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81.
Kaikai Wang Wei Zhang Yameng Qi Xiaodan Hu Xiaohong Zhang Shuquan Chang Haiqian Zhang 《先进技术聚合物》2023,34(2):539-548
Fricke gel dosimeters have great potential for three-dimensional (3D) dose verification in radiation therapy; however, they suffer from time-dependent ion diffusion after irradiation, severely affecting their stability and reliability. In this work, a pullulan-based amphiphilic molecule was synthesized, characterized, and self-assembled into nanogels. Nanogel structures were embedded into gel dosimeters to reduce the diffusion rates, and radiation-sensitive nanogel-incorporated Fricke hydrogel nanocomposites were prepared successfully. The results demonstrated that the diffusion coefficient of improved dosimeters was reduced to 0.125 ± 0.001 mm2 h−1, while maintaining the high optical dose sensitivity (0.0410 ± 0.0004 Gy−1 cm−1). It provides a powerful tool toward the practical application of 3D dosimeters. 相似文献
82.
Jerome Lozada Wen Xuan Lin Rosana M. Cao-Shen Ruyin Astoria Tai Prof. David M. Perrin 《Angewandte Chemie (International ed. in English)》2023,62(16):e202215371
Tetrafluoroborate (BF4−) has long been used as a spectator counter anion. Herein, we report an unprecedented salt metathesis between a variety of BF4− salts and a series of organoboronic acids yielding the corresponding organotrifluoroborates. We identified conditions for fast and efficient fluoridation (<1 h) with minimal workup. Fundamentally, this work discloses the proclivity of BF4− to exchange fluoride atoms with organoboronates, highlighting the lability of BF4−. 相似文献
83.
Dr. Dao-Sheng Liu Zhaoyu Zhang Dr. Yufei Zhang Dr. Minghui Ye Song Huang Shunzhang You Zijian Du Jiangfeng He Dr. Zhipeng Wen Dr. Yongchao Tang Prof. Xiaoqing Liu Prof. Cheng Chao Li 《Angewandte Chemie (International ed. in English)》2023,62(5):e202215385
The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al2(SO4)3 is proposed as decent electrolyte additive to manipulate OH−-mediated cross-communication between Zn anode and NaV3O8 ⋅ 1.5H2O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH− accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH− toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH−-mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates. 相似文献
84.
Di Liu Jiyan Pei Prof. Xu Zhang Xiao-Wen Gu Prof. Hui-Min Wen Prof. Banglin Chen Prof. Guodong Qian Prof. Bin Li 《Angewandte Chemie (International ed. in English)》2023,62(12):e202218590
Developing porous materials for C3H6/C3H8 separation faces the challenge of merging excellent separation performance with high stability and easy scalability of synthesis. Herein, we report a robust Hofmann clathrate material (ZJU-75a), featuring high-density strong binding sites to achieve all the above requirements. ZJU-75a adsorbs large amount of C3H6 with a record high storage density of 0.818 g mL−1, and concurrently shows high C3H6/C3H8 selectivity (54.2) at 296 K and 1 bar. Single-crystal structure analysis unveil that the high-density binding sites in ZJU-75a not only provide much stronger interactions with C3H6 but also enable the dense packing of C3H6. Breakthrough experiments on gas mixtures afford both high separation factor of 14.7 and large C3H6 uptake (2.79 mmol g−1). This material is highly stable and can be easily produced at kilogram-scale using a green synthesis method, making it as a benchmark material to address major challenges for industrial C3H6/C3H8 separation. 相似文献
85.
Wen Chen Yuan Zhang Prof. Hai-Bo Yi Prof. Fenglin Wang Prof. Xia Chu Prof. Jian-Hui Jiang 《Angewandte Chemie (International ed. in English)》2023,62(17):e202300162
Type I photodynamic therapy (PDT) represents a promising treatment modality for tumors with intrinsic hypoxia. However, type I photosensitizers (PSs), especially ones with near infrared (NIR) absorption, are limited and their efficacy needs improvement via new targeting tactics. We develop a NIR type I PS by engineering acridinium derived donor-π-acceptor systems. The PS exhibits an exclusive type I PDT mechanism due to effective intersystem crossing and disfavored energy transfer to O2, and shows selective binding to G-quadruplexes (G4s) via hydrogen bonds identified by a molecular docking study. Moreover, it enables fluorogenic detection of G4s and efficient O2⋅− production in hypoxic conditions, leading to immunogenic cell death and substantial variations of gene expression in RNA sequencing. Our strategy demonstrates augmented antitumor immunity for effective ablation of immunogenic cold tumor, highlighting its potential of RNA-targeted type I PDT in precision cancer therapy. 相似文献
86.
Dr. Haiyuan Zou Gang Zhao Hao Dai Dr. Hongliang Dong Wen Luo Prof. Lei Wang Prof. Zhouguang Lu Prof. Yi Luo Dr. Guozhen Zhang Prof. Lele Duan 《Angewandte Chemie (International ed. in English)》2023,62(6):e202217220
Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO2 reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cuδ+, which is found to be directly scaled with the selectivity of the electrochemical CO2-to-CH4 conversion. An optimum CH4 Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cuδ+ centers adjusted by the electron-withdrawing group decrease the pKa of adsorbed H2O, promoting the hydrogenation of intermediates toward the CH4 production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis. 相似文献
87.
Xiaotong Li Prof. Yuan Yao Chenxi Liu Xin Jia Jiahuang Jian Bao Guo Prof. Songtao Lu Prof. Wei Qin Prof. Qing Wang Prof. Xiaohong Wu 《Angewandte Chemie (International ed. in English)》2023,62(25):e202304667
Aqueous redox flow batteries (ARFBs) are a promising technology for grid-scale energy storage, however, their commercial success relies on redox-active materials (RAM) with high electron storage capacity and cost competitiveness. Herein, a redox-active material lithium ferrocyanide (Li4[Fe(CN)6]) is designed. Li+ ions not only greatly boost the solubility of [Fe(CN)6]4− to 2.32 M at room temperature due to weak intermolecular interactions, but also improves the electrochemical performance of [Fe(CN)6]4−/3−. By coupling with Zn, ZIRFBs were built, and the capacity of the batteries was as high as 61.64 Ah L−1 (pH-neutral) and 56.28 Ah L−1 (alkaline) at a [Fe(CN)6]4− concentration of 2.30 M and 2.10 M. These represent unprecedentedly high [Fe(CN)6]4− concentrations and battery energy densities reported to date. Moreover, benefiting from the low cost of Li4[Fe(CN)6], the overall chemical cost of alkaline ZIRFB is as low as $11 per kWh, which is one-twentieth that of the state-of-the-art VFB ($211.54 per kWh). This work breaks through the limitations of traditional electrolyte composition optimization and will strongly promote the development of economical [Fe(CN)6]4−/3−-based RFBs in the future. 相似文献
88.
Dr. Yinxiang Zeng Zhihao Pei Dr. Yan Guo Dr. Deyan Luan Prof. Xiaojun Gu Prof. Xiong Wen Lou 《Angewandte Chemie (International ed. in English)》2023,62(45):e202312145
Constructing multifunctional interphases to suppress the rampant Zn dendrite growth and detrimental side reactions is crucial for Zn anodes. Herein, a phytic acid (PA)-ZnAl coordination compound is demonstrated as a versatile interphase layer to stabilize Zn anodes. The zincophilic PA-ZnAl layer can manipulate Zn2+ flux and promote rapid desolvation kinetics, ensuring the uniform Zn deposition with dendrite-free morphology. Moreover, the robust PA-ZnAl protective layer can effectively inhibit the hydrogen evolution reaction and formation of byproducts, further contributing to the reversible Zn plating/stripping with high Coulombic efficiency. As a result, the Zn@PA-ZnAl electrode shows a lower Zn nucleation overpotential and higher Zn2+ transference number compared with bare Zn. The Zn@PA-ZnAl symmetric cell exhibits a prolonged lifespan of 650 h tested at 5 mA cm−2 and 5 mAh cm−2. Furthermore, the assembled Zn battery full cell based on this Zn@PA-ZnAl anode also delivers decent cycling stability even under harsh conditions. 相似文献
89.
Dr. Yunxiang Li Dr. Yan Guo Dr. Deyan Luan Prof. Xiaojun Gu Prof. Xiong Wen Lou 《Angewandte Chemie (International ed. in English)》2023,62(44):e202310847
Developing highly efficient catalytic sites for O2 reduction to H2O2, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal–organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H2O2 production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O4) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e− O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2O2 production activity and excellent stability under visible light irradiation. 相似文献
90.
Zhaoyu Zhang Dr. Yufei Zhang Dr. Minghui Ye Dr. Zhipeng Wen Dr. Yongchao Tang Prof. Xiaoqing Liu Prof. Cheng Chao Li 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311032
The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+-conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm−2, presenting a record-high cumulative capacity up to 45 Ah cm−2. The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500 cycles). This work brings inspiration for developing fast-charging Zn batteries toward grid-scale storage of renewable energy sources. 相似文献