Enhancing Persistent Luminescence through Synergy between Optimal Electron Traps and Dye Sensitization.

Due to their unique afterglow ability, long-wavelength-light rechargeable persistent luminescence (PersL) nanoparticles (PLNPs) have been emerging as an important category of imaging probes. Among them, ZnGa2O4:0.6% Cr3+ (ZGC) PLNPs have gained widespread recognition due to the ease of synthesis and uniform morphology. Unfortunately, the limited absorption arising from the low molar extinction coefficient of Cr3+ results in relatively low afterglow intensity and rapid decay after long-wavelength LED light irradiation. Herein, we discovered a strategy that boosting dye-sensitization performance was able to effectively amplify the PersL signal under white LED light. Specifically, Dil served as a highly efficient sensitizer for Cr3+, promoting the absorption of the excitation light. By adjusting the Pr dopant concentrations, ZGCP0.5 PLNPs with optimal trap densities were obtained, which showed the highest PersL intensity and dye-sensitized performance. Strikingly, ZGCP0.5-Dil PLNPs exhibited a 24.3-fold enhancement in intensity and a 2-fold prolongation of decay time over bare ZGC PLNPs through the synergy effect of optimal electron traps and dye sensitization. Photostable ZGCP0.5-Dil PLNPs enabled imaging of the HepG2 tumor and effectively guided tumor surgical resection verified by the H&E staining analysis. This strategy could be a significant reference in other dye-sensitization PLNPs to enhance longer-wavelength rechargeable PersL.

Linearly Interlinked Fe-Nx-Fe Single Atoms Catalyze High-Rate Sodium-Sulfur Batteries.

Linearly interlinked single atoms offer unprecedented physiochemical properties, but their synthesis for practical applications still poses significant challenges. Herein, linearly interlinked iron single-atom catalysts that are loaded onto interconnected carbon channels as cathodic sulfur hosts for room-temperature sodium-sulfur batteries are presented. The interlinked iron single-atom exhibits unique metallic iron bonds that facilitate the transfer of electrons to the sulfur cathode, thereby accelerating the reaction kinetics. Additionally, the columnated and interlinked carbon channels ensure rapid Na+ diffusion kinetics to support high-rate battery reactions. By combining the iron atomic chains and the topological carbon channels, the resulting sulfur cathodes demonstrate effective high-rate conversion performance while maintaining excellent stability. Remarkably, even after 5000 cycles at a current density of 10 A g-1, the Na-S battery retains a capacity of 325 mAh g-1. This work can open a new avenue in the design of catalysts and carbon ionic channels, paving the way to achieve sustainable and high-performance energy devices.

pH-Responsive Plasmon-Enhanced Persistent Luminescent ZnGa2O4:Cr3+ Nanopomegranate for Tumor Imaging.

Noble metal compositing is a promising method to enhance radiance intensity of persistent luminescent (PersL) nanoparticles (NPs) via surface plasmon resonance (SPR) for better tumor imaging, but it rarely unites with the pH-response strategy due to the challenge of realizing rigorous pH-responsive spatial distance control as a "button switch" of SPR. Here, ZnGa2O4:Cr3+ (ZGC) NPs as "pomegranate seeds" are cladded with sodium alginate to form nanoclusters (ZGC-SA), subsequently coated with carboxyl-rich polymers to acquire "pomegranate rind" (ZSPB) and finally decorated with 10 nm gold NPs (AuNPs) on the surface to obtain nanopomegranate structure (ZSPB@AuNPs). Though without deliberate distance control, there are plenty of "seeds" inside ZSPB@AuNPs fortunately at appropriate positions, which could be plasmon-enhanced by AuNPs. Furthermore, triggered by carboxyl protonation in subacid tumor, ZSPB@AuNPs aggregate and subsequently facilitate such plasmon enhancement effect, resulting in 4.4-fold PersL promotion at pH 5.5 (tumor microenvironment, TME) over pH 7.4 and in a maximum "tumor to normal tissue ratio" of PersL imaging signals of 125.9. Under surgical navigation of ZSPB@AuNPs, intramuscular tumors of mice could be resected without residue signals left. This nanopomegranate achieves TME pH-responsive plasmon-enhanced PersL for the first time and broadens the way for designing plasmon-enhanced PersL nanosystems.

A Reversible Six-Electron Transfer Cathode for Advanced Aqueous Zinc Batteries.

The electrochemical reactions for the storage of Zn2+ while embracing more electron transfer is a foundation of the future high-energy aqueous zinc batteries. Herein, we report a six-electron transfer electrochemistry of nano-sized TeO2 /C (n-TeO2 /C) cathode by facilitating the reversible conversion of TeO2 ↔Te and Te↔ZnTe. Benefitting from the integrated conductive nanostructure and the proton-rich environment in providing optimized electrochemical kinetics (facilitated Zn2+ uptake and high electronic conductivity) and feasible thermodynamic process (low Gibbs free energy change), the as-prepared n-TeO2 /C with stable cycling performance exhibits a superior reversible capacity of over 800 mAh g-1 at 0.1 A g-1 . A precise understanding of the reaction mechanism via ex situ and in situ characterizations presents that the reversible six-electron transfer reaction is proton-dependent, and a proton generating and consuming mechanism of three-phase conversion n-TeO2 /C in the weakly acidic electrolyte is thoroughly revealed.

Rationally Designed ZnTe@C Nanowires with Superior Zinc Storage Performance for Aqueous Zn Batteries.

Te-based materials with excellent electrical conductivity and ultra-high volume specific capacity have attracted much attention for the cost-efficient aqueous Zn batteries. However, the construction of functional structures with mild volume expansion and suppressed shuttle effects, enabling an expanded lifespan, is still a challenge for conversion-type materials. Herein, the carbon-coated zinc telluride nanowires (ZnTe@C NWs) are rationally designed as a high-performance cathode material for aqueous Zn batteries. The carbon-coated1D nanostructure could not only provide optimized transmission path for electrons and ions, but also help to maintain structure integrity upon volume variation and suppress intermediates dissolution, endowing the ZnTe@C NWs with improved cycling stability and reaction kinetics. Consequently, a reversible six-electron reaction mechanism of ZnTe@C NWs based on Te2- /Te4+ conversion with excellent output capacity (586 mAh g-1 at 0.1 A g-1 ) and lifespan (>250 mAh g-1 retained for 400 cycles at 1 A g-1 ) is eventually achieved.

Preparation of Bacillus-mimic liposomes destroying TAMs for the treatment of cancer.

The enrichment rate of drugs in tumors seriously affects the effect of tumor treatment. Tumor-associated macrophages (TAMs) could penetrate deeply into the tumor and accumulate in hypoxic areas. Therefore, using TAMs to deliver drugs can effectively increase the enrichment rate. However, as immune cell, macrophages will clear the internal drugs and their antitumor activity. Mycobacterium tuberculosis (M. tuberculosis) can inhibit the decomposition ability of TAMs and stay stable in macrophages. Herein, we prepared a Bacillus-mimic liposome by embedding the fragments of M. tuberculosis into the liposome. In vitro experiments showed that it can stay stable in TAMs for at least 29 h without decomposing. Then, TAMs would burst as they gobble up materials and cannot digest them. Thus, the prepared liposome could "domesticate" TAMs and kill macrophages after they are used up, further destroy the tumor microenvironment, and finally kill the tumor. Cytotoxicity experiments confirmed that it has a certain killing effect on macrophages, tumor cells, and normal cells. In vivo tumor suppression experiments confirmed that it has the effect of inhibiting tumor growth.

A novel removable template method for the preparation of persistent luminescence nanoparticles with biocompatible size and high intensity.

NIR persistent luminescence nanoparticles (PLNPs) are appealing for bio-imaging because of the properties of extremely low autofluorescence interference and deep tissue penetrating ability. However, current preparation methods can hardly simultaneously endow PLNPs with nano-scale size, long persistent luminescence (PersL) life, and high luminescence intensity, which can hardly meet the requirements of bio-imaging. Herein, we report a new synthetic route to nano-sized chromium-doped zinc gallate (ZGC) via a removable MOF template, i.e., one-pot hydrothermal synthesis of an intermediate followed by its calcination at 1100 °C in air. By exploiting the regulatory effect of the intermediate on Zn and Ga, the depth of traps in 170 nm-sized ZGC nanoparticles was enhanced to above 0.8 eV, and the PersL duration to more than 24 h, with an average lifetime of up to 216 s. An in vivo experiment shows that tumors can be accurately delineated for more than 3 hours. This strategy largely resolves the conflict between the particle size and PersL properties of PLNPs, and expands the application of PLNPs in bio-imaging.

Boosting Cathode Activity and Anode Stability of Zn-S Batteries in Aqueous Media Through Cosolvent-Catalyst Synergy.

Aqueous Zn-S battery with high energy density represents a promising large-scale energy storage technology, but its application is severely hindered by the poor reversibility of both S cathode and Zn anode. Herein, we develop a "cocktail optimized" electrolyte containing tetraglyme (G4) and water as co-solvents and I2 as additive. The G4-I2 synergy could activate efficient polar I3 - /I- catalyst couple and shield the cathode from water, thus facilitating the conversion kinetics of S and suppressing the interfacial side reactions. Simultaneously, it could stabilize Zn anode by forming an organic-inorganic interphase upon cycling. With boosted electrodes reversibility, the Zn-S cell delivers a high capacity of 775 mAh g-1 at 2 A g-1 , and retains over 70 % capacity after 600 cycles at 4 A g-1 . The advances can also be readily generalized to other ethers/water hybrid electrolytes, showing the universality of the "cocktail optimized" electrolyte design strategy.

PhyloPGM: boosting regulatory function prediction accuracy using evolutionary information.

MOTIVATION: The computational prediction of regulatory function associated with a genomic sequence is of utter importance in -omics study, which facilitates our understanding of the underlying mechanisms underpinning the vast gene regulatory network. Prominent examples in this area include the binding prediction of transcription factors in DNA regulatory regions, and predicting RNA-protein interaction in the context of post-transcriptional gene expression. However, existing computational methods have suffered from high false-positive rates and have seldom used any evolutionary information, despite the vast amount of available orthologous data across multitudes of extant and ancestral genomes, which readily present an opportunity to improve the accuracy of existing computational methods. RESULTS: In this study, we present a novel probabilistic approach called PhyloPGM that leverages previously trained TFBS or RNA-RBP binding predictors by aggregating their predictions from various orthologous regions, in order to boost the overall prediction accuracy on human sequences. Throughout our experiments, PhyloPGM has shown significant improvement over baselines such as the sequence-based RNA-RBP binding predictor RNATracker and the sequence-based TFBS predictor that is known as FactorNet. PhyloPGM is simple in principle, easy to implement and yet, yields impressive results. AVAILABILITY AND IMPLEMENTATION: The PhyloPGM package is available at https://github.com/BlanchetteLab/PhyloPGM. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.

Tumor acid microenvironment-activated self-targeting & splitting gold nanoassembly for tumor chemo-radiotherapy.

Low accumulation and penetration of nanomedicines in tumor severely reduce therapeutic efficacy. Herein, a pH-responsive gold nanoassembly is designed to overcome these problems. Polyethylene glycol linked raltitrexed (RTX, target ligand and chemotherapy drug) and two tertiary amine molecules (1-(2-aminoethyl) pyrrolidine and N, N-dibutylethylenediamine) are modified on the surface of the 6-nm gold nanoparticles by lipoic acid to form gold nanoassembly defined as Au-NNP(RTX). The Au-NNP (RTX) nanoassembly could remain at about 160 nm at the blood circulation (pH 7.4), while split into 6-nm gold nanoparticles due to tertiary amine protonation at tumor extracellular pH (pH 6.8). This pH-responsive disassembly behavior endows Au-NNP(RTX) better tumor tissue permeability through the better diffusion brought by the size reduction. Meanwhile, after disassembly, more RTXs on the surface of gold nanoparticles are exposed from the shielded state of assembly along with 2.25-fold augment of cellular uptake capability. Most importantly, the results show that Au-NNP(RTX) possesses of high tumor accumulation and effective tumor penetration, thereby enhancing the tumor chemo-radiotherapy efficiency.

Artificial interphase engineering to stabilize aqueous zinc metal anodes.

Aqueous Zn-ion system combining the advantages of energy density, intrinsic safety, and environmental benignity, has been regarded as a promising power source for future electronics. Besides cathodes and electrolytes, more attention should be paid to stabilizing zinc metal anodes since the main challenges in current aqueous Zn-ion batteries are still the hydrogen evolution and dendrite growth of the zinc anode. Thereupon, artificial interphase engineering that integrates the highly tunable, selectable, and controllable characteristics becomes one of the most effective ways to stabilize zinc anodes. In this mini-review, state-of-the-art knowledge on the rational interphase engineering of aqueous zinc metal anodes in the functional layer coating and in situ solid electrolyte interphase formation are covered. The main focus of this work is to summarize the most recent development of artificial interphases in chemical composition, structure, and function. The potential issues and perspectives regarding materials and methods are presented.

Activating Inert Surface Pt Single Atoms via Subsurface Doping for Oxygen Reduction Reaction.

The performance of single-atom catalysts strongly depends on their particular coordination environments in the near-surface region. Herein, we discover that engineering extra Pt single atoms in the subsurface (Ptsubsurf) can significantly enhance the catalytic efficiency of surface Pt single atoms toward the oxygen reduction reaction (ORR). We experimentally and theoretically investigated the effects of the Ptsubsurf single atoms implanted in different positions of the subsurface of Co particles. The local environments and catalytic properties of surface Pt1 are highly tunable via Ptsubsurf doping. Specifically, the obtained Pt1@Co/NC catalyst displays a remarkable performance for ORR, achieving mass activity of 4.2 mA µgPt-1 (28 times higher than that of commercial Pt/C) at 0.9 V versus reversible hydrogen electrode (RHE) in 0.1 M HClO4 solution with high stability over 30000 cycles.

Epitaxial Nickel Ferrocyanide Stabilizes Jahn-Teller Distortions of Manganese Ferrocyanide for Sodium-Ion Batteries.

Manganese-based Prussian Blue, Na2-δ Mn[Fe(CN)6 ] (MnPB), is a good candidate for sodium-ion battery cathode materials due to its high capacity. However, it suffers from severe capacity decay during battery cycling due to the destabilizing Jahn-Teller distortions it undergoes as Mn2+ is oxidized to Mn3+ . Herein, the structure is stabilized by a thin epitaxial surface layer of nickel-based Prussian Blue (Na2-δ Ni[Fe(CN)6 ]). The one-pot synthesis relies on a chelating agent with an unequal affinity for Mn2+ and Ni2+ ions, which prevents Ni2+ from reacting until the Mn2+ is consumed. This is a new and simpler synthesis of core-shell materials, which usually needs several steps. The material has an electrochemical capacity of 93 mA h g-1 , of which it retains 96 % after 500 charge-discharge cycles (vs. 37 % for MnPB). Its rate capability is also remarkable: at 4 A g-1 (ca. 55 C) it can reversibly store 70 mA h g-1 , which is also reflected in its diffusion coefficient of ca. 10-8  cm2 s-1 . The epitaxial outer layer appears to exert an anisotropic strain on the inner layer, preventing the Jahn-Teller distortions it normally undergoes during de-sodiation.

Tunable Electrocatalytic Behavior of Sodiated MoS2 Active Sites toward Efficient Sulfur Redox Reactions in Room-Temperature Na-S Batteries.

Room-temperature (RT) sodium-sulfur (Na-S) batteries hold great promise for large-scale energy storage due to the advantages of high energy density, low cost, and resource abundance. The research progress on RT Na-S batteries, however, has been greatly hindered by the sluggish kinetics of the sulfur redox reactions. Herein, an elaborate multifunctional architecture, consisting of N-doped carbon skeletons and tunable MoS2 sulfiphilic sites, is fabricated via a simple one-pot reaction followed by in situ sulfurization. Beyond the physical confinement and chemical binding of polarized N-doped carbonaceous microflowers, the MoS2 active sites play a key role in catalyzing polysulfide redox reactions, especially the conversion from long-chain Na2 Sn (4 ≤ n ≤ 8) to short-chain Na2 S2 and Na2 S. Significantly, the electrocatalytic activity of MoS2 can be tunable via adjusting the discharge depth. It is remarkable that the sodiated MoS2 exhibits much stronger binding energy and electrocatalytic behavior compared to MoS2 sites, effectively enhancing the formation of the final Na2 S product. Consequently, the S cathode achieves superior electrochemical performance in RT Na-S batteries, delivering a high capacity of 774.2 mAh g-1 after 800 cycles at 0.2 A g-1 , and an ultrahigh capacity retention with a capacity decay rate of only 0.0055% per cycle over 2800 cycles.

Graph neural representational learning of RNA secondary structures for predicting RNA-protein interactions.

MOTIVATION: RNA-protein interactions are key effectors of post-transcriptional regulation. Significant experimental and bioinformatics efforts have been expended on characterizing protein binding mechanisms on the molecular level, and on highlighting the sequence and structural traits of RNA that impact the binding specificity for different proteins. Yet our ability to predict these interactions in silico remains relatively poor. RESULTS: In this study, we introduce RPI-Net, a graph neural network approach for RNA-protein interaction prediction. RPI-Net learns and exploits a graph representation of RNA molecules, yielding significant performance gains over existing state-of-the-art approaches. We also introduce an approach to rectify an important type of sequence bias caused by the RNase T1 enzyme used in many CLIP-Seq experiments, and we show that correcting this bias is essential in order to learn meaningful predictors and properly evaluate their accuracy. Finally, we provide new approaches to interpret the trained models and extract simple, biologically interpretable representations of the learned sequence and structural motifs. AVAILABILITY AND IMPLEMENTATION: Source code can be accessed at https://www.github.com/HarveyYan/RNAonGraph. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.

Multiregion Janus-Featured Cobalt Phosphide-Cobalt Composite for Highly Reversible Room-Temperature Sodium-Sulfur Batteries.

Electrode materials with high conductivity, strong chemisorption, and catalysis toward polysulfides are recognized as key factors for metal-sulfur batteries. Nevertheless, the construction of such functional material is a challenge for room-temperature sodium-sulfur (RT-Na/S) batteries. Herein, a multiregion Janus-featured CoP-Co structure obtained via sequential carbonization-oxidation-phosphidation of heteroseed zeolitic imidazolate frameworks is introduced. The structural virtues include a heterostructure existing in a CoP-Co structure and a conductive network of N-doped porous carbon nanotube hollow cages (NCNHCs), endowing it with superior conductivity in both the short- and long-range and strong polarity toward polysulfides. Thus, the S@CoP-Co/NCNHC cathode exhibits superior electrochemical performance (448 mAh g-1 remained for 700 times cycling under 1 A g-1) and an optimized redox mechanism in polysulfides conversion. Density functional theory calculations present that the CoP-Co structure optimizes bond structure and bandwidth, whereas the pure CoP is lower than the corresponding Fermi level, which could essentially benefit the adsorptive capability and charge transfer from the CoP-Co surface to Na2Sx and therefore improve its affinity to polysulfides.

General Synthesis of Single-Atom Catalysts for Hydrogen Evolution Reactions and Room-Temperature Na-S Batteries.

Herein, we report a comprehensive strategy to synthesize a full range of single-atom metals on carbon matrix, including V, Mn, Fe, Co, Ni, Cu, Ge, Mo, Ru, Rh, Pd, Ag, In, Sn, W, Ir, Pt, Pb, and Bi. The extensive applications of various SACs are manifested via their ability to electro-catalyze typical hydrogen evolution reactions (HER) and conversion reactions in novel room-temperature sodium sulfur batteries (RT-Na-S). The enhanced performances for these electrochemical reactions arisen from the ability of different single active atoms on local structures to tune their electronic configuration. Significantly, the electrocatalytic behaviors of diverse SACs, assisted by density functional theory calculations, are systematically revealed by in situ synchrotron X-ray diffraction and in situ transmission electronic microscopy, providing a strategic library for the general synthesis and extensive applications of SACs in energy conversion and storage.

Electrocatalyzing S Cathodes via Multisulfiphilic Sites for Superior Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur (RT-Na/S) batteries hold great promise for sustainable and cost-effective applications. Nevertheless, it remains a great challenge to achieve high capacity and cycling stability due to the low activity of sulfur and the sluggish conversion kinetics between polysulfide intermediates and sodium sulfide. Herein, an electrocatalyzing S cathode is fabricated, which consists of porous core-shell structure and multisulfiphilic sites. The flexible carbon structure effectively buffers volume changes during cycling and provides enclosed spaces to store S8 with exceptional conductivity. Significantly, the multisulfiphilic sites (ZnS and CoS2) enhance catalysis toward multistep S conversion, which effectively suppresses long-chain polysulfides dissolution and improves the kinetics of short-chain polysulfides. Thus, the obtained S cathodes achieve an enhanced cycling performance (570 mAh g-1 at 0.2 A g-1 over 1000 cycles), decent rate capability (250 mAh g-1 at 1.0 A g-1 over 2000 cycles), and high energy density of 384 Wh kg-1 toward practical applications.

Reversible structural evolution of sodium-rich rhombohedral Prussian blue for sodium-ion batteries.

Iron-based Prussian blue analogs are promising low-cost and easily prepared cathode materials for sodium-ion batteries. Their materials quality and electrochemical performance are heavily reliant on the precipitation process. Here we report a controllable precipitation method to synthesize high-performance Prussian blue for sodium-ion storage. Characterization of the nucleation and evolution processes of the highly crystalline Prussian blue microcubes reveals a rhombohedral structure that exhibits high initial Coulombic efficiency, excellent rate performance, and cycling properties. The phase transitions in the as-obtained material are investigated by synchrotron in situ powder X-ray diffraction, which shows highly reversible structural transformations between rhombohedral, cubic, and tetragonal structures upon sodium-ion (de)intercalations. Moreover, the Prussian blue material from a large-scale synthesis process shows stable cycling performance in a pouch full cell over 1000 times. We believe that this work could pave the way for the real application of Prussian blue materials in sodium-ion batteries.

A High-Kinetics Sulfur Cathode with a Highly Efficient Mechanism for Superior Room-Temperature Na-S Batteries.

Applications of room-temperature-sodium sulfur (RT-Na/S) batteries are currently impeded by the insulating nature of sulfur, the slow redox kinetics of sulfur with sodium, and the dissolution and migration of sodium polysulfides. Herein, a novel micrometer-sized hierarchical S cathode supported by FeS2 electrocatalyst, which is grown in situ in well-confined carbon nanocage assemblies, is presented. The hierarchical carbon matrix can provide multiple physical entrapment to polysulfides, and the FeS2 nanograins exhibit a low Na-ion diffusion barrier, strong binding energy, and high affinity for sodium polysulfides. Their combination makes it an ideal sulfur host to immobilize the polysulfides and achieve reversible conversion of polysulfides toward Na2 S. Importantly, the hierarchical S cathode is suitable for large-scale production via the inexpensive and green spray-drying method. The porous hierarchical S cathode offers a high sulfur content of 65.5 wt%, and can deliver high reversible capacity (524 mAh g-1 over 300 cycles at 0.1 A g-1 ) and outstanding rate capability (395 mAh g-1 at 1 A g-1 for 850 cycles), holding great promise for both scientific research and real application.