Patients with ASPSCR1-TFE3 fusion achieve better response to ICI based combination therapy among TFE3-rearranged renal cell carcinoma.

BACKGROUND: TFE3-rearranged renal cell carcinoma (TFE3-rRCC) is a rare but highly heterogeneous renal cell carcinoma (RCC) entity, of which the clinical treatment landscape is largely undefined. This study aims to evaluate and compare the efficacy of different systemic treatments and further explore the molecular correlates. METHODS: Thirty-eight patients with metastatic TFE3-rRCC were enrolled. Main outcomes included progression-free survival (PFS), overall survival, objective response rate (ORR) and disease control rate. RNA sequencing was performed on 32 tumors. RESULTS: Patients receiving first-line immune checkpoint inhibitor (ICI) based combination therapy achieved longer PFS than those treated without ICI (median PFS: 11.5 vs. 5.1 months, P = 0.098). After stratification of fusion partners, the superior efficacy of first-line ICI based combination therapy was predominantly observed in ASPSCR1-TFE3 rRCC (median PFS: not reached vs. 6.5 months, P = 0.01; ORR: 67.5% vs. 10.0%, P = 0.019), but almost not in non-ASPSCR1-TFE3 rRCC. Transcriptomic data revealed enrichment of ECM and collagen-related signaling in ASPSCR1-TFE3 rRCC, which might interfere with the potential efficacy of anti-angiogenic monotherapy. Whereas angiogenesis and immune activities were exclusively enriched in ASPSCR1-TFE3 rRCC and promised the better clinical outcomes with ICI plus tyrosine kinase inhibitor combination therapy. CONCLUSIONS: The current study represents the largest cohort comparing treatment outcomes and investigating molecular correlates of metastatic TFE3-rRCC based on fusion partner stratification. ICI based combination therapy could serve as an effective first-line treatment option for metastatic ASPSCR1-TFE3 rRCC patients. Regarding with other fusion subtypes, further investigations should be performed to explore the molecular mechanisms to propose pointed therapeutic strategy accordingly.

Amorphous Nickel Hydroxide Shell on Ni8P3 Nanorods for Boosted Highly Stable Overall Water Splitting at High Current.

Developing highly active, highly stable, and cheap electrocatalysts for water splitting is of great significance for hydrogen production. Herein, we report an amorphous Ni(OH)2-clothed transition Ni8P3 catalyst, in which the amorphous Ni(OH)2 shell provides catalytic active sites and serves as a proton conductive encapsulation layer to ensure efficient proton supply to the active Ni8P3 sites. As expected, the Ni8P3@Ni(OH)2 catalyst exhibits significant water decomposition performance at low and high current densities of 10, 100, and 1000 mA cm-2 at 1.45, 1.71, and 2.21 V, respectively, which is comparable to those of commercial electrocatalysts. In particular, the prepared Ni8P3@Ni(OH)2 electrodes possess exceptional long-term durability (200 h) at high current (over 1 A). The significantly improved water-splitting activity and durability in alkaline medium are expected to make them attractive catalyst materials to produce renewable chemical fuels.

Magnetic Anisotropy and Relaxation in Four-Coordinate Cobalt(II) Single-Ion Magnets with a [CoIIO4] Core.

A mononuclear four-coordinate Co(II) complex with a [CoIIO4] core, namely, PPN[Li(MeOH)4][Co(L)2] (1) (PPN = bis(phosphoranediyl)iminium; H2L = perfluoropinacol), has been studied by X-ray crystallography, magnetic characterization, and theoretical calculations. This complex presents a severely distorted coordination geometry. The O-Co-O bite angle is 83.42°/83.65°, and the dihedral twist angle between the O-Co-O chelate planes is 55.6°. The structural distortion results in a large easy-axis magnetic anisotropy with D = -104(1) cm-1 and a transverse component with |E| = +4(2) cm-1. Alternating current (ac) susceptibility measurements demonstrate that 1 exhibits slow relaxation of magnetization at zero static field. However, the frequency-dependent out-of-phase (χ"M) susceptibilities of 1 at 0 Oe do not show a characteristic maximum. Upon the application of a dc field or the dilution with a diamagnetic Zn matrix, the quantum tunneling of magnetization (QTM) process can be successfully suppressed. Notably, after dilution with the Zn matrix, the obtained sample exhibits a structure different from that of the pristine complex. In this altered sample, the asymmetric unit does not contain the Li(MeOH)4+ cation, resulting in an O-Co-O bite angle of 86.05° and a dihedral twist angle of 75.84°, thereby leading to an approximate D2d symmetry. Although such differences are not desirable for magnetic studies, this study still gives some insights. Theoretical calculations reveal that the D parameter is governed by the O-Co-O bite angle, in line with our previous report for other tetrahedral Co(II) complex with a [CoIIN4] core. On the other hand, the rhombic component is found to increase as the dihedral angle deviates from 90°. These findings provide valuable guidelines for fine-tuning the magnetic properties of Co(II) complexes.

Fine Tuning Metal-Organic Frameworks with Halogen Functional Groups for Ethylene Purification.

One-step C2H4 purification from a mixture of C2H2/C2H4/C2H6 could be achieved by metal-organic framework (MOF) NTUniv-70 with an F-functional group. The selectivities of C2H4/C2H6 and C2H4/C2H2 of NTUnvi-70 based on ideal adsorbed solution theory were at least twice that of the original MOF platform, which was in line with the enthalpy of adsorption (Qst) and breakthrough testing. Grand canonical Monte Carlo simulations indicated that the C-H···F interactions played an important role in enhanced C2H4/C2H6 and C2H4/C2H2 adsorption selectivities.

Flow Channel with Recognition Corners in a Stable La-MOF for One-Step Ethylene Production.

Single-step ethylene (C2H4) production from acetylene (C2H2), ethylene (C2H4), and ethane (C2H6) mixtures was realized via the strategy of a flow channel with recognition corners in MOF NTUniv-64. Both the uptake amounts and the enthalpy of adsorption (Qst) showed the same order of C2H2 > C2H6 > C2H4. Breakthrough testing also verified the above data and the C2H4 purification ability. Grand Canonical Monte Carlo (GCMC) simulations indicated that uneven corners could precisely detain C2H2 and C2H6, in which the C-H···π interaction distance between C2H2 (2.84 Å) and C2H6 (3.03 Å) and the framework was shorter than that of C2H4 (3.85 Å).

Synergistic Lewis and Brønsted Acid Sites Promote OH* Formation and Enhance Formate Selectivity: Towards High-efficiency Glycerol Valorization.

As a sustainable valorization route, electrochemical glycerol oxidation reaction (GOR) involves in formation of key OH* and selective adsorption/cleavage of C-C(O) intermediates with multi-step electron transfer, thus suffering from high potential and poor formate selectivity for most non-noble-metal-based electrocatalysts. So, it remains challenging to understand the structure-property relationship as well as construct synergistic sites to realize high-activity and high-selectivity GOR. Herein, we successfully achieve dual-high performance with low potentials and superior formate selectivity for GOR by forming synergistic Lewis and Brønsted acid sites in Ni-alloyed Co-based spinel. The optimized NiCo oxide solid-acid electrocatalyst exhibits low reaction potential (1.219 V@10 mA/cm2) and high formate selectivity (94.0 %) toward GOR. In situ electrochemical impedance spectroscopy and pH-dependence measurements show that the Lewis acid centers could accelerate OH* production, while the Brønsted acid centers are proved to facilitate high-selectivity formation of formate. Theoretical calculations reveal that NiCo alloyed oxide shows appropriate d-band center, thus balancing adsorption/desorption of C-O intermediates. This study provides new insights into rationally designing solid-acid electrocatalysts for biomass electro-upcycling.

Palladium Enhanced Iron Active Site - An Efficient Dual-Atom Catalyst for Oxygen Electroreduction.

Metal-nitrogen-carbon (M-C/N) electrocatalysts have been shown to have satisfactory catalytic activity and long-term durability for the oxygen reduction reaction (ORR). Here, a strategy to prepare a new electrocatalyst (Fe&Pd-C/N) using a unique metal-containing ionic liquid (IL) is exploited, in which Fe & Pd ions are positively charged species atomically dispersed by coordination to the N of the N-doped C substrate, C/N. X-ray absorption fine structure, XPS and aberration-corrected transmission electron microscopy results verified a well-defined dual-atom configuration comprising Fe+2.x -N4 coupled Pd2+ -N4 sites and well-defined spatial distribution. Electronic control of a coupled Fe-Pd structure produces an electrocatalyst that exhibits superior performance with enhanced activity and durability for the ORR compared to that of commercial Pt/C (20%, Johnson Matthey) in both alkaline and acid media. Density functional theory calculations indicate that Pd atom can enhance the catalytic activity of the Fe active sites adjacent to Pd sites by changing the electronic orbital structure and Bader charge of the Fe centers. The excellent catalytic performance of the Fe&Pd-C/N electrocatalyst is demonstrated in zinc-air batteries and hydrogen-air fuel cells.

High-Efficiency CsPbI2Br Perovskite Solar Cells with over 83% Fill Factor by Synergistic Effects of a Multifunctional Additive.

All-inorganic CsPbI2Br with outstanding thermal stability and excellent photoelectric properties is considered as a promising candidate for photovoltaic applications. However, the efficiency of CsPbI2Br perovskite solar cells (PSCs) is still much lower than that of their organic-inorganic hybrid counterparts or CsPbI3-based devices. Herein, we obtained an optimized CsPbI2Br PSC (0.09 cm2) with a champion efficiency of 17.38% and a record fill factor of 83.6% by introducing potassium anthraquinone-1,8-disulfonate (DAD) in the precursor solution. The synergistic effect between the electronegative functional groups and K+ ions in the DAD structure can not only effectively regulate the crystallization growth process to improve the crystalline quality and stability of photo-active CsPbI2Br but also optimize the energy level alignment and passivate the defects to improve the carrier transport properties. The efficiency of the corresponding large-area device (5 cm × 5 cm with an active area of 19.25 cm2) reached 13.20%. Moreover, the optimized CsPbI2Br PSC exhibited negligible hysteresis and enhanced long-term storage stability as well as thermal stability. Our method produces more stable photo-active CsPbI2Br with excellent photoelectric properties for industrial applications or perovskite/silicon tandem cells.

Fine-Tuning MOFs with Amino Group for One-Step Ethylene Purification from the C2 Hydrocarbon Mixture.

Due to the similar kinetic diameters of C2H2, C2H4, and C2H6, one-step purification of C2H4 from a ternary C2H2/C2H4/C2H6 mixture by adsorption separation is still a challenge. Based on a C2H6-trapping platform and crystal engineering strategy, the N atom and amino group were introduced into NTUniv-58 and NTUniv-59, respectively. Gas adsorption testing of NTUniv-58 showed that both the C2H2 and C2H4 uptake capacities and the C2H2/C2H4 separation ability were boosted compared with the original platform. However, the C2H4 uptake value exceeds the C2H6 adsorption data. For NTUniv-59, the C2H2 uptake at low pressure increased and the C2H4 uptake decreased; thus, the C2H2/C2H4 selectivity was enhanced and the one-step purification of C2H4 from a ternary C2H2/C2H4/C2H6 mixture was realized, which was supported by the enthalpy of adsorption (Qst) and breakthrough testing. Grand canonical monte carlo (GCMC) simulation indicated that the preference for C2H2 over C2H4 originates from multiple hydrogen-bonding interactions between amino groups and C2H2 molecules.

Expanding MOF with Unexpanded Channel via Ketone Decorated Ligand for Ethylene Purification and Stability Enhancement.

The concept of an expanding MOF with unexpanded channel size was realized in MOF NTUniv-61 by the utilization of a ketone-functional-group-decorated semirigid ligand and pillar-layer platform. After this unusual expansion, the preferential C2H6 adsorption was preserved via the unchanged pore size, and the functional group was inserted into the MOF. Interestingly, the C2H2 uptake ability, C2H4 selective adsorption ability, and structural stability were obviously enhanced due to the incorporation of the ketone functional group, which were further verified by isosteric heats of adsorption (Qst), GCMC modeling, and breakthrough experiments.

Creating an Ethane Trap in a Ketone-Decorated MOF for One-Step Ethylene Separation from C2 Hydrocarbons.

One-step C2H4 purification from a mixture of C2H2/C2H4/C2H6 by physical adsorption separation was realized via creating an ethane trap in MOF NTUniv-63 by the utilization of a ketone-decorated semirigid ligand, which has further been verified by the breakthrough experiment, isosteric heats of adsorption (Qst), and Grand Canonical Monte Carlo (GCMC) modeling.

Multifunctional anthraquinone-sulfonic potassium salts passivate the buried interface for efficient and stable planar perovskite solar cells.

SnO2-based planar perovskite solar cells (PSCs) are considered as potential photovoltaic candidates due to their simple structures and cost-effective preparation processes. However, the extensive defects accumulated at the buried interface between perovskite and SnO2 greatly hinder the further improvement of PSC efficiency and stability. Herein, the potassium salt of anthraquinone-1,8-disulfonate (ASPS) is used as a novel multifunctional interfacial modifier to improve the carrier transport performance at the buried interface and optimize the quality of the upper perovskite light absorber layer (PVK) in PSCs. Owing to the synergistic effect of sulfonic acid groups, carbonyl groups and potassium ions in ASPS, the accumulated defects at the buried interface are passivated, the energy level arrangement of the interface is optimized, and the crystalline quality and optoelectronic properties of the PVK films are improved. As a result, the power conversion efficiency (PCE) improved significantly from 21.36% for the controlled device to 23.96% for the ASPS-modified device. Furthermore, the unencapsulated ASPS-modified device also exhibited better storage stability and thermal stability than the controlled device.

Heterogeneous Network Switching Strategy Based on Communication Blind Area Dwell Time.

The limitation of indoor visible light coverage and the attenuation of its signal when propagating in line-of-sight has seriously affected the stable communication of receiving devices when users move randomly and also aggravated the power consumption of visible light networking systems. According to the above situation, on the basis of the heterogeneous networking of visible light communication (VLC) and RF communication integration, this article proposes a horizontal-vertical collaborative handover strategy based on the communication blind area dwell time (CBD-HVHO). Combining asymmetrically clipped optical orthogonal frequency division multiplexing (ACO-OFDM) technology with networking handover technology, ACO-OFDM is used to determine the indoor communication blind area by calculating the bit error rate (BER) value at the signal receiver while reducing the multipath interference generated by visible light signals during channel transmission. To achieve this, set the communication blind channel interruption time as the threshold time, compare the communication blind area dwell time with the threshold time, and finally combine the horizontal and vertical collaborative handover strategies based on the communication blind area dwell time. The simulation results show that the handover probability is 0.009, the average number of handovers is 1.006, and the average network throughput is 195.2826 Mbps. Compared with the previously proposed immediate vertical handover (I-VHO) scheme and the dwell vertical handover (D-VHO) scheme, the communication stability is significantly improved, and the power consumption of the network system is reduced to a certain extent.

Highly Selective Cyclization and Isomerization of Propargylamines to Access Functionalized Quinolines and 1-Azadienes.

Developing new organic reactions with excellent atom economy and high selectivity is significant and urgent. Herein, by ingeniously regulating the reaction conditions, highly selective transformations of propargylamines have been successfully implemented. The palladium-catalyzed cyclization of propargylamines generates a series of functionalized quinoline heterocycles, while the base-promoted isomerization of propargylamines affords diverse 1-azadienes. Both reactions have good functional group tolerance, mild conditions, excellent atom economy and high yields of up to 93%. More importantly, these quinoline heterocycles and 1-azadienes could be flexibly transformed into valuable compounds, illustrating the validity and practicability of the propargylamine-based highly selective reactions.

Heteroatom-Doped Amorphous Cobalt-Molybdenum Oxides as a Promising Catalyst for Robust Hydrogen Evolution.

The simultaneous manipulation of the catalytic activity and intrinsic electrical conductivity in a unified system is difficult yet meaningful to unravel the possible strategy that can enhance the hydrogen evolution reaction (HER) performance. Therefore, we propose a simple strategy to enhance the HER performance based on low-temperature redox reaction with ZIF-67@ZIF-8 as a sacrificial template to prepare zinc-doped amorphous CoMo8Ox (denoted as Zn/aCMO). Benefiting from the excellent compositional- and amorphous-based structural advantages of more exposure active sites, optimized electron transfer as well as a stable frame structure, the as-prepared electrode can drive hydrogen evolution at current densities of 10, 50, and 100 mA cm-2, which need ultralow overpotentials of 59, 138, and 189 mV, respectively, and the Tafel slope of the electrode was 66.2 mV dec-1 (1 M KOH). Meanwhile, the intrinsic activity of the prepared low-cost electrocatalyst was also determined, and the turnover frequency was up to 1.49 s-1 at an overpotential of 100 mV. In addition, after continuous testing for 160 h, there was a slight decay at the overpotential of 130 mV.

Significantly Enhanced Carbon Dioxide Selective Adsorption via Gradual Acylamide Truncation in MOFs: Experimental and Theoretical Research.

A gradual amide truncation strategy was presented to tune the pore chemistry and CO2 capture performance of a series of tetracarboxylate-based Cu-MOFs. These MOFs exhibited a high density of Lewis basic sites (LBSs) and open metal sites and were prepared with the goal to enhance CO2 selective adsorption capacity. [Cu2(L1)(H2O)2]n (NJU-Bai42: NJU-Bai for Nanjing University Bai's group), [Cu2(L2) (H2O)2]n (NJU-Bai17), and [Cu2(L3)(H2O)2]n (NTUniv-60: NTUniv for Nantong University) were synthesized, and we observed that the CO2 adsorption capacities and MOF structures were impacted by subtle changes in ligands. Interestingly, although the NTUniv-60 was decorated with the least LBSs in these three MOFs, its CO2 adsorption capacity reached 270 (53.0 wt %) and 164 (32.2 wt %) cm3 g-1 at 273 and 296 K under 1 bar, respectively, which is the highest data reported for MOFs under similar conditions. From the grand canonical Monte Carlo (GCMC) simulation, the cooperative interactions between the CO2 molecules within the shuttle-shaped cages of NTUniv-60 could potentially explain why the CO2 uptake is high in this material.

Formation of a Polar Flow Channel with Embedded Gas Recognition Pockets in a Yttrium-Based MOF for Enhanced C2H2/C2H4 and CO2 Selective Adsorptions.

A polar flow channel with embedded gas recognition pockets was made in a 10-connected hexanuclear yttrium-based metal-organic frameworks (MOF) NTUniv-57 (NTUniv = Nantong University) by lowering the symmetry of the ligand, which showed high chemical stability and obviously enhanced gas adsorption selectivities.

MOF Pillaring Method: Ligand-to-Ligand and Axial-to-Axial Cross-Linking of "Paddlewheels".

By shortening the previous shortest tetracarboxylate ligand, the first ligand-to-ligand and axial-to-axial pillaring method was realized in the prototype MOF NTUniv-56 (NTUniv = Nantong University), which exhibit a rare (2,4,6)-connected net with a new topology and interesting gas adsorption performance.

A multifunctional chemical linker in a buried interface for stable and efficient planar perovskite solar cells.

The buried interface between a perovskite (PVK) light absorbing layer and an electron transport layer (ETL) plays an utmost important role in further improving the efficiency and stability of planar perovskite solar cells (PSCs). The interfacial properties greatly affect charge transport, perovskite crystal growth, and device stability. Herein, a variable structure broad-spectrum UV-284 absorber agent 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (HMBS) is introduced into PSCs based on SnO2 ETLs as an efficient multifunctional chemical linker to modify the buried interface properties. HMBS used to modify SnO2 can simultaneously suppress the surface trap states of ETLs, optimize the ETL/PVK interface energy level arrangement, and improve the crystallization quality of the upper perovskite films. Meanwhile, as an efficient UV absorber, HMBS can also greatly reduce the damage caused by UV light to perovskite films and thus improve the stability of devices. Consequently, HMBS-modified PSCs exhibit champion efficiencies of 23.42% (0.09 cm2) and 20.63% (1.00 cm2) along with remarkably enhanced UV stability. This work emphasizes the importance of appropriate interface treatment strategies for buried interface modification and provides an effective method for fabricating efficient and UV resistant perovskite photovoltaic devices.

Single Co Atoms Implanted into N-Doped Hollow Carbon Nanoshells with Non-Planar Co-N4-1-O2 Sites for Efficient Oxygen Electrochemistry.

Facile synthesis of cost-effective carbon-supported Co single atoms (Co-SAs) exhibits huge potential applications in energy storage and conversion devices. We here report the implantation of Co-SAs into hollow carbon spheres (Co-SAs-HCS) via a facile wet-chemistry strategy followed by controlled pyrolysis. Electron-rich histidine acted as a Lewis base effectively immobilizing Co2+ (Lewis acid) via the electrostatic effect and hydrogen bonds, thus achieving the scalable synthesis of Co-SAs-HCS. We constructed a series of histidine-Co2+ structure models to elucidate the formation of histidine-Co2+ complexes by analyzing their binding energy. X-ray absorption fine-structure results verify that central Co atoms with four N coordination atoms possess a non-planar Co-N4 structure. Electrochemical results indicate that the as-prepared Co-SAs-HCS catalyst shows a low potential difference (0.809 V) between the oxygen evolution reaction potential at 10 mA cm-2 and the oxygen reduction reaction half-wave potential, outperforming the commercial Pt/C catalysts (0.996 V). Moreover, an assembled Zn-air battery based on Co-SAs-HCS exhibits an unexpected long-term durability. We have demonstrated that non-planar Co-N4-1-O2 sites are the source for highly efficient adsorption and dissociation of O2 molecules and then reduction of the free energy of desorption of the intermediates by density functional theory. Our findings provide a new design insight into the exploration of advanced electrocatalysts, which will be applied in the design of green energy devices in the future.