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  • Xinru You, Liying Wang, Junfu Zhang, Tong Tong, Chunlei Dai, Chun Chen, Jun Wu
    Chinese Chemical Letters. 2023, 34(4): 107720-.

    The clinical efficacy of chemotherapeutic drugs is hindered by their poor aqueous solubility, low bioavailability and severe side effects. In recent years, polymeric nanocarriers have been used for drug delivery to improve the efficacy of many chemotherapeutics. In this study, a series of biodegradable phenylalanine-based poly(ester amide) (Phe-PEA) with tunable molecular weights (MWs) were synthesized to systematically investigate the relationship between the polymer MW and the efficacy of the corresponding polymeric nanoparticles (NPs). The results indicated that a range of polymers with different MWs can be obtained by varying the monomer ratio or reaction time. Doxorubicin (DOX), a classic clinical lymphoma treatment strategy, was selected as a model drug. The loading capacity and stability of the higher MW polymeric NPs were superior to those of the lower MW ones. Moreover, in vitro and in vivo data revealed that high MW polymeric NPs had better anticancer efficacy against lymphoma and higher biosafety than low MW polymeric nanoparticles and DOX. Therefore, this study suggests the importance of polymer MW for drug delivery systems and provides valuable guidance for the design of enhanced polymeric drug carriers for lymphoma treatment.

  • Dongfang Han, Xiaolei Li, Zhishan Liang, Bolin Zhao, Zhifang Wu, Fangjie Han, Dongxue Han, Li Niu
    Chinese Chemical Letters. 2023, 34(4): 107722-.

    A label-free lactic acid sensor has been successfully developed by using a Dysprosium single crystal-based photoelectric potential technique via Dy-SCN/FTO electrode. Interestingly, the proposed sensor demonstrated excellent performance for L-lactic acid analysis with a wide linear range of 0.0196~16.31 mmol/L, the detection limit of as low as 3.20 µmol/L as well as an advisable stability. The feasibility of this strategy was also verified by practical application towards human sweat samples. The mechanism studies indicated that lactic acid molecules specifically bind to the surface of semiconductor materials, which alters the charge distribution of the electrode surface and subsequently results in band bending/photoelectric potential changes. The theoretical formula for this photoelectric chemistry (PEC) strategy was then derived according to charge balance theory. We believe that the proposed Dy-SCN/FTO sensor would open a new way for rapid, non-invasive L-lactic acid level evaluation during human physical condition monitoring.

  • Meiru Hou, Xiaodie Li, Yu Fu, Lingli Wang, Dagang Lin, Zhaohui Wang
    Chinese Chemical Letters. 2023, 34(4): 107723-.

    Available online Iodinated X-ray contrast media (ICMs) are clinical drugs used to enhance the imaging effect. Triiodobenzene ring structures of ICMs lead to its extremely high chemical stability, biological inertness, which makes it difficult to be completely removed by traditional water treatment processes. Hence, considerable concentration of ICMs can be frequently detected in aquatic environment. Relying on the strong oxidation capacity of HO• or SO4•‒, various advanced oxidation processes (AOPs) have demonstrated substantial removal efficiency for ICMs. It is evident that ICMs can be decomposed mainly through (1) deiodination, (2) dehydration, (3) decarboxylation, (4) H-abstraction, (5) hydroxyl addition, (6) hydroxyl substitution, (7) oxidation of alcohol groups, (8) cleavage of amide bond, and (9) amino oxidation. However, during the ICMs removal process, the C-I bonds of ICMs molecules are broken, giving rise to the formation of cytotoxic iodination disinfection by-products (I-DBPs) that are potentially more harmful to the ecosystem and human health than their parent compounds. To better understand the technology gaps, this review elaborates the major AOPs which are effective for ICMs removal and emphasizes on the main degradation routes of ICMs in different oxidation system. Some prevailing concerns and challenges are discussed for optimizing the ICMs treatment process.

  • Yupeng Xing, Na Li, Shipeng Qiu, Gang Zhao, Shuhua Hao, Baojie Zhang
    Chinese Chemical Letters. 2023, 34(4): 107724-.

    Developing efficient electrocatalysts for hydrogen evolution reaction (HER) is of great importance in contemporary water electrolysis technology. Here, a novel hierarchically sea urchin-like electrocatalyst (Mo4O11-MoS2-VO2) is synthesized by hydrothermal deposition and post-annealing strategy. The optimized electrocatalyst behaves as a high active hydrogen evolution electrode in 0.5 mol/L H2SO4. This electrode needs overpotential of only 43 mV to achieve 10 mA/cm2 with a Tafel slope of 37 mV/dec and maintains its catalytic activity for at least 36 h. Better than most previously reported non-noble metal electrocatalysts anchored on carbon cloth. It is worth mentioning that the hierarchical sea urchin-like structure promotes the redistribution of electrons and provides more catalytic active sites. This strategy shows a way for the construction of inexpensive non-noble metal electrocatalysts in the future.

  • Huanhuan Ding, Chenguang Li, Hailing Zhang, Na Lin, Wen-Sheng Ren, Shicheng Li, Weidong Liu, Zhonghua Xiong, Binyuan Xia, Chong-Chen Wang
    Chinese Chemical Letters. 2023, 34(4): 107725-.

    Extensive application of nuclear energy has caused widespread environmental uranium contamination. New detection approaches without complicated sample pretreatment and precision instruments are in demand for on-site and in-time determination of uranyl ions in environmental monitoring, especially in an emergency situation. In this work, a simple and effective fluorescent sensor (Z)-N'-hydroxy-4-(1,2,2-triphenylvinyl)benzimidamide (TPE-A) with aggregation-induced emission (AIE) character was established and studied. It could realize to detect UO22+ via quenching the fluorescence of its aggregation-induced emission, with good selectivity and sensitivity. Such strategy shows a wide linear range from 5.0 × 10−8 mol/L to 4.5 × 10−7 mol/L (R2 = 0.9988) with exceptional sensitivity reaching 4.7 × 10−9 mol/L, which is far below the limit for uranium in drinking water (30 µg/L, ca. 1.1 × 10−7 mol/L) stipulated by the WHO. A response time less than four minutes make it rapid for uranyl ion measurement. It was applied for detection of uranyl ion in spiked river water samples with recoveries in the range of 98.7%-104.0%, comparable to those obtained by ICP-MS. With the advantages of portable apparatus, rapid detection process and high sensitivity, TPE-A can serve as a promising fluorescent sensor for the detection of UO22+ in environmental water samples.

  • Zhuoga Cirena, Yu Nie, Yanfang Li, Huilin Hu, Xiang Huang, Xin Tan, Tao Yu
    Chinese Chemical Letters. 2023, 34(4): 107726-.

    30% FeCN/ZIS (30% Fe doped g-C3N4 composited ZnIn2S4) was synthesized by a simple water bath method, via in-situ growth of abundant well-dispersed ZnIn2S4 nanosheets on the Fe doped g-C3N4 surface. Experimental results showed the optimized 30% FeCN/ZIS achieved the best photoreduction of Cr(Ⅵ) performance within a wide pH range, which was 9.5 times and 700 times higher than that of pure ZnIn2S4 and 30% FeCN (Fe doped g-C3N4). This is due to the intense synergy between the Fe-Nx bond and close interface contact produces a high-speed charge transfer channel, thus significantly improving the efficiency of optical carrier separation and migration. Meanwhile, UV-vis diffuse reflection spectra and photoluminescence spectroscopy showed that iron doping significantly narrowed the bandgap of g-C3N4, preventing electron-hole pair recombination. Further, the microstructures and charge separation properties were analyzed by scanning electron microscope, Photoluminescence Spectroscopy and time-resolved photoluminescence, which revealed the structure-activity relationship of composite structure and the synergistic mechanism of each functional component. This research should provide a viable technique for creating composites with high photocatalytic activity for the treatment of chromium-containing wastewater.

  • Yuhao Chu, Chaofan Zhang, Xi Chen, Xue Li, Nanqi Ren, Shih-Hsin Ho
    Chinese Chemical Letters. 2023, 34(4): 107727-.

    Recently, the use of microalgae for bioremediation of pharmaceuticals (PhAs) has attracted increasing interest. However, most studies focused more on microalgae removal performance, its defensive response to the PhAs during wastewater treatment remains unexplored. Herein, microalgal three defensive systems have been investigated in synthetic wastewater, with six PhAs as the typical drug. Results show that PhAs could bind to EPS, and this action in turn could help to alleviate the direct toxicity of PhAs to microalgae. Subsequently, the physiological analyses revealed the increase of superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) activities, potentially reducing the oxidative stress induced by PhAs. Furthermore, the enzyme activities of cytochrome P450 (CYP450) and glutathione-S-transferase (GST) were significantly upregulated after exposure to SMX, CIP and BPA, followed by a significant decrease in biodegradation rates after the addition of CYP450 inhibitors, suggesting that the biotransformation and detoxification of PhAs occurred. Meanwhile, molecular docking further revealed that CYP450 could bind with PhAs via hydrogen bond and hydrophobic interaction, which proved their abilities to be metabolized and form transformation products in microalgae. These findings provide an advancing understanding of microalgae technologies to improve the treatment of wastewater contaminated with PhAs.

  • Zengming Fan, Wenting Sun, Yue Yang, Jiaxiang Guo, Chuandong Dou, Yue Wang
    Chinese Chemical Letters. 2023, 34(4): 107729-.

    Stimuli-responsive macrocycles are of importance for synthetic chemistry and smart materials. In this manuscript, we report two novel organoborane cyclophanes, which were successfully synthesized by ruthenium-catalyzed olefin metathesis. They are composed of one/two boron-doped helicene π-skeletons and flexible alkyl chain linkers, thus representing a new kind of non-conjugated organoborane macrocycles. Their cyclic structures and photophysical properties, as well as Lewis acidity were theoretically and experimentally investigated. Notably, two enantiomers in one single crystal are observed for one organoborane cyclophane, owning to the presence of helical π-framework in its cyclic structure. Moreover, their Lewis acid-base adducts may dissociate in the excited state and thus display intriguing photo-responsive fluorescence properties, which can be further modulated by temperature. This study thus provides a novel design strategy for non-conjugated organoborane macrocycles, which may promote the development of stimuli-responsive macrocyclic materials with fascinating properties.

  • Qi-Long Hu, Jia-Tian Liu, Guangjin Fan, Jian Li, Yixian Li, Albert S.C. Chan, Xiao-Feng Xiong
    Chinese Chemical Letters. 2023, 34(4): 107730-.

    On-resin peptide modification renders an easy-to-operate method that combines solid-phase peptide synthesis efficiency and avoids tedious purification procedures. Herein, we report the transition-metal-free and redox-neutral approach for solid-phase Met diversification with substrate diversity, which could be applied to synthesize cyclic peptides of different sizes.

  • Jiaxin Guo, Jun Tang, Hui Xi, Sheng-Yin Zhao, Weiping Liu
    Chinese Chemical Letters. 2023, 34(4): 107731-.

    The manganese-catalyzed dehydrogenative coupling between methanol and amines for the synthesis of ureas and polyureas is described. Importantly, catalytic efficiency can be improved by the newly synthesized MACHO ligands. Furthermore, this highly atom-economical protocol demonstrates a broad substrate scope with good functional group tolerance, producing H2 as the sole byproduct. Mechanistic studies disclose that formamide is formed through manganese-catalyzed formylation of amine with methanol. Subsequent dehydrogenation affords a transient isocyanate, which is attacked by another equivalent of amine to provide the final product.

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