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  • Tao Long, Peng Chen, Bin Feng, Caili Yang, Kairong Wang, Yulei Wang, Can Chen, Yaping Wang, Ruotong Li, Meng Wu, Minhuan Lan, Wei Kong Pang, Jian-Fang Wu, Yuan-Li Ding
    Chinese Chemical Letters. 2024, 35(4): 109267-.

    Realizing high-rate capability and high-efficiency utilization of polyanionic cathode materials is of great importance for practical sodium-ion batteries (SIBs) since they usually suffer from extremely low electronic conductivity and limited ionic diffusion kinetics. Herein, taking Na3.5V1.5Mn0.5(PO4)3 (NVMP) as an example, a reinforced concrete-like hierarchical and porous hybrid (NVMP@C@3DPG) built from 3D graphene ("rebar") frameworks and in situ generated carbon coated NVMP ("concrete") has been developed by a facile polymer assisted self-assembly and subsequent solid-state method. Such hybrids deliver superior rate capability (73.9 mAh/g up to 20 C) and excellent cycling stability in a wide temperature range with a high specific capacity of 88.4 mAh/g after 5000 cycles at 15 C at room temperature, and a high capacity retention of 97.1% after 500 cycles at 1 C (−20 ℃), and maintaining a high reversible capacity of 110.3 mAh/g in full cell. This work offers a facile and efficient strategy to develop advanced polyanionic cathodes with high-efficiency utilization and 3D electron/ion transport systems.

  • Liliang Chu, Xiaoyan Zhang, Jianing Li, Xuelei Deng, Miao Wu, Ya Cheng, Weiping Zhu, Xuhong Qian, Yunpeng Bai
    Chinese Chemical Letters. 2024, 35(4): 108896-.

    Polysubstituted chiral γ-butyrolactones are the core structural units of many natural products and high value-added flavors and fragrances used in the food and cosmetic industry. Current enzymatic cascade synthesis of these molecules faces the problems of low enzyme activity and phase separation in batch reaction, resulting in low productivity. Herein, we report a new continuous-flow process to synthesize the optically pure Nicotiana tabacum lactone (3S,4S)-4a and whisky lactone (3R,4S)-4b from α,β-unsaturated γ-ketoesters. A new ene reductase (ER) from Swingsia samuiensi (SsER) and a carbonyl reductase (SsCR) were engineered by directed evolution to improve their activity and thermostability. The continuous-flow preparative reactions were performed in two 3D microfluidic reactors, generating (3S,4S)-4a (99% ee and 87% de) and (3R,4S)-4b (99% ee and 98% de) with space-time yields 3 and 7.4 times higher than those of the batch reactions. The significant enhancement in the productivity of enzyme cascade catalysis brought by cutting-edge continuous microfluidic technology will benefit the general multi-enzyme catalytic systems in the future.

  • Caixia Li, Yi Qiu, Yufeng Zhao, Wuliang Feng
    Chinese Chemical Letters. 2024, 35(4): 108846-.

    The poor interfacial contact is one of the biggest challenges that solid-state lithium batteries suffer from. Reducing the solid-state electrolyte surface energy by transforming the interface from lithiophobic to lithiophilic is effective to promote the interfacial contact, but electronic conductive interphases usually increase the risk of electron attack, thus leading to uncontrollable Li dendrite growth. Herein, we propose a self-assembled thermodynamic stable LiI interphase to simultaneously improve the interfacial contact between the garnet electrolyte Li7La3Zr2O12 (LLZO) and Li anode, and prohibit the electron attack. The direct contact between LLZO and Li and the high temperature Li melting process was ascribed to Zr4+ reduction, which facilitated Li dendrite formation and propagation. With the modification of the high lithiophilic I2 thin film, the area specific interfacial resistance of LLZO/Li was reduced from 1525 Ω/cm2 to 57 Ω/cm2. More importantly, LLZO was protected from being reduced due to the outstanding electronic insulativity of the LiI interphase, which leaded to a high critical current density of 1.2/7.0 mA/cm2 in the time/capacity-constant modes, respectively.

  • Tao Yu, Vadim A. Soloshonok, Zhekai Xiao, Hong Liu, Jiang Wang
    Chinese Chemical Letters. 2024, 35(4): 108901-.

    Schiff base metal complexes are of great importance in pharmaceutical science owing to their unique chemical properties, which enable them to exhibit diverse biological activities such as anti-bacterial, anti-oxidant, anti-inflammatory, and anti-tumor properties. Furthermore, Schiff base metal complexes can serve as reagents and catalysts in chemical reactions. This review aims to provide an overview of our recently published studies on Cu(Ⅱ) and Pd(Ⅱ) complexes derived from proline Schiff base ligands. We also discuss the potential applications of these metal complexes in the fields of antibacterial and chiral resolution.

  • Yuqing Zhu, Haohao Chen, Li Wang, Liqun Ye, Houle Zhou, Qintian Peng, Huaiyong Zhu, Yingping Huang
    Chinese Chemical Letters. 2024, 35(4): 108884-.

    Piezoelectric catalysis, a new catalytic method, is widely used in the field of environmental sanitation, including waste water treatment and dye degradation. However, in the face of the growing environmental pollution problem, the efficiency of piezoelectric catalysis is still hampered by the stress variation in the natural environment. Therefore, it is particularly important to improve the catalytic efficiency of piezoelectric materials. We divide piezoelectric materials into two categories: inorganic piezoelectric materials and organic piezoelectric materials. Then the mainstream inorganic piezoelectric materials are divided into four subcategories, namely: (1) MTiO3 (M = Ba, Sr), (2) bi-class catalytic materials, (3) MoX2 (X = S, Se), and (4) ZnO piezoelectric materials. The mainstream organic piezoelectric materials are divided into PVDF and g-C3N4 materials. At the same time, the above materials are summarized to explain the excellent performance of materials from the perspective of structure and piezoelectric principle. In addition, we summarized the modification methods that can be applied to piezoelectric materials: (1) Morphology methods, (2) composites with heterojunctions, and (3) surface modification. Finally, we summarized the prospects of piezoelectric materials in the field of environment and water treatment.

  • Sajid Mahmood, Haiyan Wang, Fang Chen, Yijun Zhong, Yong Hu
    Chinese Chemical Letters. 2024, 35(4): 108550-.

    Electrochemical nitrogen reduction reaction (ENRR) provides a promising strategy to achieve sustainable synthesis of ammonia. However, despite great efforts devoted to this research field, the problems such as low energy efficiency and weak selectivity still impede its practical implementation. Most of the research to date has been concentrated on creating sophisticated electrocatalysts, and adequate knowledge of electrolytes is still lacking. Herein, the recent progress in electrolytes for ENRR, including alkaline, neutral, acidic, water-in-salt, organic, ionic liquid, and mixed water-organic electrolytes, is thoroughly reviewed to obtain an in-depth understanding of their effects on electrocatalytic performance. Recently developed representative electrocatalysts in various types of electrolytes are also introduced, and future research priorities of different electrolytes are proposed to develop new and efficient ENRR systems.

  • Songtao Cai, Liuying Wu, Yuan Li, Soham Samanta, Jinying Wang, Bing Liu, Feihu Wu, Kaitao Lai, Yingchao Liu, Junle Qu, Zhigang Yang
    Chinese Chemical Letters. 2024, 35(4): 108599-.

    The photothermal therapy (PTT) has come across as a promising noninvasive therapeutic strategy for tumor treatment. However, low photothermal conversion efficiency (PCE) and hydrophobicity may impede the therapeutic efficacy of organic photothermal agents and an efficient PTT-agent must overcome these two major challenges. In this work, we developed a new strategy to promote higher PCE wherein the intermolecular hydrogen-bonding interaction between the single dye molecule and water facilitated the transformation of the absorbed energy into the heat. A hydrophilic squaraine dye (SCy1) with the second near-infrared region (NIR-II) absorption and extremely low emission were designed to exhibit much higher PCE than that of the analogues of pentamethine-dyes (PCy1, PCy2). The presence of the '–O' at middle of squaric cycle enabled the intermolecular H-bonding formation between the SCy1 and water to promote the energy dissipation channel. Moreover, the introduction of long-chain phenylsulfonate groups helped in to improve the water solubility apart from serving as an additional means of further enhancing PCE through fluorescence quenching. Therefore, SCy1 with a squaraine backbone and long-chain sulfonate moieties revealed outstanding photothermal stability and anti-aggregation activity apart from showing exceptionally high PCE (74%) in water. SCy1 demonstrated excellent therapeutic efficacy when applied in the PTT treatment of tumor-bearing mice under a laser irradiation of 915 nm.

  • Lumin Zheng, Ying Bai, Chuan Wu
    Chinese Chemical Letters. 2024, 35(4): 108589-.

    Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO2 are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn3+ type polaron have been identified by investigating four types of δ-MnO2 (O3, O'3, P2 and T1). Although Al insert into δ-MnO2 leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO2 keeps the long (spacious pathways) and stable (2.007–2.030 Å) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 eV. By eliminated the influence of Mn3+ (low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 eV in P2 type, confirming the obviously effect of Mn3+ polaron. On the contrary, although the T1 type MnO2 has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer, causing by H2O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO2 achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2 (1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO2 should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.

  • Yi Cao, Xiaojiao Ge, Yuanyuan Wei, Lulu He, Aiguo Wu, Juan Li
    Chinese Chemical Letters. 2024, 35(4): 108672-.

    Peptide-drug conjugates have achieved considerable development and application as a novel strategy for targeted delivery of anticancer drugs. Bioactive peptides induced calcium deposition can irreversibly assist inhibition of tumors. However, active regulation of calcium level through signal transduction of bioactive substances has not been reported yet. In this study, novel neuropeptide-doxorubicin conjugates (NP-DOX) with lysosome-specific acid response were described for neuropeptide Y1 receptor (Y1R)-overexpressed triple-negative breast cancer. The delivery mechanism of NP-DOX was clarified that diverse pathways were involved, including intracellular and intercellular transport. Importantly, up-regulation of Y1R-mediated intracellular calcium level via second messenger inositol triphosphate was presented in NP-DOX treated MDA-MB-231 cells. In vivo antitumor efficacy demonstrated that NP-DOX showed less organ toxicity and enhanced tumor inhibition benefited from its controlled release and Y1R-mediated calcium deposition, compared with free DOX. This bioconjugate is a proof-of-concept confirming that neuropeptide-mediated control of signaling responses in neuropeptide-drug conjugates enables great potential for further applications in tumor chemotherapy.

  • Hongxia Li, Xiyang Wang, Du Qiao, Jiahao Li, Weiping Zhu, Honglin Li
    Chinese Chemical Letters. 2024, 35(4): 108747-.

    Using gas-liquid segmented micromixers to prepare nanoparticles that have a homogeneous particle size, controllable shape, and monodispersity advantages. Although nanoparticle aggregation within a microfluid has been shown to be affected by the shear effect, the shear effect triggering conditions in gas-liquid two-phase flow is unclear and the aggregation behavior of nanoparticles under the shear effect is difficult to predict, resulting in uncontrollable physical and chemical properties of nanoparticle aggregates. In this study, a numerical simulation of nanoparticle aggregation in gas-liquid two-phase flow under the shear effect is performed using the CFD-DEM method. Then, the effects of total flow rate, gas-liquid two-phase flow ratio, and particle volume fraction on particle aggregation were analyzed to achieve control of particle aggregation shape and size. Meanwhile, the triggering mechanism of the shear effect and the mechanism of the shear effect on the aggregation of nanoparticles were clarified. The results show that increasing the total flow rate or decreasing the gas-liquid two-phase flow rate ratio can induce the shear effect, which reduces the particle aggregation size and makes the morphology tend to be spherical. Moreover, increasing the particle volume fraction, and total flow rate or decreasing the gas-liquid two-phase flow rate ratio also increases the number of particle collisions and induce interparticle adhesion. Hence, particle adhesion and the shear effect compete with each other and together affect particle aggregation.

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