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  • Peng Meng, Qian-Cheng Luo, Aidan Brock, Xiaodong Wang, Mahboobeh Shahbazi, Aaron Micallef, John McMurtrie, Dongchen Qi, Yan-Zhen Zheng, Jingsan Xu
    Chinese Chemical Letters. 2024, 35(4): 108542-.

    Coordination complex of a copper cyanurate (Cu(Ⅱ)-CA) was transformed into coordination polymers upon the stimulus of extra Cu(Ⅱ) through "directed Ostwald ripening". By increasing the molar ratio of Cu(Ⅱ) to CA, we obtained two coordination polymers with selective coordination sites: Cu(Ⅱ)-κN(HCA)κN-Cu(Ⅱ) and Cu(Ⅱ)-κN(HCA)κO-Cu(Ⅱ), which display disparate magnetic interactions.

  • Lu Li, Suticha Chunta, Xianzi Zheng, Haisheng He, Wei Wu, Yi Lu
    Chinese Chemical Letters. 2024, 35(4): 108662-.

    Lipid-based nanocarriers have staged a remarkable comeback in the oral delivery of proteins and peptides, but delivery efficiency is compromised by lipolysis. β-Lactoglobulin (β-lg) stabilized lipid nanoparticles, including nanoemulsions (NE@β-lg) and nanocapsules (NC@β-lg), were developed to enhance the oral absorption of insulin by slowing down lipolysis due to the protection from β-lg. Cremophor EL stabilized nanoemulsions (NE@Cre-EL) were prepared and set as a control. The lipid nanoparticles produced mild and sustained hypoglycemic effects, amounting to oral bioavailability of 3.0% ± 0.3%, 7.0% ± 1.1%, and 7.7% ± 0.8% for NE@Cre-EL, NE@β-lg, and NC@β-lg, respectively. Aggregation-caused quenching (ACQ) probes enabled the identification of intact nanoparticles, which were used to investigate the in vivo and intracellular fates of the lipid nanoparticles. In vitro digestion/lipolysis and ex vivo imaging confirmed delayed lipolysis from β-lg stabilized lipid nanoparticles. NC@β-lg was more resistant to intestinal lipolysis than NE@β-lg due to the Ca2+-induced crosslinking. Live imaging revealed the transepithelial transport of intact nanoparticles and their accumulation in the liver. Cellular studies confirmed the uptake of intact nanoparticles. Slowing down lipolysis via food proteins represents a good strategy to enhance the oral absorption of lipid nanoparticles and thus co-formulated biomacromolecules.

  • Jun Jiang, Tong Guo, Wuxin Bai, Mingliang Liu, Shujun Liu, Zhijie Qi, Jingwen Sun, Shugang Pan, Aleksandr L. Vasiliev, Zhiyuan Ma, Xin Wang, Junwu Zhu, Yongsheng Fu
    Chinese Chemical Letters. 2024, 35(4): 108565-.

    Popularization of lithium-sulfur batteries (LSBs) is still hindered by shuttle effect and volume expansion. Herein, a new modularized sulfur storage strategy is proposed to solve above problems and accomplished via employing 100% space utilization host material of cobalt loaded carbon nanoparticles derived from ZIF-67. The modular dispersed storage of sulfur not only greatly increases the proportion of active sulfur, but also inhibits the occurrence of volume expansion. Meanwhile, 100% space utilization host material can greatly improve the conductivity of the cathode, provide a larger electrolyte wetting interface and effectively suppress the shuttle effect. Moreover, loaded cobalt particles have high catalytic activity for electrochemical reaction and can effectively improve the redox kinetics. The cell with new cathode host material carbonized at 650 ℃ (ZIF-67 (650 ℃)) exhibits superior rate performance and can maintain a high specific capacity of 950 mAh/g after 100 cycles at 0.2 C, showing a good cycle stability.

  • Yixin Zhang, Ting Wang, Jixiang Zhang, Pengyu Lu, Neng Shi, Liqiang Zhang, Weiran Zhu, Nongyue He
    Chinese Chemical Letters. 2024, 35(4): 108619-.

    In the physiological environment, nanoparticles (NPs) interact with proteins to form a protein-rich layer on the surface which is called "protein corona". Understanding and analyzing the formation process of protein corona and protein corona-nanoparticles is of great significance for biological related nano research. Many separation techniques have been used to analyze the composition of protein corona, but in situ analysis of protein corona is still absent. With the development of detection technology, sum frequency generation (SFG) is an effective instrument to analyze the surface protein structure and dynamic changes of protein corona in situ. In this work the molecular mechanism and surface structure effect of the interaction between nanoparticles with surface protein corona (S-NPP) and phospholipid membrane were studied. When S-NPP interacts with phospholipid membrane, the bond affinity network formed by the binding water can stabilize S-NPP around the lipid bilayer. In this process, S-NPP can be found wrapped in the hydration shell. This ultimately leads to a more moderate interaction between particles and phospholipid membrane.

  • Hui Jin, Qin Cai, Peiwen Liu, Yan Chen, Derong Wang, Weiping Zhu, Yufang Xu, Xuhong Qian
    Chinese Chemical Letters. 2024, 35(4): 108721-.

    Erlotinib is an orally administered, highly effective, specific epidermal growth factor receptor tyrosine kinase inhibitor, used to treat non-small cell lung cancer and pancreatic cancer. The traditional synthetic methods for Erlotinib exhibit long reaction time and safety concern. Herein, we describe a novel five-step route for the synthesis of Erlotinib in flow. These five steps comprise etherification, nitration, reduction, addition and cyclization reactions. All steps were optimized and converted to continuous flow process, which drastically reduces the reaction time and considerably improves the process safety as well as the total yield. Enabled by five continuous flow units, Erlotinib is efficiently afforded with an E-factor of 38, an overall yield of 83%, and a total residence time of 25.1 min. Majority steps in this process have been optimized for quantitative conversion, which offers the possibility of telescoping the entire process.

  • Peide Zhu, Yangjia Liu, Yaoyao Tang, Siqi Zhu, Xinyang Liu, Lei Yin, Quan Liu, Zhiqiang Yu, Quan Xu, Dixian Luo, Juncheng Wang
    Chinese Chemical Letters. 2024, 35(4): 108689-.

    Liposomes are one of the significant classes of antitumor nanomaterials and the most successful nanomedicine drugs in clinical translation. However, it is difficult to accurately reveal liposome delivery modes and drug release rates at different pH values to assess the biodistribution and drug delivery pathways in vivo. Here, we established a strategy to integrate Bi-doped carbon quantum dots (CQDs) with liposomes to produce fluorescence visualization and therapeutic effects, namely lipo/Bi-doped CQDs. Lipo/Bi-doped CQDs show good water solubility and physicochemical properties, which can be used for in vitro labeling of colon cancer (CT26) cells and in vivo imaging localization tracking tumors for monitoring. Simultaneously, thanks to the excellent pH sensitivity and ion doping characteristic of Bi-doped CQDs, lipo/Bi-doped CQDs can be used to reveal the drug release rate of liposomes at different pH values and exhibit potential effects in vivo antitumor therapy.

  • Fanjun Kong, Yixin Ge, Shi Tao, Zhengqiu Yuan, Chen Lu, Zhida Han, Lianghao Yu, Bin Qian
    Chinese Chemical Letters. 2024, 35(4): 108552-.

    Tin-based chalcogenides have attracted tremendous attention as an anode material for sodium storage owing to their unique structure and high theoretical capacity. Unfortunately, the large volume change and poor conductivity lead to sluggish reaction kinetics and poor cycling performance. Herein, SnS0.5Se0.5 nanoparticles coupled with N/S/Se triple-doped carbon nanofibers (SnS0.5Se0.5@NSSe-C) are designed and synthesized through electrospinning and annealing process. Benefiting from the synergistic effects of SnS0.5Se0.5 and NSSe-C, the SnS0.5Se0.5@NSSe-C nanofibers exhibit a high reversible capacity and ultralong cycle life at higher current density for sodium-ion batteries. Furthermore, the sodium storage mechanism and electrochemical reaction kinetics of the SnS0.5Se0.5@NSSe-C composite are characterized by the in-situ measurements. The theoretical calculations further reveal the structural advantages of SnS0.5Se0.5@NSSe-C composite, which exhibits a high adsorption energy of Na+. This work can provide a novel idea for the synthesis of ternary tin-based chalcogenides and is beneficial for the investigation of their reaction kinetics.

  • Yanling Yang, Zhenfa Ding, Huimin Wang, Jianhui Li, Yanping Zheng, Hongquan Guo, Li Zhang, Bing Yang, Qingqing Gu, Haifeng Xiong, Yifei Sun
    Chinese Chemical Letters. 2024, 35(4): 108585-.

    Supported Pd based catalysts are considered as the efficient candidates for low-carbon alkane oxidation for their outstanding capability to break C-H bond. Whereas, the irreversible deactivation of Pd based catalysts was still frequently observed. Herein, we reinforced the extruded Pd nanoparticles with quantitive Pt to assemble the evenly distributed PdPt nanoalloy onto ferrite perovskite (PdPt-LCF) matrix with strengthened robustness of metal/oxide support interface. We further co-achieved the enhanced performance, anti-overoxidation as well as resistance of vapor-poisoning in durability measurement. The operando X-ray photoelectron spectroscopy (O-XPS) combined with various morphology characterizations confirms that the accumulation of surface deep-oxidation species of Pd4+ is the culprit for fast activity loss in exsolved Pd system, especially at high temperature of 400 ℃. Conversely, it could be completely suppressed by in-situ alloying Pd with equal amount of Pt, which helps maintain the metastable Pd2+/Pd shell and metallic solid-solution core structure. The density function theory (DFT) calculations further buttress that the dissociation of CH was facilitated on alloy/perovskite interface which is, on the contrary, resistant toward O–H bond cleavage, as compared to Pd/perovskite. Our work suggests that the modification of exsolved metal/oxide catalytic interface could further enrich the toolkit of heterogeneous catalyst design.

  • Xuebing Jiang, Siyi Wang, Li Zhang, Xian Jiang, Maling Gou
    Chinese Chemical Letters. 2024, 35(4): 108686-.

    Lidocaine hydrochloride (LIDH) as an anesthetic is widely used in local anesthesia. Dissolving microneedles (MNs) have great application value in the field of skin anesthesia. However, the limited drug-loading of dissolving MNs is an existing challenge that affects clinical use. In this study, we have screened isomaltulose (ISO) as the proper matrix material for the MNs by using molecular dynamics (MD) simulation. Our findings indicate that ISO has good compatibility with LIDH, and the LIDH-loaded ISO MNs (LI-MNs) have high drug-loading capacity. The drug-loading capacity of LI-MNs could reach 80%, and it could effectively puncture the skin. In addition, the preparation method of customized LI-MNs was established based on three-dimensional (3D) printing technology. It was shown that the administration time of LI-MNs could be controlled within 3 min. Also, the LI-MNs were able to provide the local anesthetic efficacy within 2 min and sustained for more than 2 h. Significantly, LI-MNs had more efficient drug efficacy compared to the topical creams and the majority of existing LIDH-loaded dissolving MNs. They even provided a longer duration of action than the injections. Overall, the LI-MNs with high drug-loading have a promising application prospect.

  • Cheng-Da Zhao, Huan Yao, Shi-Yao Li, Fangfang Du, Li-Li Wang, Liu-Pan Yang
    Chinese Chemical Letters. 2024, 35(4): 108879-.

    Selective molecular recognition in water is routine for bioreceptors, but remains challenging for synthetic hosts. This is principally because noncovalent interactions are usually less efficient in aqueous environments. By mimicking the cavity feature of bioreceptors, Prof. Wei Jiang proposed and clarified the concept of "endo-functionalized cavity". Through situating polar binding sites into a deep hydrophobic cavity, we designed and synthesized several macrocyclic hosts, among which amide naphthotubes are the most representative. The hosts can selectively recognize various polar molecules including organic micropollutants, drug molecules, and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding. In addition, these biomimetic hosts have been applied in spectroscopic analysis, adsorptive separation and self-assembly. In this review, we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group. We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.

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