Electronic structure, colour-tunable emission and energy transfer in Li3Ba2Y3(WO4)8:Bi3+,Eu3+ phosphors for white light-emitting diodes.

Solid-state phosphor-converted white light-emitting diodes (pc-WLEDs) are the leading trend of the lighting industry in the 21st century. To pursue high quality WLED lighting, the development of highly efficient phosphors with tunable luminescence has become a hot research topic. Herein, we reported for the first time on Bi3+/Eu3+-doped Li3Ba2Y3(WO4)8 phosphors that exhibited tunable emission and high energy transfer efficiency of 89.90% from Bi3+ to Eu3+. The phase purity, microstructure, electronic structure and photoluminescence properties of these phosphors were studied in detail. Bi3+ and Eu3+ were effectively doped in Li3Ba2Y3(WO4)8 with an optical bandgap of 3.81 eV. The band structure and density of states were quantitatively evaluated by density functional theory simulation. At an excitation wavelength of 342 nm, the Bi3+-doped phosphor achieved yellow-green emission. By alloying Eu3+ into Li3Ba2Y3(WO4)8:Bi3+, the luminescence gradually turned red due to the energy transfer from Bi3+ to Eu3+. Moreover, the activation energy of the prepared phosphor was 0.1897 eV, demonstrating excellent thermal stability. Eventually, by combining Li3Ba2Y3(WO4)8:4%Bi3+,4%Eu3+ and a blue-emitting BAM:Eu2+ phosphor with a 365 nm ultraviolet chip, a WLED device with a high colour rendering index (Ra) of 78.7, chromaticity coordinates of (0.3401, 0.3131) and correlated colour temperature of 5080 K was successfully achieved. This work provided new insights into the design and development of color-tunable phosphors for white LEDs.

Toward the Integration of Machine Learning and Molecular Modeling for Designing Drug Delivery Nanocarriers.

The pioneering work on liposomes in the 1960s and subsequent research in controlled drug release systems significantly advances the development of nanocarriers (NCs) for drug delivery. This field is evolved to include a diverse array of nanocarriers such as liposomes, polymeric nanoparticles, dendrimers, and more, each tailored to specific therapeutic applications. Despite significant achievements, the clinical translation of nanocarriers is limited, primarily due to the low efficiency of drug delivery and an incomplete understanding of nanocarrier interactions with biological systems. Addressing these challenges requires interdisciplinary collaboration and a deep understanding of the nano-bio interface. To enhance nanocarrier design, scientists employ both physics-based and data-driven models. Physics-based models provide detailed insights into chemical reactions and interactions at atomic and molecular scales, while data-driven models leverage machine learning to analyze large datasets and uncover hidden mechanisms. The integration of these models presents challenges such as harmonizing different modeling approaches and ensuring model validation and generalization across biological systems. However, this integration is crucial for developing effective and targeted nanocarrier systems. By integrating these approaches with enhanced data infrastructure, explainable AI, computational advances, and machine learning potentials, researchers can develop innovative nanomedicine solutions, ultimately improving therapeutic outcomes.

Self-Assembling and Pore-Forming Peptoids as Antimicrobial Biomaterials.

Bacterial infections have been a serious threat to mankind throughout history. Natural antimicrobial peptides (AMPs) and their membrane disruption mechanism have generated immense interest in the design and development of synthetic mimetics that could overcome the intrinsic drawbacks of AMPs, such as their susceptibility to proteolytic degradation and low bioavailability. Herein, by exploiting the self-assembly and pore-forming capabilities of sequence-defined peptoids, we discovered a family of low-molecular weight peptoid antibiotics that exhibit excellent broad-spectrum activity and high selectivity toward a panel of clinically significant Gram-positive and Gram-negative bacterial strains, including vancomycin-resistant Enterococcus faecalis (VREF), methicillin-resistant Staphylococcus aureus (MRSA), methicillin-resistant Staphylococcus epidermidis (MRSE), Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae. Tuning the peptoid side chain chemistry and structure enabled us to tune the efficacy of antimicrobial activity. Mechanistic studies using transmission electron microscopy (TEM), bacterial membrane depolarization and lysis, and time-kill kinetics assays along with molecular dynamics simulations reveal that these peptoids kill both Gram-positive and Gram-negative bacteria through a membrane disruption mechanism. These robust and biocompatible peptoid-based antibiotics can provide a valuable tool for combating emerging drug resistance.

Protein Corona-Directed Cellular Recognition and Uptake of Polyethylene Nanoplastics by Macrophages.

The widespread use of plastic products in daily life has raised concerns about the health hazards associated with nanoplastics (NPs). When exposed, NPs are likely to infiltrate the bloodstream, interact with plasma proteins, and trigger macrophage recognition and clearance. In this study, we focused on establishing a correlation between the unique protein coronal signatures of high-density (HDPE) and low-density (LDPE) polyethylene (PE) NPs with their ultimate impact on macrophage recognition and cytotoxicity. We observed that low-density and high-density lipoprotein receptors (LDLR and SR-B1), facilitated by apolipoproteins, played an essential role in PE-NP recognition. Consequently, PE-NPs activated the caspase-3/GSDME pathway and ultimately led to pyroptosis. Advanced imaging techniques, including label-free scattered light confocal imaging and cryo-soft X-ray transmission microscopy with 3D-tomographic reconstruction (nano-CT), provided powerful insights into visualizing NPs-cell interactions. These findings underscore the potential risks of NPs to macrophages and introduce analytical methods for studying the behavior of NPs in biological systems.

Hydrophobic Carbon Nitride Nanolayer Enables High-Flux Oil/Water Separation with Photocatalytic Antifouling Ability.

Efficient oil/water separation tackles various issues in occasions of oil leakage and oil discharge, such as environmental pollution, recollection of the oil, and saving the water. Herein, a compact superhydrophobic/superoleophilic graphitic carbon nitride nanolayer coated on carbon fiber networks (CNBA/CF) is designed and synthesized for efficient gravity-driven oil/water separation. The CNBA/CF shows excellent oil absorption and an impressive oil/water filtration separation performance. The flux reaches the state-of-art value of 4.29 × 105 L/m2/h for dichloromethane with separation efficiency up to 99%. Successive oil absorption tests, long-term filtration separation, and harsh conditions experiments confirm the remarkable separation and chemical structure stability of the CNBA/CF filter. Besides, the CNBA/CF demonstrates good photocatalytic antifouling ability thanks to the extended visible light absorption and improved charge separation. This work combines the material surface wettability modulation with a photocatalytic self-cleaning property in the fabrication of efficient oil/water separation materials while overcoming the filter fouling issue.

Optimizing the Spatial Density of Single Co Sites via Molecular Spacing for Facilitating Sustainable Water Oxidation.

Advances in single-atom (-site) catalysts (SACs) provide a new solution of atomic economy and accuracy for designing efficient electrocatalysts. In addition to a precise local coordination environment, controllable spatial active structure and tolerance under harsh operating conditions remain great challenges in the development of SACs. Here, we show a series of molecule-spaced SACs (msSACs) using different acid anhydrides to regulate the spatial density of discrete metal phthalocyanines with single Co sites, which significantly improve the effective active-site numbers and mass transfer, enabling one of the msSACs connected by pyromellitic dianhydride to exhibit an outstanding mass activity of (1.63 ± 0.01) × 105 A·g-1 and TOFbulk of 27.66 ± 1.59 s-1 at 1.58 V (vs RHE) and long-term durability at an ultrahigh current density of 2.0 A·cm-2 under industrial conditions for oxygen evolution reaction. This study demonstrates that the accessible spatial density of single atom sites can be another important parameter to enhance the overall performance of catalysts.

Self-Supporting Co/CeO2 Heterostructures for Ampere-Level Current Density Alkaline Water Electrolysis.

Remodeling the active surface through fabricating heterostructures can substantially enhance alkaline water electrolysis driven by renewable electrical energy. However, there are still great challenges in the synthesis of highly reactive and robust heterostructures to achieve both ampere-level current density hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a new Co/CeO2 heterojunction self-supported electrode for sustainable overall water splitting. The self-supporting Co/CeO2 heterostructures required only low overpotentials of 31.9 ± 2.2, 253.3 ± 2.7, and 316.7 ± 3 mV for HER and 214.1 ± 1.4, 362.3 ± 1.9, and 400.3 ± 3.7 mV for OER at 0.01, 0.5, and 1.0 A·cm-2, respectively, being one of the best Co-based bifunctional electrodes. Electrolyzer constructed from this electrode acting as an anode and cathode merely required cell voltages of 1.92 ± 0.02 V at 1.0 A·cm-2 for overall water splitting. Multiple characterization techniques combined with density functional theory calculations disclosed the different active sites on the anode and cathode, and the charge redistributions on the heterointerfaces that can optimize the adsorption of H and oxygen-containing intermediates, respectively. This study presents the tremendous prospective of self-supporting heterostructures for effective and economical overall water splitting.

Two-dimensional metal-phase layered molybdenum disulfide for electrocatalytic hydrogen evolution reaction.

The two-dimensional (2D) basal plane of metal-phase molybdenum disulphide (1T-MoS2) provides a large area of active sites to significantly reduce the overpotential of the hydrogen evolution reaction (HER), but the long preparation period limits its industrial application. Here, 1T-MoS2 catalysts derived from molybdenum blue solution (MBS) were prepared in one step using a rapid high-pressure microwave (MW-MoS2) strategy. This method eliminated the thermodynamic process with a long time required for Mo-O trioxide bond breakage and reduction (MoVI → MoIV) of the conventional hydrothermal method. Additionally, the introduction of heteroatomic oxygen atoms effectively reduced the build-up of MW-MoS2 and improved the monolayer/few-layer state and stability. Impressively, MW-MoS2 has outstanding electrocatalytic performance, with a low overpotential (62 mV) at 10 mA cm-2 and a small Tafel slope (42 mV dec-1). This provides a simple strategy for the rapid preparation of a 2D sulphide HER catalyst with performance close to that of commercial Pt/C.

A Metal-Organic Frameworks Derived 1T-MoS2 with Expanded Layer Spacing for Enhanced Electrocatalytic Hydrogen Evolution.

Metal phase molybdenum disulfide (1T-MoS2 ) is considered a promising electrocatalyst for hydrogen evolution reaction (HER) due to its activated basal and superior electrical conductivity. Here, a one-step solvothermal route is developed to prepare 1T-MoS2 with expanded layer spacing through the derivatization of a Mo-based organic framework (Mo-MOFs). Benefiting from N,N-dimethylformamide oxide as external stress, the interplanar spacing of (002) of the MoS2 catalyst is extended to 10.87 Å, which represents the largest one for the 1T-MoS2 catalyst prepared by the bottom-up approach. Theoretical calculations reveal that the expanded crystal planes alter the electronic structure of 1T-MoS2 , lower the adsorption-desorption potentials of protons, and thus, trigger efficient catalytic activity for HER. The optimal 1T-MoS2 catalyst exhibits an overpotential of 98 mV at 10 mA cm-2 for HER, corresponding to a Tafel slope of 52 mV dec-1 . This Mo-MOFs-derived strategy provides a potential way to design high-performance catalysts by adjusting the layer spacing of 2D materials.

Clear-Box Machine Learning for Virtual Screening of 2D Nanozymes to Target Tumor Hydrogen Peroxide.

Targeting tumor hydrogen peroxide (H2 O2 ) with catalytic materials has provided a novel chemotherapy strategy against solid tumors. Because numerous materials have been fabricated so far, there is an urgent need for an efficient in silico method, which can automatically screen out appropriate candidates from materials libraries for further therapeutic evaluation. In this work, adsorption-energy-based descriptors and criteria are developed for the catalase-like activities of materials surfaces. The result enables a comprehensive prediction of H2 O2 -targeted catalytic activities of materials by density functional theory (DFT) calculations. To expedite the prediction, machine learning models, which efficiently calculate the adsorption energies for 2D materials without DFT, are further developed. The finally obtained method takes advantage of both interpretability of physics model and high efficiency of machine learning. It provides an efficient approach for in silico screening of 2D materials toward tumor catalytic therapy, and it will greatly promote the development of catalytic nanomaterials for medical applications.

Cu-Modified La2Si2O7/TiO2 composite materials: preparation, characterization and photothermal properties.

Cu-Modified La2Si2O7/TiO2 composite materials were prepared by the molten salt method and a solid-phase reduction strategy. Due to the surface plasmon resonance (SPR) of copper, the optical response from the UV to the visible region and near-infrared is increased. In the meantime, it enhances the absorption of visible light by the titanium dioxide and acts as a plasma catalyst. The combination enhances the photothermal properties of the composite. The particle size of Cu/La2Si2O7/TiO2 is in the range of 100 to 230 nm. Results show that the composite has a good photothermal effect. The 1 mg ml-1 solution can be warmed up to 63.1 °C at 0.5 W cm-2 laser power density with a maximum temperature difference of 45 °C. It has potential applications in solar energy conversion, photothermal catalysis, etc.

Transcriptome analyses of potential regulators of pre- and post-ovulatory follicles in the pigeon (Columba livia).

To identify the dominant genes controlling follicular maturation, ovulation and regression for pigeon, we used RNA-seq to explore the gene expression profiles of pre- and post-ovulatory follicles of pigeon. We obtained total of 4.73million (96% of the raw data) high-quality clean reads, which could be aligned with 20282 genes. Gene expression profile analysis identified 1461 differentially expressed genes (DEGs) between the pre- (P4) and post-ovulatory follicles (P5). Of these, 843 genes were upregulated, and 618 genes were down-regulated. Furthermore, many DEGs were significantly enriched in some pathways closely related to follicle maturation, ovulation and regression, such as ECM-receptor interaction, vascular smooth muscle contraction, progesterone-mediated oocyte maturation, phagosome. Importantly, the DGEs in ECM-receptor interaction pathway included COL1A1 , COL1A2 , COL4A1 , COL4A2 , ITGA11 , ITGB3 and SDC3 , in the progesterone-mediated oocyte maturation pathway involved CDK1 , CDC25A , CCNB3 , CDC20 and Plk1 , and in the vascular smooth muscle contraction covered CALD1 , KCNMA1 , KCNMB1 , CACNA1 , ACTA2 , MYH10 , MYL3 , MYL6 , MYL9 , closely related to promoting follicular maturation and ovulation in pre-ovulatory follicles. Moreover, it seems that the lysosomal cathepsin family has a decisive role in the regression of early stage of post-ovulatory follicle. Taken together, these data enrich the research of molecular mechanisms of pigeon follicular activities at the transcriptional level and provide novel insight of breeding-related physiology for birds.

Combining functional hairpin probes with disordered cleavage of CRISPR/Cas12a protease to screen for B lymphocytic leukemia.

One of the causes of B lymphocytic leukemia is abnormal expression of the Pax-5a gene. Detection of the Pax-5a gene can provide effective technical means for early screening of B lymphocytic leukemia. In this work, we designed a sensing scheme to detect the Pax-5a gene based on the signal amplification system, which is based on dual-enzyme assisted target gene circulation, and the disordered cleavage of CRISPR/Cas12a protease. The hairpin probe (HP) in this scheme not only contains the binding sites of the target gene and the primer, but also cleverly contains half of the Nt.BbvCI splicing sites. When the target gene is present, through the synergistic effect of KF and Nt.BbvCI, a large number of single strands of a specific sequence can be produced. At the same time, the target gene falls off from the first hairpin and opens the other hairpin to realize the cycle of the target gene. The resulting single-strand can bind to the Cas12a/crRNA binary complex and unlock the anti-cleavage activity of the CRISPR/Cas12a protease. The single strands labeled with the fluorescent group (FAM) and the quenching group (BHQ) around the solution are cleaved, the fluorescence signal of FAM is restored, and a detectable fluorescence signal is generated. The detection limit is as low as 6.77 fM, and the target gene and the mismatch sequence can also be distinguished well. Therefore, the sensing scheme provides a new detection direction for the early diagnosis and screening of B lymphocytic leukemia.

Transcriptome analyses to reveal the dynamic change mechanism of pigeon magnum during one egg-laying cycle.

We analyzed the transcriptome of pigeon magnum in three stages (C1: pre-ovulation, C2: post-ovulation, C3: 5-6 days after ovulation) to elucidate the molecular and cellular events associated with morphological changes during the laying cycle. We observed that C1 was highly developed, apoptosis rate was highest in C2, and C3 attained the smallest size. Through RNA-sequencing, we obtained 54,764,938 (97.2%) high-quality clean reads that aligned to 20,767 genes. Gene expression profile analysis showed the greatest difference between C1 and C3; 3966 differentially expressed genes (DEGs) were identified, of which 2250 genes were upregulated and 1716 genes were downregulated in C1. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes analyses revealed that protein processing and transport activities were prominent in C1, and upregulated genes included those related to signal recognition particle (SRP), signal recognition particle receptor (SRPR), translocon, GRP78, RRBP1, TRAP, TRAM1, and OST. Egg white protein-related gene expression was highest, with OVALY being the most highly expressed. In C2, apoptosis-related gene expression was higher than in C1, and fatty acid metabolism was active, which may be correlated with magnum tissue regression. Collagen- and laminin-related gene expression was prominent in C1 and C3, indicating roles in egg white protein generation and magnum reconstruction. PR gene expression was highest and exhibited drastic change in the three groups, indicating that PR and its regulation may be involved in changes in magnum morphology and function. Through the identification and functional analysis of DEGs and other crucial genes, this may contribute to understand the egg white protein production, magnum tissue regression, and magnum regeneration mechanisms.

Scandium Molybdate Microstructures with Tunable Phase and Morphology: Microwave Synthesis, Theoretical Calculations, and Photoluminescence Properties.

In this paper, scandium molybdate microstructures have been prepared from solution via a microwave heating method. By controlling the experimental parameters such as molar ratio of reagent and reaction time, scandium molybdates with tunable phase and diverse morphologies including snowflakes, microflowers, microsheets, and branched spindles were obtained. The density of states and surface energies of Sc2Mo3O12 were primarily studied from first-principles calculations. An indirect band gap of 3.56 eV was observed for crystalline Sc2Mo3O12, and the surface energies of various facets were determined to be 0.27-0.91 J/m2. The influence of n(Sc3+): n(Mo7O246-) (short for Sc/Mo) molar ratio was systematically investigated and well-characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and UV-vis absorption spectroscopy (UV-vis). Results indicate that the Sc/Mo molar ratio has a great effect on the phase and morphology. Diffuse reflection spectra (DRS) revealed the Egap can be readily tuned from 3.69 to 4.16 eV, which is in accordance with the theoretical result. The photoluminescence (PL) properties of Eu3+-doped Sc2Mo3O12 were discussed. This facile synthesis strategy could be extended to the synthesis of other molybdates.

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor.

The investigation and development of advanced multifunctional and sensitive sensors with high luminescent quantum yield and the capability of detecting different analytes, such as metal ions, is imperative. Due to its inherent properties the lanthanide coordination complex is one candidate for sensing applications, particularly for multifunctional sensors. Herein, we present two series of alkali ion decorated lanthanide coordination polymers (Ln-CPs), which show ultrahigh luminescence quantum yields (QYs) of 77% (1a) and 92% (2a). To the best of our knowledge, 1a represents the first trifunctional lanthanide complex sensor that can simultaneous detect and discriminate three different analytes, namely H+/Cd2+/Cr3+ through a multimode optical response. Furthermore, the limit of detection (LOD) for Cr3+ is an ultralow value of 2.0 × 10-9 M with a sensing time of 2 h, which is comparable to the most sensitive Cr3+ chemosensor. More interestingly, 92% (2a) is an unprecedented luminescence QY among the reported lanthanide coordination complexes.

Detailed structure information a highly thermostable Tb-cluster that based on a prodrug ligand of 2,4,5-trifluoro-3-methoxybenzoic acid.

In this brief data article, we present the precise structural information, PARD data and thermographic analysis of the Tb-cluster. Detailed structure, luminescence and detecting properties were discussed in our previous study (Zhao et al., 2017) [1]. The data includes the coordination modes of ligand, PXRD patterns of these Ln-MOFs, thermostability, detailed bond lengths and bond angles of the Tb-cluster.

Structural data of structure variation and luminescence of 3D, 2D and 1D lanthanide coordination polymers with 1,3-adamantanediacetic acid.

In this data article, we report the structure, Fourier transform infrared spectroscopy(FT-IR), powder X-ray diffraction (PARD), luminescence decay, thermogravimetric analysis (TGA) and UV-vis data of three series Ln-MOFs. Detailed structure and luminescence properties were discussed in our previous study (Zhao et al., 2018) [1]. The data includes the structure patterns of ligand H2ADA, FT-IR, PXRD and thermostability of Ln-MOFs in the air, detailed structure information for these structures are listed in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, Table 7.

Structural data of thermostable 3D Ln-MOFs that based on flexible ligand of 1,3-adamantanediacetic acid.

In this data article, we present the structural and PARD data of the Ln-MOFs. Detailed structure, luminescence and sensing properties were discussed in our previous study (Zeng et al., in press) [1] The data includes the SBU structure patterns of these Ln-MOFs, thermostability of Ln-MOFs in water and also detailed structure information listed in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, Table 7, Table 8.

Multi-shelled ceria hollow spheres with a tunable shell number and thickness and their superior catalytic activity.

In this work, ceria multi-shelled nanospheres with a tunable shell number and thickness were prepared by a facile coordination polymer (CP) precursor method without the use of any template and surfactant. Interestingly, the number, thickness and structure of the shell can be tuned by varying the reaction time, reaction temperature, ratio of reagent and calcination temperature. The formation process of the multi-shelled hollow spheres was also investigated, which experienced a core contraction and shell separation process. Moreover, the multi-shelled CeO2 hollow nanospheres displayed excellent photocatalytic activity in the degradation of RhB. Au and AuPd nanoparticle loaded multi-shelled CeO2 nanocomposites were also prepared. Results show that Au/CeO2 multi-shelled hollow nanospheres showed eximious catalytic activity for the reduction of p-nitrophenol with a reaction rate constant k of 0.416 min. In addition, AuPd/CeO2 exhibited a remarkable catalytic activity for the conversion of CO. Employing this method, heavy rare earth oxide multi-shelled structures and light rare earth oxide solid spheres were obtained. This method may be employed for the preparation of other materials with complex structures.