KMT2D mutations promoted tumor progression in diffuse large B-cell lymphoma through altering tumor-induced regulatory T cell trafficking via FBXW7-NOTCH-MYC/TGF-ß1 axis.

Histone methyltransferase KMT2D is one of the most frequently mutated genes in diffuse large B-cell lymphoma (DLBCL) and has been identified as an important pathogenic factor and prognostic marker. However, the biological relevance of KMT2D mutations on tumor microenvironment remains to be determined. KMT2D mutations were assessed by whole-genome/exome sequencing (WGS/WES) in 334 patients and by targeted sequencing in 427 patients with newly diagnosed DLBCL. Among all 761 DLBCL patients, somatic mutations in KMT2D were observed in 143 (18.79%) patients and significantly associated with advanced Ann Arbor stage and MYC expression ≥ 40%, as well as inferior progression-free survival and overall survival. In B-lymphoma cells, the mutation or knockdown of KMT2D inhibited methylation of lysine 4 on histone H3 (H3K4), downregulated FBXW7 expression, activated NOTCH signaling pathway and downstream MYC/TGF-ß1, resulting in alterations of tumor-induced regulatory T cell trafficking. In B-lymphoma murine models established with subcutaneous injection of SU-DHL-4 cells, xenografted tumors bearing KMT2D mutation presented lower H3K4 methylation, higher regulatory T cell recruitment, thereby provoking rapid tumor growth compared with wild-type KMT2D via FBXW7-NOTCH-MYC/TGF-ß1 axis.

Targeted agents plus CHOP compared with CHOP as the first-line treatment for newly diagnosed patients with peripheral T-cell lymphoma (GUIDANCE-03): an open-label, multicentre phase 2 clinical trial.

Background: Peripheral T-cell lymphoma (PTCL) is a heterogeneous disease with dismal outcomes. We conducted an open-label, phase 2 nonrandomised, externally controlled study to evaluate the efficacy and safety of targeted agents plus CHOP (cyclophosphamide, doxorubicin, vincristine, and prednisolone) (CHOPX) for PTCL in the front-line setting. Methods: Eligible patients were ≥18 years of age and newly diagnosed PTCL. Patients in the CHOPX group received standard CHOP at Cycle 1. Specific targeted agents were added from Cycle 2, decitabine if TP53 mut, azacytidine if TET2/KMT2D mut, tucidinostat if CREBBP/EP300 mut, and lenalidomide if without mutations above. Patients in the CHOP group received CHOP for 6 cycles. The primary endpoint was the complete response rate (CRR) at the end of treatment (EOT). Secondary endpoints included overall response rate (ORR), progression-free survival (PFS), overall survival (OS), and safety. The study was registered with ClinicalTrials.gov, NCT04480099. Findings: Between July 29, 2020, and Sep 22, 2022, 96 patients were enrolled and included for efficacy and safety analysis with 48 in each group. The study met its primary endpoint. CRR at EOT in the CHOPX group was superior to the CHOP group (64.6% vs. 33.3%, OR 0.27, 95%CI 0.12-0.64; p = 0.004). At a median follow-up of 24.3 months (IQR 12.0-26.7), improved median PFS was observed in the CHOPX group (25.5 vs. 9.0 months; HR 0.57, 95%CI 0.34-0.98; p = 0.041). The median OS was similar between two groups (not reached vs. 30.9 months; HR 0.55, 95%CI 0.28-1.10; p = 0.088). The most common grade 3-4 hematological and non-hematological adverse events in the CHOPX group were neutropenia (31, 65%) and infection (5, 10%). Interpretation: Targeted agents combined with CHOP demonstrated effective and safe as first-line treatment in PTCL. Biomarker-driven therapeutic strategy is feasible and may lead to promising efficacy specifically toward molecular features in PTCL. Funding: This study was supported by the National Key Research and Development Program (2022YFC2502600) and the General Program of the Shanghai Municipal Health Commission (202040400).

Enhanced boron removal via seed-induced crystal growth of barium perborate in sequential fluidized-bed crystallization.

Chemical oxo-precipitation (COP) is an enhanced precipitation method for boron removal with the conversion of boric acid to perborate anions. When using barium-based precipitant, the boron can be effectively precipitated as barium perborates (BaPBs). The phase transformation of BaPBs from amorphous (A-BaPB, Ba(B(OH)3OOH)2) to crystalline (C-BaPB, BaB2(OO)2(OH)4) form is crucial for effective boron removal. However, scaling up this phase transformation of BaPBs is hindered by poor diffusion. This study aims to promote the growth of C-BaPB through seed-induced crystal growth, eliminating the need for phase transformation. By examining the relationship between crystal growth rate and supersaturation, surface spiral growth was identified as the rate-limiting step of the growth of micron-sized seeds near pHpzc. To enable continuous crystal growth, granular seeds of C-BaPB were prepared and employed as the medium for fluidized-bed crystallization (FBC). The system reached steady state 3 hydraulic retention times, achieving 90% boron removal. The effect of surface loading, ionic strength, and dosages on steady-state crystal growth rate was studied, revealing a shift of the rate-limiting step in FBC to diffusion. Lastly, the system that constituted of two FBCs in-series for sequential crystallization of A-BaPB and C-BaPB was demonstrated. The integrated system provided 97.8% of boron removal from synthetic wastewater containing 500 mg-B/L, with 92.3% of boron crystallized on the granular seeds of BaPBs.

Exciton Dissociation into Charge Carriers in Porphyrinic Metal-Organic Frameworks for Light-Assisted Li-O2 Batteries.

Light-assisted Li-O2 batteries exhibit a high round-trip efficiency attributable to the assistance of light-generated electrons and holes in oxygen reduction and evolution reactions. Nonetheless, the excitonic effect arising from Coulomb interaction between electrons and holes impedes carrier separation, thus hindering efficient utilization of photo-energy. Herein, porphyrinic metal-organic frameworks with (Fe2Ni)O(COO)6 clusters are used as photocathodes to accelerate exciton dissociation into charge carriers for light-assisted Li-O2 batteries. The coupling of Ni 3d and Fe 3d orbitals boosts ligand-to-metal cluster charge transfer, and hence drives exciton dissociation and activates O2 for superoxide (•O2 -) radicals, rather than singlet oxygen (1O2) under photoexcitation. These enable the light-assisted Li-O2 batteries with a low total overvoltage of 0.28 V and round-trip efficiency of 92% under light irradiation of 100 mW cm-2. This work highlights the excitonic effect in photoelectrochemical processes and provides insights into photocathode design for light-assisted Li-O2 batteries.

Surface Coordination Modulated Morphological Anisotropic Engineering of Iron-Benzoquinone Frameworks for Lithium-Ion Batteries.

Morphological anisotropic engineering is powerful to synthesize metal-organic frameworks (MOFs) with versatile physicochemical properties for diverse applications ranging from gas storage/separation to electrocatalysis and batteries, etc. Herein, we developed a carbon substrate guided strategy to manipulate the facet-dependent coordination for morphology engineering of Fe-THBQ (tetrahydroxy-1,4-benzoquinone) frameworks, which is built with cubic Fe octamer bridged by two parallel THBQ ligands along three orthogonal axes, extending to a three-dimensional (3D) framework with pcu-e network topology. The electronegative O-containing functional groups on carbon surfaces compete with THBQ linkers to selectively interact with the unsaturated coordinated Fe cations on the {111} facets and inhibit crystal growth along the <111> direction. The morphology of Fe-THBQ evolves from thermodynamically favored truncated cube to cuboctahedron depending on the content of O-containing functional groups on the carbon substrate. The Fe-THBQ with varied morphologies exhibits facet-dependent performances for electrochemical lithium storage. This work will shed light on the morphology modulation of MOFs for promising applications.

Application of fluidized bed homogeneous crystallization for simultaneous recovery of Fe(II) and Cu(II) as particles from wastewater.

The mixture of copper and iron often results in materials with favorable properties. The material production processes involving these metals including electroplating produce hazardous wastewater. In this study, the Fluidized Bed Homogeneous Crystallization (FBHC) process was applied to treat iron and copper-containing wastewater. The initial iron copper particles were successfully recovered from synthetic wastewater with [Fe]0:[Cu]0 of 2:1, the total metal concentration of 3 mM, at effluent pH = 7.75 ± 0.75, with the upflow velocity (U) of 1.76 m/h. The agglomerates hardening process is a crucial step for initial particle synthesis. The SEM analysis reveals the spherical particle's densified crust and porous core. The particle formation mechanism which includes the formation of the nucleus, attachment of precipitate flakes, and densification of particles was proposed after microscopic observation. The initial particles synthesized were used to initiate the treatment of synthetic wastewater at the operating condition pH = 7.75 ± 0.5, [Fe]0:[Cu]0 of 2:1, the total metal concentration of 3 mM, [CO32-]0:[M]0 = 1.2:1, and U of 28.66 m/h which results in the total metal removal of 99% and crystallization ratio of 90% and 88% for iron and copper respectively. The conditions were then applied to treat electroplating wastewater and resulted in the total metal removal of 99% for both iron and copper and a crystallization ratio of 83% and 79% for iron and copper, respectively. The treatment provided advantages in terms of treating larger amounts of sludge while eliminating the need to provide seed thus yielding a higher purity of product.

Genomic and transcriptomic profiling of peripheral T cell lymphoma reveals distinct molecular and microenvironment subtypes.

Peripheral T cell lymphoma (PTCL) is a heterogeneous group of non-Hodgkin's lymphomas varying in clinical, phenotypic, and genetic features. The molecular pathogenesis and the role of the tumor microenvironment in PTCL are poorly understood, with limited biomarkers available for genetic subtyping and targeted therapies. Through an integrated genomic and transcriptomic study of 221 PTCL patients, we delineate the genetic landscape of PTCL, enabling molecular and microenvironment classification. According to the mutational status of RHOA, TET2, histone-modifying, and immune-related genes, PTCL is divided into 4 molecular subtypes with discrete patterns of gene expression, biological aberrations, and vulnerabilities to targeted agents. We also perform an unsupervised clustering on the microenvironment transcriptional signatures and categorize PTCL into 4 lymphoma microenvironment subtypes based on characteristic activation of oncogenic pathways and composition of immune communities. Our findings highlight the potential clinical rationale of future precision medicine strategies that target both molecular and microenvironment alterations in PTCL.

Regulating Ion-Dipole Interactions in Weakly Solvating Electrolyte towards Ultra-Low Temperature Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are recognized as promising energy storage devices. However, they suffer from rapid capacity decay at ultra-low temperatures due to high Na+ desolvation energy barrier and unstable solid electrolyte interphase (SEI). Herein, a weakly solvating electrolyte (WSE) with decreased ion-dipole interactions is designed for stable sodium storage in hard carbon (HC) anode at ultra-low temperatures. 2-methyltetrahydrofuran with low solvating power is incorporated into tetrahydrofuran to regulate the interactions between Na+ and solvents. The reduced Na+-dipole interactions facilitate more anionic coordination in the first solvation sheath, which consistently maintains anion-enhanced solvation structures from room to low temperatures to promote inorganic-rich SEI formation. These enable WSE with a low freezing point of -83.3 °C and faster Na+ desolvation kinetics. The HC anode thus affords reversible capacities of 243.2 and 205.4 mAh g-1 at 50 mA g-1 at -40 and -60 °C, respectively, and the full cell of HC||Na3V2(PO4)3 yields an extended lifespan over 250 cycles with high capacity retention of ~100 % at -40 °C. This work sheds new lights on the ion-dipole regulation for ultra-low temperature SIBs.

Regulation of anion-Na+ coordination chemistry in electrolyte solvates for low-temperature sodium-ion batteries.

High-performance sodium storage at low temperature is urgent with the increasingly stringent demand for energy storage systems. However, the aggravated capacity loss is induced by the sluggish interfacial kinetics, which originates from the interfacial Na+ desolvation. Herein, all-fluorinated anions with ultrahigh electron donicity, trifluoroacetate (TFA-), are introduced into the diglyme (G2)-based electrolyte for the anion-reinforced solvates in a wide temperature range. The unique solvation structure with TFA- anions and decreased G2 molecules occupying the inner sheath accelerates desolvation of Na+ to exhibit decreased desolvation energy from 4.16 to 3.49 kJ mol-1 and 24.74 to 16.55 kJ mol-1 beyond and below -20 °C, respectively, compared with that in 1.0 M NaPF6-G2. These enable the cell of Na||Na3V2(PO4)3 to deliver 60.2% of its room-temperature capacity and high capacity retention of 99.2% after 100 cycles at -40 °C. This work highlights regulation of solvation chemistry for highly stable sodium-ion batteries at low temperature.

Negative Lattice Expansion in an O3-Type Transition-Metal Oxide Cathode for Highly Stable Sodium-Ion Batteries.

The sodium extraction/insertion in layered transition-metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni-based layered cathode of Na0.9 Ni0.32 Zn0.08 Fe0.1 Mn0.3 Ti0.2 O2 upon Na+ extraction. It is attributed to the weak Zn2+ -O2- orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O-O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti-O bonds accommodate the internal distortion of TMO6 octahedra due to the flexibility of TiO6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g-1 and excellent cycling performance of pouch-type sodium-ion batteries with 93 % capacity retention after 3600 cycles.

New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li-O2 Batteries.

Aprotic Li-O2 battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O2 - ) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O2 - disproportionation and its kinetics in both the discharge and charge processes. RB captures O2 - dimer and promotes their intramolecular charge transfer, and it decreases the energy barrier of the disproportionation reaction from 7.70 to 0.70 kcal mol-1 . This facilitates the discharge and charge processes and simultaneously mitigates O2 - and singlet oxygen related side reactions. These endow the Li-O2 battery with reduced discharge/charge voltage gap of 0.72 V and prolonged lifespan for over 230 cycles when coupled with RuO2 catalyst. This work highlights the vital role of superoxide disproportionation for Li-O2 battery.

ABCF1/CXCL12/CXCR4 Enhances Glioblastoma Cell Proliferation, Migration, and Invasion by Activating the PI3K/AKT Signal Pathway.

Glioblastoma (GBM) is the most prevalent and fatal form of brain tumor, which is associated with a poor prognosis. ATP-binding cassette subfamily F member 1 (ABCF1) is an E2 ubiquitin-conjugating enzyme, which is implicated in regulating immune responses and tumorigenesis. Aberrant E3 ubiquitylation has been evidenced in GBM. However, the role of ABCF1 in GBM needs to be further explored. The expression of ABCF1, CXC chemokine ligand 12 (CXCL12), and CXC chemokine receptor 4 (CXCR4) in GBM tissues was examined by the GEPIA tool, real-time PCR and Western blotting. HMC3, U251MG, and LN-229 cells were cultured and transfected with shRNA targeting ABCF1 and ABCF1 plasmids. The proliferative, migrative, and invasive ability of cells was detected. Western blotting was used to detect the levels of phosphorylated phosphatidylinositol 3-kinase (PI3K) and phosphorylated protein kinase B (AKT). We observed that GBM tissues had higher ABCF1, CXCL12, and CXCR4 expression levels. The expression levels of CXCL12 and CXCR4 were enhanced by ABCF1 overexpression, which were significantly reversed by silence of ABCF1 in GBM cells. Silencing ABCF1 or CXCR4 inhibition weakened the capacity of GBM cell growth, migration, and invasion, while ectopic ABCF1 expression or CXCL12 treatment enhanced the cellular function of GBM cells. Furthermore, p-PI3K and p-AKT protein levels were downregulated by ABCF1 knockdown or CXCR4 blockade, which were prompted by ABCF1 overexpression or CXCL12 supplement. The ABCF1-CXCL12-CXCR4 axis was identified as a key player in GBM cell survival and metastasis by activating the PI3K/AKT signaling pathway in GBM cells.

Application of Fe0.66Cu0.33@Al(OH)3 catalyst from fluidized-bed crystallizer by-product for RB5 azo dye treatment using visible light-assisted photo-Fenton technology.

This study aims to explore the reusability of wastewater treatment by-product for photo-Fenton process to treat an organic pollutant model. The optimal condition, reactive oxygen species (ROS), and kinetic approach in photo-Fenton process was discussed. The Metal oxide crystal pellets from are a by-product of the Fluidized-Bed Crystallization (FBC) process and can be used as a catalyst in the Photo-Fenton process. Electroplating wastewater containing iron and copper was treated via the FBC process using granulated Al(OH)3 as carrier seeds. The binary oxide of FeOOH and Cu2O on the Al(OH)3 surface (Fe0.66Cu0.33@Al(OH)3) was identified as the FBC by-product after characterization using FTIR and XPS analysis. In the photo-Fenton process, visible light from a fluorescence lamp with a wavelength of 400-610 nm was chosen as an irradiation source. Oxalic acid was added as chelating agent to form photosensitive iron oxalate species and hydrogen peroxide was applied as oxidant to generate active radical to decolorize and mineralize RB5 synthesized solution (100 mg/L). The operating conditions including the oxalic acid to pollutant ratio ([OA]0/[RB5]0) of 4.5-13.0, reaction pH (pHr) of 3-7 and initial to theoretical hydrogen peroxide molar ratio [H2O2]0/[ H2O2]theoretical of 35%-120% were optimized. Under the optimal conditions, pHr = 5.0; [H2O2]0/[RB5]0 at 75% stoichiometric and [OA]0/[RB5]0 = 9, the RB5 is almost completely decolorized after 210 min of operation and the mineralization efficiency is 58%. The contribution of •OH, O2•-, and O21 to the Photo-Fenton system was determined using ESR analysis with the addition of DMPO and TEMP as spin trap agents. The kinetic analysis reveals the observed rate constants kRB5, kOA and kR from fitting are 0.0120, 0.0054 and 0.0001 M-1s-1, respectively.

Whole-Voltage-Range Solid-Solution Reaction in Layered Oxide Cathode of Sodium-Ion Batteries.

Layered manganese-based oxides (LMOs) are promising cathode materials for sodium-ion batteries (SIBs) due to their versatile structures. However, the Jahn-Teller effect of Mn3+ induces severe distortion of MnO6 octahedra, and the resultant low symmetry is responsible for the gliding of MnO2 layers and then inferior multiple-phase transitions upon Na+ extraction/insertion. Here, hexagonal P2-Na0.643 Li0.078 Mn0.827 Ti0.095 O2 is synthesized through the incorporation of Li and Ti into the distorted orthorhombic P'2-Na0.67 MnO2 to function as a phase-transition-free oxide cathode. It is revealed that Li in both the transition-metal and Na layers enhances the covalency of Mn-O bonds and allows degeneracy of Mn 3d eg orbitals to favor the formation of hexagonal phase, and the high strength of Ti-O bonds reduces the electrostatic interaction between Na and O for suppressed Na+ /vacancy rearrangements. These collectively lead to a whole-voltage-range solid-solution reaction between 1.8 and 4.3 V with a small volume variation of 1.49%. This rewards its excellent cycling stability (capacity retention of 90% after 500 cycles) and rate capability (89 mAh g-1 at 2000 mA g-1 ).

Heterogeneous temporal representation for diabetic blood glucose prediction.

Background and aims: Blood glucose prediction (BGP) has increasingly been adopted for personalized monitoring of blood glucose levels in diabetic patients, providing valuable support for physicians in diagnosis and treatment planning. Despite the remarkable success achieved, applying BGP in multi-patient scenarios remains problematic, largely due to the inherent heterogeneity and uncertain nature of continuous glucose monitoring (CGM) data obtained from diverse patient profiles. Methodology: This study proposes the first graph-based Heterogeneous Temporal Representation (HETER) network for multi-patient Blood Glucose Prediction (BGP). Specifically, HETER employs a flexible subsequence repetition method (SSR) to align the heterogeneous input samples, in contrast to the traditional padding or truncation methods. Then, the relationships between multiple samples are constructed as a graph and learned by HETER to capture global temporal characteristics. Moreover, to address the limitations of conventional graph neural networks in capturing local temporal dependencies and providing linear representations, HETER incorporates both a temporally-enhanced mechanism and a linear residual fusion into its architecture. Results: Comprehensive experiments were conducted to validate the proposed method using real-world data from 112 patients in two hospitals, comparing it with five well-known baseline methods. The experimental results verify the robustness and accuracy of the proposed HETER, which achieves the maximal improvement of 31.42%, 27.18%, and 34.85% in terms of MAE, MAPE, and RMSE, respectively, over the second-best comparable method. Discussions: HETER integrates global and local temporal information from multi-patient samples to alleviate the impact of heterogeneity and uncertainty. This method can also be extended to other clinical tasks, thereby facilitating efficient and accurate capture of crucial pattern information in structured medical data.

Photocatalytic oxidation of Reactive Red 195 by bimetallic Fe-Co catalyst: Statistical modeling and optimization via Box-Behnken design.

Response surface methodology (RSM) is an effective tool for process optimization with multi-complex operational factors. The present work aims to model and optimize the photocatalytic oxidation (PCO) parameters of Reactive Red 195 (RR195) dye decoloration with the SiO2-supported Fe-Co catalyst (FCS) derived from a novel catalyst synthesis method, fluidized-bed crystallization (FBC) process, using Box-Behnken design (BBD) as the RSM statistical model. The Fe-Co@SiO2 catalyst was successfully fabricated using the FBC process, and it showed good catalytic activity and performance toward the degradation of RR195. The extent of the effects of pH, H2O2 dosage (HD), catalyst loading (CL), and operating time (t) on the decoloration of RR195 was studied. Hence, the order of variable significance follows the sequence: pH > t > CL > HD. pH has the most significant effect among the variables for RR195 decoloration. The decoloration efficiency predicted by the BBD model was 88.3% under the optimized operation conditions of initial pH of 3.15, 0.76 mM H2O2, 1.18 g L-1 FCS and 59.4 min of operating time. The actual decoloration efficiency was very close to the predicted value indicating that BBD can efficiently be utilized to optimize RR195 degradation with FCS under the PCO system.

Sulfide recovery using fluidized bed homogeneous crystallization technology to produce nickel sulfide from wastewater that contains sulfides.

Sulfide-containing wastewater, characterized by its foul odor, corrosiveness, and toxicity, can endanger human health. Fluidized-bed homogeneous crystallization (FBHC) avoids the excessive sludge production commonly associated with conventional chemical precipitation methods. In this study, FBHC is used to treat sulfur-containing synthetic wastewater. Furthermore, nickel-containing wastewater was utilized as a precipitant in the system, hence the advantage of simultaneous sulfur and nickel removal from the wastewater. The operating parameters, including pH, a precipitant dosage of [Ni2+]0/[S2-]0, and cross-sectional surface loading (LS, kg/m2h) are optimized. The optimum operating conditions of pH 9.8 ± 0.3, [Ni2+]0/[S2-]0 = 0.8, and LS = 1.5 kg/m2h results in total sulfur removal (TR) of 95.7% and crystallization ratio (CR) of 94.8%. The effect of organic compounds (acetic acid, oxalic acid, EDTA, and citric acid) and inorganic ions (NO3-, CO32-, PO43-, F-, and Cl-) on the nickel sulfide granulation process was discussed.

Visible-Light-Responsive 2D Photocatalysts Assembled by Evans-Showell-Type POMs and Metalloviologen Frameworks for Sulfide-Sulfoxide Transformation.

Sulfide-sulfoxide aerobic photo-oxidation is of great interest in organic and medicinal chemistry; however, developing efficient and facile heterogeneous photocatalytic systems without additional additives remains challenging. Herein, we intentionally designed and synthesized two polyoxometalate (POM)-based metalloviologen frameworks, formulated as [MII(4-PBPY)2(H2O)][MII(H2O)4][CoIII2MoVI10H4O38]·nH2O (M = Cu, n = 10 for 1; M = Co, n = 11 for 2), prepared by the mild one-step synthesis strategy and characterized in detail. X-ray single-crystal diffraction analysis shows that they present a two-dimensional layered structure formed by two parallel metalloviologen layers pillared by dimeric Evans-Showell-type POMs. The connection of POM to the metalloviologen framework enables easier flow of electrons to the POM port, which can theoretically further induce O2 to generate reactive oxygen species (O2•-) to oxidize substrates to form target products. As expected, both 1 and 2 exhibit outstanding photocatalytic activity in the oxidation of sulfides. Within 6 h, methyl phenyl sulfide can be quantitatively converted into methyl phenyl sulfoxide. The in-depth mechanism reveals that there is also a synergistic energy-transfer pathway in the catalytic system in addition to the electron-transfer pathway. In addition, the corresponding catalytic activity and structure can be well maintained after at least 10 cycle experiments.

Solvation Structure with Enhanced Anionic Coordination for Stable Anodes in Lithium-Oxygen Batteries.

Li-O2 batteries have garnered much attention due to their high theoretical energy density. However, the irreversible lithium plating/stripping on the anode limits their performance, which has been paid little attention. Herein, a solvation-regulated strategy for stable lithium anodes in tetraethylene glycol dimethyl ether (G4) based electrolyte is attempted in Li-O2 batteries. Trifluoroacetate anions (TFA- ) with strong Li+ affinity are incorporated into the lithium bis(fluorosulfonyl)imide (LiTFSI)/G4 electrolyte to attenuate the Li+ -G4 interaction and form anion-dominant solvates. The bisalt electrolyte with 0.5 M LiTFA and 0.5 M LiTFSI mitigates G4 decomposition and induces an inorganic-rich solid electrolyte interphase (SEI). This contributes to decreased desolvation energy barrier from 58.20 to 46.31 kJ mol-1 , compared with 1.0 M LiTFSI/G4, for facile interfacial Li+ diffusion and high efficiency. It yields extended lifespan of 120 cycles in Li-O2 battery with a limited Li anode (7 mAh cm-2 ). This work gains comprehensive insights into rational electrolyte design for Li-O2 batteries.

Immunosuppressive tumor microenvironment contributes to tumor progression in diffuse large B-cell lymphoma upon anti-CD19 chimeric antigen receptor T therapy.

Anti-CD19 chimeric antigen receptor (CAR)-T cell therapy has achieved 40%-50% long-term complete response in relapsed or refractory diffuse large B-cell lymphoma (DLBCL) patients. However, the underlying mechanism of alterations in the tumor microenvironments resulting in CAR-T cell therapy failure needs further investigation. A multi-center phase I/II trial of anti-CD19 CD28z CAR-T (FKC876, ChiCTR1800019661) was conducted. Among 22 evaluable DLBCL patients, seven achieved complete remission, 10 experienced partial remissions, while four had stable disease by day 29. Single-cell RNA sequencing results were obtained from core needle biopsy tumor samples collected from long-term complete remission and early-progressed patients, and compared at different stages of treatment. M2-subtype macrophages were significantly involved in both in vivo and in vitro anti-tumor functions of CAR-T cells, leading to CAR-T cell therapy failure and disease progression in DLBCL. Immunosuppressive tumor microenvironments persisted before CAR-T cell therapy, during both cell expansion and disease progression, which could not be altered by infiltrating CAR-T cells. Aberrant metabolism profile of M2-subtype macrophages and those of dysfunctional T cells also contributed to the immunosuppressive tumor microenvironments. Thus, our findings provided a clinical rationale for targeting tumor microenvironments and reprogramming immune cell metabolism as effective therapeutic strategies to prevent lymphoma relapse in future designs of CAR-T cell therapy.