Image_1_Efficacy and Safety of TACE Combined With Lenvatinib Plus PD-1 Inhibitors Compared With TACE Alone for Unresectable Hepatocellular Carcinoma Patients: A Prospective Cohort Study.tif

PurposeTo compare the efficacy and safety of the combination of transcatheter arterial chemoembolization (TACE), Lenvatinib, and programmed cell death protein-1 (PD-1) inhibitors (combination group) with TACE (TACE group) in the treatment of patients with unresectable hepatocellular carcinoma (uHCC).MethodsWe consecutively enrolled 110 patients with uHCC in this prospective cohort study, with 56 patients receiving combination treatment and 54 patients receiving TACE from November 2017 to September 2020. The differences in tumor response, survival benefit, and adverse events (AEs) were compared between the two groups. Factors affecting survival were identified via Cox regression analysis.ResultsCompared with the TACE group, the combination group had a higher objective response rate (ORR) (67.9% vs. 29.6%, p 3.11). There were no unexpected toxicities in the combination group.ConclusionCompared with TACE, the combination treatment demonstrated an improved clinical efficacy and manageable safety profile in patients with uHCC. Combination treatment showed better therapeutic efficacy in patients with low NLR; therefore, this ratio could be used to identify patients who will benefit from this treatment.</p

Removing the Oxygen-Induced Donor-like Effect for High Thermoelectric Performance in n‑Type Bi₂Te₃‑Based Compounds

Bismuth telluride-based alloys are the best performing thermoelectric materials near room temperature. Grain size refinement and nanostructuring are the core stratagems for improving thermoelectric and mechanical properties. However, the donor-like effect induced by grain size refinement strongly restricts the thermoelectric properties especially in the vicinity of room temperature. In this study, the formation mechanism for the donor-like effect in Bi2Te3-based compounds was revealed by synthesizing five batches of polycrystalline samples. We demonstrate that the donor-like effect in Bi2Te3-based compounds is strongly related to the vacancy defects (VBi‴ and VTe···) induced by the fracturing process and oxygen in air for the first time. The oxygen-induced donor-like effect dramatically increases the carrier concentration from 2.5 × 1019 cm–3 for the zone melting ingot and bulks sintered with powders ground under an inert atmosphere to 7.5 × 1019 cm–3, which is largely beyond the optimum carrier concentration and seriously deteriorates the thermoelectric performance. Moreover, it is found that both avoiding exposure to air and eliminating the thermal vacancy defects (VBi‴ and VTe···) via heat treatment before exposure to air can effectively remove the donor-like effect, producing almost the same carrier concentration and Seebeck coefficient as those of the zone melting ingot for these samples. Therefore, a defect equation of oxygen-induced donor-like effect was proposed and was further explicitly corroborated by positron annihilation measurement. With the removal of donor-like effect and improved texturing via multiple hot deformation (HD) processes, a maximum power factor of 3.5 mW m–1 K–2 and a reproducible maximum ZT value of 1.01 near room temperature are achieved. This newly proposed defect equation of the oxygen-induced donor-like effect will provide a guideline for developing higher-performance V2VI3 polycrystalline materials for near-room-temperature applications

Image_2_Efficacy and Safety of TACE Combined With Lenvatinib Plus PD-1 Inhibitors Compared With TACE Alone for Unresectable Hepatocellular Carcinoma Patients: A Prospective Cohort Study.tif

PurposeTo compare the efficacy and safety of the combination of transcatheter arterial chemoembolization (TACE), Lenvatinib, and programmed cell death protein-1 (PD-1) inhibitors (combination group) with TACE (TACE group) in the treatment of patients with unresectable hepatocellular carcinoma (uHCC).MethodsWe consecutively enrolled 110 patients with uHCC in this prospective cohort study, with 56 patients receiving combination treatment and 54 patients receiving TACE from November 2017 to September 2020. The differences in tumor response, survival benefit, and adverse events (AEs) were compared between the two groups. Factors affecting survival were identified via Cox regression analysis.ResultsCompared with the TACE group, the combination group had a higher objective response rate (ORR) (67.9% vs. 29.6%, p 3.11). There were no unexpected toxicities in the combination group.ConclusionCompared with TACE, the combination treatment demonstrated an improved clinical efficacy and manageable safety profile in patients with uHCC. Combination treatment showed better therapeutic efficacy in patients with low NLR; therefore, this ratio could be used to identify patients who will benefit from this treatment.</p

Reversible Emulsions from Polyoxometalate–Polymer: A Robust Strategy to Cyclic Emulsion Catalysis and High-Internal-Phase Emulsion Materials

Reversible Pickering emulsions, achieved by switchable, interfacially active colloidal particles, that enable on-demand emulsification/demulsification or phase inversion, hold substantial promise for biphasic catalysis, emulsion polymerization, cutting fluids, and crude oil pipeline transportation. However, particles with such a responsive behavior usually require complex chemical syntheses and surface modifications, limiting their extensive use. Herein, we report a simple route to generate emulsions that can be controlled and reversibly undergo phase inversion. The emulsions are prepared and stabilized by the interfacial assembly of polyoxometalate (POM)–polymer, where their electrostatic interaction at the interface is dynamic. The wettability of the POMs that dictates the emulsion type can be readily regulated by tuning the number of polymer chains bound to POMs, which, in turn, can be controlled by varying the concentrations of both components and the water/oil ratio. In addition, the number of polymer chains anchored to the POMs can be varied by controlling the number of negative charges on the POMs through an in situ redox reaction. As such, a reversible inversion of the emulsions can be triggered by switching between exposure to ultraviolet light and the introduction of oxygen. Combining the functions of POM itself, a cyclic interfacial catalysis system was realized. Inversion of the emulsion also affords a pathway to high-internal-phase emulsions. The diversity of the POMs, the polymers, and the responsive switching groups open numerous new, simple strategies for designing a wide range of responsive soft matter for cargo loading, controlled release, and delivery in biomedical and engineering applications without time-consuming particle syntheses

Unassisted Uranyl Photoreduction and Separation in a Donor–Acceptor Covalent Organic Framework

The donor–acceptor covalent organic framework (COF) TTT–DTDA (TTT = thieno­[3,2-b]­thiophene-2,5-dicarbaldehyde and DTDA = 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)­trianiline) was prepared and found to have long-lived excited states (>100 ms) characterized by transient absorption spectroscopy. These excited-state lifetimes were sufficient to perform the direct photoreduction of uranium at ppm concentration levels. The photoreduction of soluble uranyl species to insoluble reduced uranium products is an attractive separation for uranium, typically accomplished with sacrificial reagents and protective gases. In the case of TTT–DTDA, illumination in aqueous solutions containing only uranyl ions produced crystalline uranyl peroxide species ([UO2(O2)]) at the COF that were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, and infrared spectroscopy. The maximum absorption capacity of TTT–DTDA was found to be 123 mg U/g COF at pH 5 after 10 h of illumination in solutions devoid of sacrificial reagents or protective gases. The TTT–DTDA COF was recyclable and maintained high selectivity for uranium in competing ion experiments, which are necessary requirements for a practical uranium extraction strategy based on photochemical uranium reduction

Radiation-Induced De Novo Defects in Metal–Organic Frameworks Boost CO₂ Sorption

Defects in metal–organic frameworks (MOFs) can significantly change their local microstructures, thus notably leading to an alteration-induced performance in sorption or catalysis. However, achieving de novo defect engineering in MOFs under ambient conditions without the scarification of their crystallinity remains a challenge. Herein, we successfully synthesize defective ZIF-7 through 60Co gamma ray radiation under ambient conditions. The obtained ZIF-7 is defect-rich but also has excellent crystallinity, enhanced BET surface area, and hierarchical pore structure. Moreover, the amount and structure of these defects within ZIF-7 were determined from the two-dimensional (2D) 13C–1H frequency-switched Lee–Goldburg heteronuclear correlation (FSLG-HETCOR) spectra, continuous rotation electron diffraction (cRED), and high-resolution transmission electron microscopy (HRTEM). Interestingly, the defects in ZIF-7 all strongly bind to CO2, leading to a remarkable enhancement of the CO2 sorption capability compared with that synthesized by the solvothermal method

Reversible Amine-to-Imine Chemistry at a Covalent Organic Framework for Sustainable Uranium Redox Separation

The interconversion chemistry of amine-to-imine sites in a covalent organic framework (COF) was developed for the redox-based separation of uranium. Compared to traditional approaches using sacrificial reagents or material decomposition for the reduction and separation of uranium, amine-COF served as the electron donor and was regenerated repeatedly following the oxidation and uranium reduction/separation. The amine-COF, PI-3-AR, was formed from the sodium borohydride (NaBH4) reduction of the imine-linked COF, PI-3, prepared from the solvothermal synthesis of 1,3,5-triformyl benzene (TFB) and 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)trianiline (TTA). PI-3-AR could be converted back to PI-3 via oxidative amination using an excess of the oxidant iodine, I2, or in the photochemical reduction of uranyl ions (UO22+). In consecutive photochemical uranium reduction and separation cycling experiments, the reduced amine COF, PI-3-AR, underwent: (i) oxidation alongside uranium photoreduction and deposition; (ii) acid treatment and uranium extraction; and (iii) NaBH4 reduction and material recovery. The COF, PI-3-AR, and novel separation process involving amine-to-imine interconversion effectively removed uranium (maximum adsorption = 278 mg U/g COF) and maintained >98% uranium recovery over five recycling steps at pH 4.0

Weather and climate extremes in a changing Arctic

Weather and climate extremes are increasingly occurring in the Arctic. In this Review, we evaluate historical and projected changes in rare Arctic extremes across the atmosphere, cryosphere and ocean, and elucidate their driving mechanisms. Comparison of probability density functions pre- and post-2000 highlights clear shifts in the mean and extreme distributions. Indeed, the frequency and amplitude of extremes consistently increased since the turn of the 21st century, with probability increase by 20.0% for atmospheric heatwaves; 76.7% for Atlantic layer warm events; 83.5% for sea ice extent loss; and 62.9% for Greenland Ice Sheet melt extent. These changes can be explained using a ‘pushing and triggering’ concept, representing interplay between external forcing and internal variability: long-term warming destabilizes the climate system and ‘pushes’ it to a new state, allowing subsequent variability associated with large-scale atmosphere-ocean-ice interactions and synoptic systems to ‘trigger’ extreme events over different timescales. The apparent increase in extremes ~2000. Ongoing anthropogenic warming is expected to further increase the frequency and magnitude of extremes, such that probability increases by 72.6% for atmospheric heatwaves; 68,7% for Atlantic layer warm events; and 93.3% for Greenland Ice Sheet melt rate at the end of this century. A summer ice-free would occur in the mid century. Future research should prioritize the development of physically based metrics, enhance high-resolution observation and modelling capabilities, and improve understanding of multiscale Arctic climate drivers.</p