The Universal Super Cation-Conductivity in Multiple-cation Mixed Chloride Solid-State Electrolytes

As exciting candidates for next-generation energy storage, all-solid-state lithium batteries (ASSLBs) are highly dependent on advanced solid-state electrolytes (SSEs). Here, using cost-effective LaCl₃ and CeCl₃ lattice (UCl₃-type structure) as the host and further combined with a multiple-cation mixed strategy, we report a series of UCl₃-type SSEs with high room-temperature ionic conductivities over 10⁻³ S cm⁻¹ and good compatibility with high-voltage oxide cathodes. The intrinsic large-size hexagonal one-dimensional channels and highly disordered amorphous phase induced by multi-metal cation species are believed to trigger fast multiple ionic conductions of Li⁺, Na⁺, K⁺, Cu⁺, and Ag⁺. The UCl₃-type SSEs enable a stable prototype ASSLB capable of over 3000 cycles and high reversibility at −30 °C. Further exploration of the brand-new multiple-cation mixed chlorides is likely to lead to the development of advanced halide SSEs suitable for ASSLBs with high energy density.     

Absolute CO2/Xenon Separation in Ultramicropore MOF for Anesthetic Gases Regeneration

Xe is an ideal anesthetic gas, but it has not been widely used in practice due to its high cost and low output. Closed-circuit Xe recovery and recycling is an economically viable method to ensure adequate supply in medical use. Herein, we design an innovative way to recover Xe by using a stable fluorinated metal-organic framework (MOF) NbOFFIVE-1-Ni to eliminate CO₂ from moist exhaled anesthetic gases. Unlike other Xe recovery MOFs with low Xe/CO₂ selectivity (less than 10), NbOFFIVE-1-Ni could achieve absolute molecular sieve separation of CO₂/Xe with excellent CO₂ selectivity (825). Mixed-gas breakthrough experiments assert the potential of NbOFFIVE-1-Ni as a molecular sieve adsorbent for the effective and energy-efficient removal of carbon dioxide with 99.16 % Xe recovery. Absolute CO₂/Xe separation in NbOFFIVE-1-Ni makes closed-circuit Xe recovery and recycling can be easily realized, demonstrating the potential of NbOFFIVE-1-Ni for important anesthetic gas regeneration under ambient conditions.     

Visible Light Induced Copper-Catalyzed Enantioselective Deaminative Arylation of Amino Acid Derivatives Assisted by Phenol

The exploration of value-added conversions of naturally abundant amino acids has received considerable attention from the synthetic community. Compared with the well-established asymmetric decarboxylative transformation, the asymmetric deaminative transformation of amino acids still remains a formidable challenge, mainly due to the lack of effective strategies for the C−N bond activation and the potential incompatibility with chiral catalysts. Here, we disclose a photoinduced Cu-catalyzed asymmetric deaminative coupling reaction of amino acids with arylboronic acids. This new protocol provides a series of significant chiral phenylacetamides in generally good yields and excellent stereoselectivity under mild and green conditions (42–85 % yields, up to 97 % ee). Experimental investigations and theoretical calculations were performed to reveal the crucial role of additional phenols in improving catalytic efficiency and enantiocontrol.     

Evoking Ferroptosis by Synergistic Enhancement of a Cyclopentadienyl Iridium-Betulin Immune Agonist

Ferroptosis is a form of programmed cell death driven by iron-dependent lipid peroxidation (LPO) with the potential for antitumor immunity activation. In this study, a nonferrous cyclopentadienyl metal-based ferroptosis inducer [Ir(Cp*)(Bet)Cl]Cl ( Ir-Bet ) was developed by a metal-ligand synergistic enhancement (MLSE) strategy involving the reaction of [Ir(Cp*)Cl]₂Cl₂ with the natural product Betulin. The fusion of Betulin with iridium cyclopentadienyl (Ir-Cp*) species as Ir-Bet not only tremendously enhanced the antiproliferative activity toward cancer cells, but also activated ferritinophagy for iron homeostasis regulation by PI3K/Akt/mTOR cascade inhibition with a lower dosage of Betulin, and then evoked an immune response by nuclear factor kappa-B (NF-κB) activation of Ir-Cp* species. Further immunogenic cell death (ICD) occurred by remarkable ferroptosis through glutathione (GSH) depletion, glutathione peroxidase 4 (GPX4) deactivation and ferritinophagy. An in vivo vaccination experiment demonstrated desirable antitumor and immunogenic effects of Ir-Bet by increasing the ratio of cytotoxic T cells (CTLs)/regulatory T cells (Tregs).     

Dimensional and Optoelectronic Tuning of Lead-free Perovskite Cs3Bi2I9−nBrn Single Crystals for Enhanced Hard X-ray Detection

Inorganic Bi-based perovskites have shown great potential in X-ray detection for their large absorption to X-rays, diverse low-dimensional structures, and eco-friendliness without toxic metals. However, they suffer from poor carrier transport properties compared to Pb-based perovskites. Here, we propose a mixed-halogen strategy to tune the structural dimensions and optoelectronic properties of Cs₃Bi₂I_9−nBr_n (0≤n≤9). Ten centimeter-sized single crystals are successfully grown by the Bridgman technique. Upon doping bromine to zero-dimensional Cs₃Bi₂I₉, the crystal transforms into a two-dimensional structure as the bromine content reaches Cs₃Bi₂I₈Br. Correspondingly, the optoelectronic properties are adjusted. Among these crystals, Cs₃Bi₂I₈Br exhibits negligible ion migration, moderate resistivity, and the best carrier transport capability. The sensitivities in 100 keV hard X-ray detection are 1.33×10⁴ and 1.74×10⁴ μC Gy_air⁻¹ cm⁻² at room temperature and 75 °C, respectively, which are the highest among all reported bismuth perovskites. Moreover, the lowest detection limit of 28.6 nGy_air s⁻¹ and ultralow dark current drift of 9.12×10⁻⁹ nA cm⁻¹ s⁻¹ V⁻¹ are obtained owing to the high ionic activation energy. Our work demonstrates that Br incorporation is an effective strategy to enhance the X-ray detection performance by tuning the dimensional and optoelectronic properties.     

Catalytic Performance of Amorphous Ti/SiO2 in the Gas-Phase Epoxidation of Propylene with H2O2

The epoxidation of propylene with dilute H₂O₂ aqueous solution over titanium silicalite-1 (TS-1) zeolite catalyst is a green chemical reaction for propylene oxide (PO) production. Carrying out the reaction in gas-phase can get rid of problems caused by using methanol solvent. This paper reports an attempt of using non-zeolite catalyst for the gas-phase epoxidation. Amorphous Ti/SiO₂, obtained by grafting amorphous SiO₂ with TCl₄ in ethanol solvent in a chemical liquid-phase deposition (CLD) process, has been used as the catalyst. Results show that the CLD Ti/SiO₂ with appropriate Si/Ti molar ratio is an active catalyst for gas-phase epoxidation, achieving 9.8 % propylene conversion and 66.9 % PO selectivity with 40.3 % H₂O₂ utilization, which indicates that this amorphous Ti/SiO₂ catalyst deserves extensive studies in the future.     

酸溶-电感耦合等离子体发射光谱法测定白云石和菱镁石中主次元素

利用电感耦合等离子体原子发射光谱仪( ICP-AES)建立白云石和菱镁石中铝、钙、铁、镁、锰、磷、硅、锶的测定方法。研究了酸体系、温度及消解方式对试样消解的影响,结果表明,使用5 mL盐酸和硝酸混合酸(1：3)-0.75 mL氢氟酸-5 mL水以密闭消解的方式在150 ℃下消解白云石和菱镁石30min,并以2mL饱和硼酸络合多余的氢氟酸,可以得到澄清消解液。通过白云石和菱镁石中铝、钙、铁、镁、锰、磷、硅、锶的谱线干扰情况,选择Al 308.215 nm、Ca 318.127 nm、Fe 261.187 nm、Mg 277.983 nm、Mn 257.61 nm、P 213.618 nm、Si 251.611 nm、Sr 421.552 nm作为分析线,各元素的校准曲线在线性范围内线性关系良好,相关系数均不小于0.999。按照实验方法测定白云石和菱镁石标准物质,各元素结果的相对标准偏差 (RSD, n=6)为0.89~3.19%,测定值与认定值无显著性差异。本方法有效解决了白云石和菱镁石快速有效溶解及准确测定问题。     

Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity

This study demonstrates the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate (Co₃[Co(CN)₆]₂), a typical cobalt Prussian Blue Analogue (CoCo-PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number-average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0–3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen-sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo-PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.     

Covalent immobilization of tyrosinase on magnetic multi-walled carbon nanotubes for inhibitor screening

The inhibition of tyrosinase is considered to be a common therapeutic strategy for some hyperpigmentation disorders. Screening of tyrosinase inhibitors is of great significance to the treatment of pigmentation diseases. In this study, tyrosinase was covalently immobilized on magnetic multi-walled carbon nanotubes for the first time, and the immobilized tyrosinase was applied for ligand fishing of tyrosinase inhibitors from complex medicinal plants. The immobilized tyrosinase was characterized by transmission electron microscopy, atomic force microscopy, Fourier-transform infrared spectroscopy, vibrating sample magnetometry, and thermo-gravimetric analyzer, which indicated that tyrosinase was immobilized onto magnetic multi-walled carbon nanotubes. The immobilized tyrosinase showed better thermal stability and reusability than the free one. The ligand was fished out from Radix Paeoniae Alba and identified as 1,2,3,4,6-pentagalloylglucose by ultra-performance liquid chromatography-quadrupole time-of-flight high-resolution mass spectrometry. 1,2,3,4,6-pentagalloylglucose was found to be a tyrosinase inhibitor with similar half maximal inhibitory concentration values of 57.13 ± 0.91 μM compared to kojic acid (41.96 ± 0.78 μM). This work not only established a new method for screening tyrosinase inhibitors but also holds considerable potential for exploring the new medicinal value of medicinal plants.     

Separation,identification, and structural characterization of sucrose ester isomers from tobacco

Sucrose esters (SEs) are crucial tobacco smoke flavor precursors and play a significant role in tobacco's functionality. Due to their structural complexity, the separation and analysis of SEs in tobacco remain a major challenge, and massive structures of SEs have not yet been fully identified. In this study, the fractions enriched in SEs were obtained from oriental and flue-cured tobacco through a series of pretreatments, and two types of SEs (Types I and II) were distinguished by liquid chromatography-tandem mass spectrometry (LC-MSⁿ) analysis, with Type II SEs newly characterized in tobacco. Five groups of main SEs were further purified using preparative high-performance LC (HPLC) coupled to an evaporative light scattering detector, and their structures were characterized by nuclear magnetic resonance spectrometry techniques including ¹H, ¹³C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. By combining LC-MSⁿ and nuclear magnetic resonance spectrometry, the structures of eight SE isomers were finally proposed, of which four were newly identified. These findings further enhance the understanding of the structural diversity of SEs in tobacco, serving as a valuable reference for future research on the elucidation, synthesis, and metabolism of SEs.