NaTbCl6 NCs are observed, the monitoring of the growth process indicates that micrometer-sized NaCl is the initial product, and then the NaCl would convert into Cs2NaTbCl6 NCs through the diffusion of Cs+ and Tb3+ into NaCl lattice, and the faster outward diffusion of Na+ results in the formation of hollow NCs. The double perovskite NCs exhibit green light emission, and the photoluminescence intensity can be significantly enhanced through Ce3+ doping. In particular, the Cs2NaTbCl6:5%Ce3+ scintillator exhibits a linear response and a low detection limit of 79.09 nGy/s when exposed to X-rays. Furthermore, a flexible scintillator film for X-ray imaging is prepared by mixing NCs with polymer, showing a high spatial resolution imaging capability of 10 lp/mm. This work provides a new strategy for hollow perovskite NCs and may shed light on the synthesis of related hollow NCs and their applications in X-ray detection.

Seed-mediated growth synthesis and tunable narrow-band luminescence of quaternary Ag-In-Ga-S alloyed nanocrystals.

Silver-based I-III-VI-type semiconductor nanocrystals have received extensive attention due to their narrow-band luminescence properties. Herein, we demonstrated a seed-mediated growth of quaternary Ag-In-Ga-S (AIGS) nanocrystals (NCs) with narrow-band luminescence. By conducting partial cation exchange with In3+ and Ga3+ based on Ag2S NCs and controlling the Ag/In feeding ratios (0.25 to 2) of Ag-In-S seeds as well as the inventory of 1-dodecanethiol, we achieved optimized luminescence performance in the synthesized AIGS NCs, characterized by a narrow full width at half maximum of less than 40 nm. Meanwhile, narrow-band luminescent AIGS NCs exhibit a tetragonal AgGaS2 crystal structure and a gradient alloy structure, rather than a core-shell structure. Most importantly, the kinetics decay curves of time-resolved photoluminescence and the ground state bleaching in transient absorption generally agree with each other regarding the lifetime of the second decay component, which indicates that the narrow-band luminescence is due to the slow radiative recombination between trapped electrons and trapped holes located at the edge of the conduction band and the deep silver-related trap states (e.g., silver vacancy), respectively. This study provides new insights into the correlation between the narrow-band luminescence properties and the structural characteristics of AIGS NCs.

Analysis of key genes for the survival of Pantoea agglomerans under nutritional stress.

The absolute amount of nutrients on plant leaves is usually low, and the growth of epiphytic bacteria is typically limited by nutrient content. Thus, is of great significance to study the survival mechanism of epiphytes under nutritional stress for plant disease control. In this paper, Pantoea agglomerans CHTF15 isolated from walnut leaves was used to detect the key genes for the survival of the bacterium under simulated nutrient stress in artificial medium. Genome sequencing was combined with transposon insertion sequencing (Tn-seq) for the detection technique. A total of 105 essential genes were screened from the whole genome. The genes were mainly related to the nucleotide metabolism, protein metabolism, biological oxidation and the gene repair of bacteria analyzed by gene ontology (GO) enrichment analysis. Volcano map analysis demonstrated that the functions of the 15 genes with the most significant differences were generally related to the synthesis of amino acids or proteins, the nucleotide metabolism and homologous recombination and repair. Competitive index analysis revealed that the deletion of the genes dksA and epmA regulating protein synthesis, the gene ribB involved in the nucleotide metabolism and the gene xerD involved in recombination repair induced a significant reduction in the survival ability of the corresponding mutants in the 0.10 % YEP medium and the walnut leaf surface. The results act as a foundation for further in-depth research on the infection process and the mechanisms of pathogenic bacteria.

One-Dimensional Hybrid Copper(I) Iodide Single Crystal with Renewable Scintillation Properties.

Low-dimensional hybrid copper(I) halides attract considerable attention in the field of light emissions. In this work, we obtained the centimeter-sized single crystal of 1,3-propanediamine copper(I) iodide (PDACuI3) with a solvent evaporation method. The single crystal X-ray diffraction of PDACuI3 reveals that the [CuI4] tetrahedra form the corner-connected chains separated by PDAs, forming a one-dimensional structure with an orthorhombic space group of Pbca. The band gap is determined to be 4.03 eV, and the room temperature photoluminescence (PL) quantum yield is determined to be 26.5%. The thermal quenching and negative thermal quenching of emission are observed via temperature-dependent PL spectra, and our study shows that the intermediate nonradiative state below the self-trapped exciton state may get involved in these temperature-dependent behaviors. The X-ray scintillation performance of PDACuI3 single crystals is also evaluated, and the relative light output renewed to 94.3% of the fresh one after a low-temperature annealing. On the basis of our results, PDACuI3 single crystals provide nontoxicity and renewable scintillation performance, thus showing potential application in the area of low-cost radiation detectors.

Complete Genome Sequence of Pantoea agglomerans CHTF15, a Walnut Pathogen.

The phytopathogen Pantoea agglomerans belongs to the Bacteria, Proteobacteria, Gammaproteobacteria, Enterobacterales, Erwiniaceae in species classification. It causes disease symptoms in many plants such as corn, banana, and walnut. This study aimed to report the complete genome of P. agglomerans CHTF15, which represents the first whole-genome sequence of an isolate from diseased walnut leaves. The total length of the assembled genome was 4,820,607 bp, with an average GC content of 55.3%, including a circular chromosome and three circular plasmids, two of which were previously unreported sequences and one was announced previously. The CHTF15 genome helps understand the pathogenic mechanism of this important plant pathogen and provides an important theoretical basis for disease epidemic and field control. [Formula: see text] The author(s) have dedicated the work to the public domain under the Creative Commons CC0 "No Rights Reserved" license by waiving all of his or her rights to the work worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law, 2023.

Highly Effective Hybrid Copper(I) Iodide Cluster Emitter with Negative Thermal Quenched Phosphorescence for X-Ray Imaging.

The low efficiency triplet emission of hybrid copper(I) iodide clusters is a critical obstacle to their further practical optoelectronic application. Herein, we present an efficient hybrid copper(I) iodide cluster emitter (DBA)4 Cu4 I4 , where the cooperation of excited state structure reorganization and the metallophilicity interaction enables ultra-bright triplet yellow-orange emission with a photoluminescence quantum yield over 94.9 %, and the phonon-assisted de-trapping process of exciton induces the negative thermal quenching effect at 80-300 K. We also investigate the potential of this emitter for X-ray imaging. The (DBA)4 Cu4 I4 wafer demonstrates a light yield higher than 104  photons MeV-1 and a high spatial resolution of ≈5.0 lp mm-1 , showing great potential in practical X-ray imaging applications. Our new copper(I) iodide cluster emitter can serve as a model for investigating the thermodynamic mechanism of photoluminescence in hybrid copper(I) halide phosphorescence materials.

Metabolomic and Transcriptome Analysis of the Inhibitory Effects of Bacillus subtilis Strain Z-14 against Fusarium oxysporum Causing Vascular Wilt Diseases in Cucumber.

Controlling cucumber Fusarium wilt caused by Fusarium oxysporum f. sp. cucumerinum (FOC) with Bacillus strains is a hot research topic. However, the molecular mechanism of Bacillus underlying the biocontrol of cucumber wilt is rarely reported. In this study, B. subtilis strain Z-14 showed significant antagonistic activity against FOC, and the control effect reached 88.46% via pot experiment. Microscopic observations showed that strain Z-14 induced the expansion and breakage of FOC hyphae. The cell wall thickness was uneven, and the organelle structure was degraded. The combined analysis of metabolome and transcriptome showed that strain Z-14 inhibited the FOC infection by inhibiting the synthesis of cell wall and cell membrane, energy metabolism, and amino acid synthesis of FOC mycelium, inhibiting the clearance of reactive oxygen species (ROS) and the secretion of cell wall-degrading enzymes (CWDEs), thereby affecting mitogen-activated protein kinase (MAPK) signal transduction and inhibiting the transport function.

Vapor-Deposited Amino Coupling of Hybrid Perovskite Single Crystals and Silicon Wafers toward Highly Efficient Multiwavelength Photodetection.

The complementary integration of perovskite single crystals (PSCs) and silicon-based circuitry provides a feasible way to combine their superiority toward efficient multiwavelength photodetection and imaging readout; however, it suffers from distinct lattice mismatch as well as the ambiguous coupling interface effect. Herein, we develop a vacuum-assisted vapor deposition strategy to realize an ultrauniform aminosiloxane interface-modified silicon wafer, which enables the monolithic epitaxial growth of PSCs with the highest mechanical coupling strength up to 340,000 N m-2 achieved so far. According to the molecular coupling engineering development with different aminosiloxanes, we achieve a highly efficient multiwavelength-responsive integrated photodetector, possessing specific photodetectivity values of 4.36 × 1012 jones and 4.55 × 1011 jones within the visible and NIR regions, respectively, as well as the lowest X-ray detection limit of 42.6 nGyair s-1. Moreover, a particularly wide -3dB cut-off frequency of 6350 Hz as well as a 120 dB linear dynamic range (LDR) also endows the integrated device with excellent dynamic photodetection capability. This work provides an efficacious approach in the integration technology for PSC-based optoelectronic applications.

Thermally Activated Delayed Fluorescence Zirconium-Based Perovskites for Large-Area and Ultraflexible X-ray Scintillator Screens.

Flexible scintillator screens with environmental stability, high sensitivity, and low cost have emerged as candidates for X-ray imaging applications. Here, a large-scale and cost-efficient solution synthesis of the vacancy-ordered double perovskite Cs2 ZrCl6 , which is characterized by thermal activation delayed fluorescence (TADF) dominated by triplet emission under X-ray irradiation, is demonstrated. The large Stokes shift and efficient luminescence collection of TADF effectively ensure the light outcoupling efficiency. Further, flexible X-ray scintillator screens with an area of 400 cm2 are prepared using poly(dimethylsiloxane) (PDMS) as the carrier, exhibiting excellent scintillation properties with light yields as high as 49 400 photons MeV-1 , spatial resolutions up to 18 lp mm-1 and detection limits as low as 65 nGy s-1 . Finally, the high-quality imaging results of non-planar and dynamic objects by such screens are demonstrated. It is believed that the explored Cs2 ZrCl6 @PDMS flexible scintillator screens would offer a big step toward expanding the application range of scintillators in different environments.

Influence of Bacillus subtilis strain Z-14 on microbial communities of wheat rhizospheric soil infested with Gaeumannomyces graminis var. tritici.

Wheat take-all disease caused by Gaeumannomyces graminis var. tritici (Ggt) spreads rapidly and is highly destructive, causing severe reductions in wheat yield. Bacillus subtilis strain Z-14 that significantly controlled wheat take-all disease effectively colonized the roots of wheat seedlings. Z-14 increased the metabolic activity and carbon source utilization of rhizospheric microorganisms, thus elevating average well-color development (AWCD) values and functional diversity indexes of soil microbial communities. Z-14 increased the abundance of Bacillus in the rhizosphere, which was positively correlated with AWCD and functional diversity indexes. The Z-14-treated samples acquired more linkages and relative connections between bacterial communities according to co-occurrence network analyses. After the application of Ggt, the number of linkages between fungal communities increased but later decreased, whereas Z-14 increased such interactions. Whole-genome sequencing uncovered 113 functional genes related to Z-14's colonization ability and 10 secondary metabolite gene clusters in the strain, of which nine substances have antimicrobial activity. This study clarifies how bacterial agents like Z-14 act against phytopathogenic fungi and lays a foundation for the effective application of biocontrol agents.

Metal Ions as the Third Component Coordinate with the Guest to Stereoscopically Enhance the Phosphorescence Properties of Doped Materials.

The construction of multicomponent doped systems is an important direction for the development of phosphorescence materials. Herein, benzophenone is selected as the host, phenylquinoline isomers are designed as guests, and seven metal ions are selected as the third component (Al3+, Cu+/2+, Zn2+, Ga3+, Ag+, Cd2+, and In3+) to construct the three-component doped system. Ag+ and Cd2+ can considerably increase the emission intensity up to 38 times, and the highest phosphorescence quantum efficiency reaches 70%. Al3+, Ga3+, and In3+ can prolong the emission wavelength, and the phosphorescence wavelength can be red-shifted up to 60 nm. Cu2+, Ga3+, and In3+ can extend the phosphorescence lifetime by a maximum of 3.6 times. A series of experiments demonstrated that the coordination of metals and guests is the key to improve the phosphorescence properties. This work presents a simple and effective strategy to enhance the phosphorescence properties of doped materials.

Temperature-Dependent Luminescence and Anisotropic Optical Properties of Centimeter-Sized One-Dimensional Perovskite Trimethylammonium Lead Iodide Single Crystals.

Low-dimensional hybrid halide perovskite materials with self-trapped exciton (STE) emissions and anisotropic properties are highly attractive for their great potential in many applications. However, to date, reports on large one-dimensional (1D) perovskite single crystals have been limited. Here, centimeter-sized 1D single crystals of trimethylammonium lead iodide (TMAPbI3) with typical STE emission are synthesized by an antisolvent vapor-assisted crystallization method. Thermal quenching and antiquenching with a high relative sensitivity of photoluminescence (PL) are observed and studied via temperature-dependent photoluminescence spectroscopy. Further analysis indicates that the temperature-dependent PL behaviors are influenced by the self-trapping of the free exciton and the migrations between self-trapped excitons and intermediate nonradiative states. The TMAPbI3 single crystal also exhibits a linearly polarized emission and a large birefringence that is higher than those of commercial birefringent crystals. This 1D perovskite with high structural anisotropy has promise for applications in versatile optical- and luminescence-related fields.

All-Inorganic Manganese-Based CsMnCl3 Nanocrystals for X-Ray Imaging.

Lead-based halide perovskite nanomaterials with excellent optical properties have aroused great attention in the fields of solar cells, light-emitting diodes, lasing, X-ray imaging, etc. However, the toxicity of lead prompts researchers to develop alternatives to cut down the usage of lead. Herein, all-inorganic manganese-based perovskite derivatives, CsMnCl3 nanocrystals (NCs), with uniform size and morphology have been synthesized successfully via a modified hot-injection method. These NCs have a direct bandgap of 4.08 eV and a broadband emission centered at 660 nm. Through introducing modicum lead (1%) into the CsMnCl3 NCs, the photoluminescence intensity greatly improves, and the quantum yield (PLQY) increases from 0.7% to 21%. Furthermore, the CsMnCl3 :1%Pb NCs feature high-efficiency of X-ray absorption and radioluminescence, which make these NCs promising candidates for X-ray imaging.

Single-atom sites on perovskite chips for record-high sensitivity and quantification in SERS.

Surface enhanced Raman scattering (SERS) is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds. Sensitive SERS quantification is vital for practical applications, particularly for portable detection of biomolecules such as amino acids and nucleotides. However, few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology. Herein, a noble-metal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite, which provides sensitive SERS quantification for various analytes, including rhodamine, tyrosine and cytosine. The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine (10-6-1 mmol L-1), tyrosine (0.06-1 mmol L-1) and cytosine (0.2-45 mmol L-1), respectively, which all achieve record-high enhancement factors among plasmonic-free semiconductors. The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site, which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes. Furthermore, the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument, which can be readily extended to various biomolecules for low-cost, widely demanded and more precise point-of-care testing or in-vitro detection. Electronic Supplementary Material: Supplementary material is available for this article at 10.1007/s40843-022-1968-5 and is accessible for authorized users.

Halogen Bonding: A New Platform for Achieving Multi-Stimuli-Responsive Persistent Phosphorescence.

Monotonous luminescence has always been a major factor limiting the application of organic room-temperature phosphorescence (RTP) materials. Enhancing and regulating the intermolecular interactions between the host and guest is an effective strategy to achieve excellent phosphorescence performance. In this study, intermolecular halogen bonding (CN⋅⋅⋅Br) was introduced into the host-guest RTP system. The interaction promoted intersystem crossing and stabilized the triplet excitons, thus helping to achieve strong phosphorescence emission. In addition, the weak intermolecular interaction of halogen bonding is sensitive to external stimuli such as heat, mechanical force, and X-rays. Therefore, the triplet excitons were easily quenched and colorimetric multi-stimuli responsive behaviors were realized, which greatly enriched the luminescence functionality of the RTP materials. This method provides a new platform for the future design of responsive RTP materials based on weak intermolecular interactions between the host and guest molecules.

Highly efficient copper halide scintillators for high-performance and dynamic X-ray imaging.

Progress towards high performance X-ray detection and dynamic imaging applications, including nondestructive inspection, homeland security, and medical diagnostics, requires scintillators with a high light yield, a reasonable decay time, low cost, and eco-friendliness. Recently, copper halide scintillators have drawn tremendous attention due to their outstanding radioluminescence performance. Here, we first employed ß-Cs3Cu2Cl5 as a high-performance scintillator, with a photoluminescence quantum yield (PLQY) of 94.6%, a radioluminescence light yield of 34 000 ± 4000 photons per MeV, a low detection limit of 81.7 nGyair s-1, and good operational stability under a total X-ray dose of 174.6 Gyair in air. In addition, this scintillator presents a high spatial resolution of 9.6 lp mm-1 at the modulation transfer function of 0.2 and a superb performance at 60 frames per second in our X-ray imaging system. Overall, this highly efficient scintillator demonstrates outstanding comprehensive performance and shows great potential for broad applications in X-ray detection and dynamic imaging.

Activity of Fengycin and Iturin A Isolated From Bacillus subtilis Z-14 on Gaeumannomyces graminis Var. tritici and Soil Microbial Diversity.

Bacillus subtilis Z-14 can inhibit phytopathogenic fungi, and is used as a biocontrol agent for wheat take-all disease. The present study used the soil-borne fungus Gaeumannomyces graminis var. tritici (Ggt), which causes wheat take-all disease, and the soil microbial community as indicators, and investigated the antifungal effects of fengycin and iturin A purified from strain Z-14 using high performance liquid chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, respectively. The results showed that fengycin destroyed the internal structure of Ggt cells by digesting the cytoplasm and organelles, forming vacuoles, and inducing hyphal shrinkage and distortion. Iturin A induced cell wall disappearance, membrane degeneration, intracellular material shrinkage, and hyphal fragmentation. A biocontrol test demonstrated a 100% control effect on wheat take-all when wheat seedlings were treated with fengycin at 100 µg/ml or iturin A at 500 µg/ml. Iturin A and fengycin both reduced the relative abundance of Aspergillus and Gibberella. At the genus level, iturin A reduced the relative abundance of Mortierella and Myrothecium, while fengycin reduced that of Fusarium. Only fengycin treatment for 7 days had a significant effect on soil bacterial diversity.