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  • Xiali Xiong, Wei Geng, Minna Cao, Rong Cao
    Chinese Chemical Letters. 2023, 34(6): 107717-.

    Developing efficient and stable electrocatalyst to hydrogen evolution reaction adaptable for electrolytes with different pH is a big challenge. In this work, a hierarchically structured ternary nanohybrid composed of flower-like Ru nanoparticles, rigid macrocyclic cucurbit[6]uril (CB[6]) and carboxylated multi-walled carbon nanotubes (MWCNTs) was successfully prepared by chemical wet method. Benefited by the structural merits of flower-like Ru nanoparticles exposed abundant active sites supported by the MWCNTs holding superior mass transport and electrons transfer ability as well as the existence of CB[6], the obtained catalyst exhibited outstanding HER activities with overpotentials of 27, 37 and 70 mV at −10 mA/cm2 in alkaline, acidic, and neutral electrolytes, respectively. Under the same electrocatalytic operation conditions, the HER performance is comparable or superior to commercial Pt/C catalyst (47, 27 and 49 mV). Besides, chronopotentiometric and accelerated stability test also revealed its extraordinary stability, which could be further employed for electrocatalytic procedure in a broad pH range.

  • Jiajing Wang, Xiaotian Guo, Qingling Jing, Wenting Li, Tingting Chen, Rongmei Zhu, Huan Pang
    Chinese Chemical Letters. 2023, 34(6): 107675-.

    MOF-based composites have aroused widespread concern due to their controllable morphology and pore characteristics. Nevertheless, the poor conductivity and volume expansion hinder its practical application in LIBs. Herein a classical structure HKUST-1, as the precursor, was used to fabricate quasi-Cu-MOF composite through a facile thermal decomposition strategy. The results showed that quasi-Cu-MOF composite had superior reversible specific capacity (627.5 mAh/g at 100 mA/g) and outstanding cycle stability (514.6 mAh/g at 500 mA/g after 400 cycles) as anodes for LIBs. The results demonstrated that the low-temperature calcination strategy played a significant role in morphology retaining during cycling and the derived copper framework play a crucial part in conductivity improvement. This work is helpful to the design of high-performance electrodes with advanced three-dimensional hierarchical structures.

  • Yongyin Geng, Tianze Wu, Qiuyue Han, Yongtai Yang, Zhenxia Chen, Xuanxuan Li, Bo Yin, Yaming Zhou, Yun Ling
    Chinese Chemical Letters. 2023, 34(6): 107685-.

    It is greatly desired to develop novel gadolinium-based contrast agents (GBCAs) as improved platforms for magnetic resonance imaging (MRI). Herein, we report the syntheses of a series of nonionic cyclen-based GBCAs by precisely tuning carboxylate group on DO3A-pyridine scaffold. [Gd-DO3A-4cp] is isolated which adopts an octadentate coordination mode with a free carboxylate group at 4-position of pyridine. It shows the r1 relaxivity of 5.8 (mmol/L)−1 s-1 (3 T, 25 ℃), which is 75% higher than 3.3 (mmol/L)−1 s-1 of the clinic used [Gd-DOTA]. The possible mechanisms behind the enhanced relaxivity are investigated and proposed by structure-property relationship studies. After validation of low cytotoxicity and considerable kinetic inertness, in-vivo studies are further examined, demonstrating its good MRI performance, biodistribution as well as the way of excretion.

  • Ruonan Guo, Ying Chen, Ying Yang, Jiangwei Shang, Xiuwen Cheng
    Chinese Chemical Letters. 2023, 34(5): 107837-.

    More and more antibiotics that are difficult to biodegrade have been detected in water environments threatening ecosystems and human health. Therefore, it is urgent to develop efficient water treatment methods to degrade antibiotics. In this work, Co-Fe Prussian blue analogues (PBAs) with different molar ratios were synthesized for peroxymonosulfate (PMS) activation to degrade sulfacetamide (SAM, 10 mg/L). By increasing Co molar ratio, the PMS activation capability and electrochemical properties of PBAs were enhanced. Due to its excellent reactivity (degradation efficiency of 84.2% and mineralization efficiency of 52.79%), cost benefit (electrical energy per order, 0.01019 kWh/L) and lower metal leaching ([Co] = 0.259 mg/L, [Fe] = 0.128 mg/L), PBA-1, the as-prepared catalyst with a molar ratio of cobalt to iron of 1:1, was selected for further study. The radical scavenging experiments and an electron paramagnetic resonance (EPR) trapping experiments were performed and revealed that PBA-1 addition was required to produced OH and SO4•− from PMS activation. Accordingly, we proposed a PMS activation mechanism and SAM decomposition pathways for PBA-1/PMS reaction system. Besides, a PBA-1@polyvinylidene fluoride (PVDF) catalytic membrane was further prepared to expand the application potential of PBA nanoparticles. The PBA-1@PVDF catalytic membrane was highly effective and exhibited a great reusability; thus, it could be considered for applications in actual water treatment processes.

  • Ming Chen, Ying Xie, Qian Luo, Jiarui Xu, Yuxin Ren, Rui Liu, Huihui Zhao, Yuling Chen, Hexuan Feng, Yafei Du, Jianwei Li, Guiling Wang, Wanliang Lu
    Chinese Chemical Letters. 2023, 34(5): 107744-.

    Cisplatin is broad-spectrum chemotherapeutic agent that has been widely used for the treatment of a variety of malignant tumors including breast cancer. However, the cisplatin chemoresistance, which derives from the inactivation by glutathione (GSH) depletion, remains a scientific issue to solve. Here, we report a novel type of smart disulfide switchable nanoparticles complexing cisplatin (switch NPs-cisplatin) that is rationally designed, and engineered by synthesizing a hyaluronic acid disulfide bonded polyaspartic acid (HA-ss-Pasp) and complexing cisplatin. The results showed that the switch NPs-cisplatin had a nanoscale of particle size (150 nm), higher drug encapsulation efficiency (> 90%), and suitable drug release profile. They demonstrated evident pH responsiveness and GSH responsiveness, and targeting effect in the resistant breast cancer cells. Furthermore, they were able to block the cisplatin depletion by GSH in the resistant cancer cells, thereby circumventing the chemoresistance. Consequently, switch NPs-cisplatin displayed a remarkable killing effect in the resistant breast cancer cells in vitro, and in the resistant breast cancer-bearing mice. In conclusion, switch NPs-cisplatin could be used as a smart formulation of cisplatin for overcoming the chemoresistance of breast cancer. The present study also offers a universal drug delivery carrier platform for highly efficient but low systemic toxic chemotherapy.

  • Kun Chen, Guoyong Dai, Shengqiu Liu, Yongge Wei
    Chinese Chemical Letters. 2023, 34(5): 107638-.

    Obesity, characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs, is frequently accompanied by chronic low-grade inflammation. As long-acting insulin sensitizers, the organically-derivatized polyoxovanadates (POVs), can extend the dosing interval of antidiabetic drugs from hourly to almost daily. In this work, the protective activity of POVs is investigated by an eight-week in vivo experiment, in which a small amount of POVs was administrated orally to a mouse model of diet-induced obesity every day. The present study shows that administration of POVs significantly decreases the body weight of mice, reduces adipose tissue accumulation, and simultaneously reduces adipose tissue inflammation. In addition, the anti-obesogenic population of iNKT cells is protected potentially by POVs, which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet (HFD)-fed mice against diet-induced obesity. By contrast, the change in body weight after POV treatment is the result of a substantial reduction in fat mass, with no obvious effects on lean body mass. These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.

  • Yushan Zhu, Weina Zhao, Binghua Jing, Junhui Zhou, Bihai Cai, Didi Li, Zhimin Ao
    Chinese Chemical Letters. 2023, 34(5): 107816-.

    Formaldehyde (HCHO) is a common indoor gaseous pollutant, and long-term exposure to it may cause serious damage to the human immune system. Photocatalytic degradation of HCHO is a promising technique. However, most photocatalysts have the disadvantage of rapid recombination of photo-generated electron-hole pairs. In this work, the recombination of photogenerated electron holes was proposed to inhibit through the piezoelectric effect. A two-dimensional (2D) piezoelectric material, 2H-MoS2, was selected to investigate the catalytic performance for HCHO degradation by the synergy of the piezoelectric and photocatalysis properties. The results show that the piezoelectric effect can induce the polarization in 2H-MoS2 and inhibit the recombination of photogenerated electron-hole pairs, thus improving the photogeneration of hydroxyl radicals for HCHO degradation. Therefore, the piezoelectric-photo-catalysis synergistic effect based on density functional theory (DFT) calculation was proposed to elucidate the HCHO degradation performance. This work could provide important guidance for the development of effective catalysts for HCHO degradation and the application of 2D piezoelectric materials.

  • Yuhan Sun, He Zhang, Guangzhao Lu, Huan Wang, Ying Lu, Li Fan
    Chinese Chemical Letters. 2023, 34(5): 107817-.

    Mitochondria are critical for tumor growth and metastasis. A number of traditional antitumor drugs have poor water solubility and must penetrate multiple cellular barriers to reach the mitochondria. Because mitochondria have a unique transmembrane potential and an inner membrane with a low permeability, it is difficult for most drugs to enter mitochondria. In recent years, mitochondria-targeted delivery systems that use functional peptides to modify drugs have received increasing attention. Introducing functional peptides can change the original physicochemical properties of drugs and actively target mitochondria. Functional peptide-drug conjugates (PDCs, peptide-drug conjugates) can decompose and release drugs over time or due to certain stimuli in tumors. This preserves the biological activity of the drug while increasing intratumor uptake through the enhanced permeability and retention effect (EPR, the enhanced permeability and retention effect). In this review, we focus on the direction of cancer therapy and review the application of different functional peptides in the mitochondria-targeted tumor treatments reported in recent years.

  • Jingdong Wang, Fangjun Huo, Yongbin Zhang, Caixia Yin
    Chinese Chemical Letters. 2023, 34(5): 107818-.

    Intracellular pH homeostasis is foundation of maintaining normal physiological functions. More and more evidences show that intracellular pH fluctuations were usually associated with many diseases (such as cancer, epilepsy and neurodegenerative diseases). It is very important to develop in situ real-time determination of pH. In recent years, it has been verified that pH can regulate the isomerization process of spiropyran. Thus, we report a pH fluorescent probe BSL, which is a closed loop spiropyran structure by coupling benzothiazole derivatives with indole salts. We utilizes the process of spiropyran isomerization as the trigger of excited state intramolecular proton transfer (ESIPT) effect, and adjust the process of spiropyran isomerization through pH, and then the molecular transformation from enol to ketone (enol: 525 nm, ketone: 677 nm) through the ESIPT effect. This process achieved accurate measurement of pH. The probe BSL showed sensitive and reversible fluorescence response to pH in vitro. Ultimately, BSL was successfully applied to detect pH fluctuations in cell oxidative stress model.

  • Shuqi Xia, Jiangfei Pan, Deshen Dai, Zong Dai, Mengsu Yang, Changqing Yi
    Chinese Chemical Letters. 2023, 34(5): 107799-.

    Point-of-care testing (POCT) technology is highly desirable for clinical diagnosis, healthcare monitoring, food safety inspection, and environment surveillance, because it enables rapid detection anywhere, anytime, and by anyone. Electrochemiluminescence (ECL) has been widely used in chemo-/bio analysis due to its advantages such as high sensitivity, simplicity, rapidity and easy to control, and is now attracting increasing attention for POCT applications. However, to realize the accurate on-site quantitation, it is still challenging to develop portable devices which can precisely collect, analyze, transmit and display the ECL signals. This review will focus on how to develop a portable ECL device by summarizing recent examples and analyzing their key components part by part. Then the possible solutions to the existing challenges in the development and applications of portable ECL devices are summarized and discussed in detail, followed by offering future perspectives. We attempted to provide an appealing viewpoint to inspire interested researchers to comprehend and explore portable ECL sensing systems for practical applications and even commercialization.

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