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01 February 2025, Volume 41 Issue 1

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Chemical Research in Chinese Universities Vol.41 No.1 February 2025

2025, 41(1):  0-0. 

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Review

Multi-Dimensional Role of Amino Acid Metabolism in Immune Regulation: From Molecular Mechanisms to Therapeutic Strategies

QIN Changjuan, YANG Guanqing, WEI Qi, XIN Hua, DING Jianxun, CHEN Xuesi

2025, 41(1):  1-14.  doi:10.1007/s40242-024-4180-8

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Immune cells are essential components of the human immune system, playing a critical role in maintaining human health and defending against diseases. Changes in nutritional metabolism influence the activation, proliferation, apoptosis, differentiation direction, and other behaviors of immune cells, affecting immune functions. Amino acids, fundamental nutrients in all living organisms, are crucial for maintaining redox balance, regulating energy, supporting biosynthesis, and preserving homeostasis. The availability of amino acids influences the behaviors and functions of immune cells significantly. Therefore, understanding the intricate relationship between amino acid metabolism and immune cell behaviors leads to identifying unique therapeutic targets and improving clinical outcomes. The review summarizes the impact of different types of amino acid metabolism on the behaviors of dendritic cells and T cells, hoping to provide a valuable reference for researchers and clinicians in related fields.



Articles

Co-loading Pd and CeO₂ on Silicalite-1 as High-performance Catalyst for Methane Dry Reforming Reaction

XU Jing, ZHANG Rui, WANG Ke, WANG Xiao, SONG Shuyan, ZHANG Hongjie

2025, 41(1):  15-20.  doi:10.1007/s40242-024-4194-2

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The methane dry reforming (DRM) reaction can convert CO₂ and CH₄, both of which contribute to climate change, into syngas, which holds great significance in mitigating specific environmental issues stemming from the greenhouse effect. Nonetheless, the challenges that persist include the substantial energy consumption and the catalyst's susceptibility to deactivation, both of which necessitate solutions. Herein, we developed a catalyst, PdCe/S1, featuring small-sized Pd species and CeO₂ stabilized on pure silicon zeolite (silicalite-1), which is employed in the DRM reaction. It can achieve 97% CH₄ conversion and 98% CO₂ conversion at 750 °C, surpassing binary Pd/CeO₂ and Pd/S1 catalysts. The small size of CeO₂ stabilized by silicalite-1 promotes oxygen defects formation and enhances the CO₂ adsorption capacity. The introduction of silicalite-1 further enhances the interaction between Pd and CeO₂, boosting DRM performance.



A Computer Simulation Study on Deposition Patterns of Cyclic Diblock Copolymer Solution Nanodroplets: Influence of Polymer Length and Concentration

PEI Hanwen, ZHANG Jun, SUN Zhaoyan

2025, 41(1):  21-32.  doi:10.1007/s40242-024-4181-7

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Molecular dynamics simulations are conducted to investigate the deposition patterns of cyclic diblock copolymer solution nanodroplets on solid surfaces (walls). The primary focus is how initial polymer concentration, chain length, and solvent-wall interaction affect these patterns. Deposition patterns are categorized into phase diagrams, mainly composed of multihollow, coffee-ring, and multilayer structures. We also study the deposition of polymer blocks with different adsorption behavior by adjusting the interaction strength between the polymer block and the wall [ε_A(B)W], including weakly adsorbable (ε_A(B)W=0.6), moderately adsorbable (ε_A(B)W=1.0), and strongly adsorbable (ε_A(B)W=1.2) polymer blocks. This study identifies the key factors influencing the droplet's deposition structure and elucidates the mechanisms behind pattern formation. The findings contribute to the design of deposition patterns for cyclic diblock copolymer solution nanodroplets, enhancing applications related to droplet evaporation.



Synthesis and Photochromism of Diazocine Derivatives: Relationship Between Photoswitching Properties and Molecular Structures

WANG Yaxin, CHEN Yulan

2025, 41(1):  33-39.  doi:10.1007/s40242-024-4185-3

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We design and synthesize five novel diazocine derivatives, using diazocine as the core, amide or imine bonds as the connecting units attached with different peripheral substituents. The photoisomerization yield and thermal stability of these derivatives are tested by ¹H NMR and UV-Vis absorption spectroscopy. Among them, the imine-linked derivative exhibits the lowest photoisomerization efficiency, while the amide-linked ones show an elevated switching efficiency in transitioning from the cis to the trans configuration, compared to the unmodified 3,3'-diamino-diazocine. Furthermore, based on experiments together with density functional theory (DFT) calculations, we find that the thermal stability of these derivatives is associated with the electron cloud density and steric hindrance of their substituents. Owing to these unique photophysical properties, diazocine derivatives provide a foundation for the development and application of molecular optical switches.



Large-scale Preparation of Black CeO_x with Stable Oxygen Vacancies

PENG Huan, JIANG Mengmeng, YE Jinfeng, WANG Lei, DING Shunmin, CHEN Chao

2025, 41(1):  40-47.  doi:10.1007/s40242-024-4028-2

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Oxygen vacancy in ceria is a crucial regulation factor for modifying materials. The reduced oxygen vacancy will undergo rapid recombination and deactivation due to the imbalance perturbation of active oxygen species, thereby restricting their larger-scale application. In this work, we proposed a strategy to stabilize oxygen vacancy in four black CeO_x(Si) (0<x<2) by quartz sand doping reduction. The formation of a Ce-O_v-Si (O_v denoted as oxygen vacancy) interface, instrumental in constructing stable oxygen vacancies, is facilitated by rich hydroxyl groups. Characterizations of CeO_x(Si) reveal that the heterogeneous hydrogen at the Ce-O-Si interface encourages the lattice distortion in ceria to obtain stable oxygen vacancies. Guided by the reusable feature, quartz sand doping reduction is a facile and feasible strategy to stabilize the oxygen vacancy of black CeO_x for advanced materials on a large scale.



Lewis Acid-catalyzed Regioselective Addition of Allenoates to Indoles for Synthesis of Bisindolylesters

XIE Fuyu, HE Jianghua, ZHANG Yuetao

2025, 41(1):  48-58.  doi:10.1007/s40242-024-4128-z

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Indole derivatives, especially bisindolylesters, have attracted intense attention due to their important applications in medicinal chemistry and organic synthesis. Here we develop a Lewis acid-catalyzed efficient and regioselective strategy to prepare a series of symmetric and unsymmetric bisindolylesters in high to excellent yields under mild conditions. The systematic investigations, which include stoichiometric nuclear magnetic resonance (NMR) experiments and structural characterization of intermediates, have provided insights into the possible reaction mechanism for this B(C₆F₅)₃-catalyzed addition reaction. Moreover, the sequential employment of Al(C₆F₅)₃ and B(C₆F₅)₃ as catalysts enabled us to successfully prepare the unsymmetric bisindolyl-compounds in one-pot two-step manner without the separation step.



Impact of Various Silicon Sources on the Synthesis of Mordenite and Differences in the Carbonylation Reaction of Dimethyl Ether

CHEN Long, WANG Yunzheng, LV Jiangang, YANG Weimin

2025, 41(1):  59-65.  doi:10.1007/s40242-024-4131-4

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This study introduces an innovative method for synthesizing mordenite (MOR) by employing a combination of water glass and fumed silica as the silica source. The zeolite produced through this method exhibits a smaller grain size, a larger specific surface area, and a greater number of Brønsted acid sites compared to the conventionally synthesized mordenite using silica sol. Furthermore, the chemical environment of framework Al in MOR zeolites is influenced by different silica sources, leading to varied acid properties between the two MOR zeolites, which results in an enhanced activity of dimethyl ether carbonylation from 50% to over 83%.



Design, Synthesis and Pharmacological Evaluation of Novel 4-Phenoxyquinoline Derivatives as VEGFR2 Kinase Inhibitors for Tumor Treatment

JIANG Wei, CHEN Jiayan, WANG Haifeng, XUE Aiqi, ZHANG Xinyang, GUAN Jichi, WEI Lulu, CAI Jianfeng, HU Yong, LIU Dan

2025, 41(1):  66-78.  doi:10.1007/s40242-024-4132-3

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Vascular endothelial growth factor 2 (VEGFR2) plays a vital role in regulating of tumor metastasis and angiogenesis, which has emerged as one of the effective targets for clinical tumor therapy. Herein, a series of novel facilely accessible 4-phenoxyquinoline derivatives was prepared and assessed for their antitumor activity against three human tumor cell lines (SGC-7901, HepG2 and A549). Among these compounds, 6a, 6b and 6c show strong antitumor activity on HepG2 cells [the drug concentration of eliminating half of tumor cells (IC₅₀)=9.33, 1.84, 8.54 μmol/L]. Notably, compound 6b shows potent selective inhibitory activity against VEGFR2 kinase with an IC₅₀ value of 4.66 nmol/L. The excellent anti-angiogenesis capability of compound 6b was confirmed by tube formation and chick chorioallantoic membrane (CAM) assay. In vivo studies confirmed that compound 6b was able to inhibit tumor growth in HepG2 xenografts of BALB/c nude mice without obvious side or toxic effects. The results demonstrated that compound 6b exhibited remarkable anti-angiogenesis and tumor growth inhibitory effects with less toxicity in vitro and in vivo models. These findings highlighted the potential of compound 6b as a promising VEGFR2 kinase inhibitor for the development of antitumor drugs.



A Dibenzo-18-crown-6-based Symmetric Dual-coumarin Lead Ion Fluorescent Probe and Its Imaging in Living Cells

LIU Xiaolei, GONG Chongzhen, PENG Xiujing, SUN Guoxin, YAO Wei, CHU Yongjie, ZHANG Tianyong

2025, 41(1):  79-85.  doi:10.1007/s40242-024-4145-y

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Herein, a turn-on fluorescent probe for the detection of lead ions was developed using 7-diethylaminocoumarin as the fluorophore and dibenzo-18-crown-6 as the recognition unit. The response performance to lead ions was systematically studied. The probe showed specific selectivity and high sensitivity to lead ions, with fluorescence intensity at 496 nm increasing linearly with lead ion concentration (R²=0.995) over the range of 1.0×10^-7―1.0×10^-6 mol/L, and an LOD of 11.4 nmol/L. Job’s plot revealed that the probe forms a 1:1 stoichiometry complex with lead ions during the recognition process. Furthermore, the sensing mechanism of the probe was confirmed by density functional theory calculations, indicating that the recognition mechanism is based on photoinduced electron transfer (PET). The introduction of lead ions blocks PET, resulting in fluorescence enhancement. Finally, it was applied in the detection of practical water samples and bioimaging, demonstrating high application value in the field of chemosensors.



Integration of Melanin-Resveratrol Nanosystem for the Diagnostic-therapeutic of Renal Fibrosis

LI Tingting, JIA Mengni, JI Huifang, ZHANG Ruiping

2025, 41(1):  86-94.  doi:10.1007/s40242-024-4146-x

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In this work, melanin nanoparticle-resveratrol (MNP-RES) nanosystem was excogitated and constructed for the treatment and imaging of folate-induced renal fibrosis (RF) mice model to fulfill the combination of diagnosis and therapeutic. Physicochemical characterization indicated that MNP-RES was a monodisperse spherical framework with a uniform diameter of (18.6±2.7) nm and the drug loading content of RES was 44.8%. The inhibition ratios of reactive oxygen species, such as ^·OH,^·O₂^-, ABTS^· and DPPH were all greater than 80%. After systemic therapy with MNP-RES, the levels of serum creatinine (SCr) and blood urea nitrogen (BUN) were decreased, and the extent of renal fibrosis was considerably relieved, which was verified by H&E, Masson and terminal-deoxynucleoitidyl transferase mediated nick end labeling (TUNEL) staining. The MNP-RES nanosystem can diagnose and monitor the therapeutic efficacy of RF in real time and noninvasively via photoacoustic/magnetic resonance imaging (PA/MRI) dual-modality imaging, and the MNP-RES diagnostic-therapeutic nanosystem had satisfactory biocompatibility in vivo, which facilitated its future bio-transformation for RF treatment in clinical application.



Supramolecular Ion Channel with Controlled K⁺/Na⁺ Transport Behaviors

HE Lei, LUO Yichen, ZHANG Yang, YAN Tengfei, LIU Junqiu

2025, 41(1):  95-100.  doi:10.1007/s40242-024-4149-7

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Dysfunction of ion channels, often caused by mutations in natural proteins, can lead to various channelopathies. Their artificial analogs have shown great promise to substitute the abnormal channels. Here, we report a supramolecular potassium channel that forms through the self-assembly of pyrene-crown ether conjugated by intermolecular π-π interactions. The self-assembled dimer of this channel was optimized and calculated to have a binding energy of -27.4 kcal/mol (1 kcal=4.18 kJ). Evidence for the formation of an active ion channel by PC5 was confirmed using a planar lipid bilayer (BLM) workstation, while no such activity was observed for R-PC5. The K⁺/Na⁺ selectivity was reversed in the reduced form, R-PC5, due to the elimination of the planar structure of PC5, resulting in R-PC5 functioning as a Na⁺ carrier. Additionally, incorporating the pyrene group facilitates imaging in living cells, providing a potentially viable method for investigating the behaviors of artificial ion channels in living systems.



Mo₂C Nanoparticles Supported on N, P Co-doped Carbon by Molten Salts Strategy for Efficient Electrocatalyst Towards Hydrogen Evolution Reaction

BI Xinyue, ZHANG Wenting, TANG Duihai, XIN Shigang, ZHAO Zhen

2025, 41(1):  101-105.  doi:10.1007/s40242-024-4151-0

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In view of recent environmental concerns, electrochemical water splitting for hydrogen (H₂) as one of the important reactions has getting more and more attention in these years. Herein, we synthesized a series of Mo, N, and P co-doped carbons as efficient electrocatalysts to replace the expensive platinum-based catalysts. As the final products, the combination of Mo₂C nanoparticles (NPs) and N, P co-doped carbons were fabricated using a simple molten salt process. More notably, KCl as the template could be recycled and reused via water washing. The ratios of the precursors could affect the structure of the final production, and therefore further determine the performance of electrocatalytic towards hydrogen evolution reaction (HER). Owing to extensive supplies of active sites and heterogeneous structures that provide transfer channels for electrons, the optimal sample of GUPMo-2.00KCl exhibited the best HER activity among the as-synthesized samples, including low overpotentials, small Tafel slope, and good stability. This work opens up a novel prospect for the designing of high-performance electrocatalysts.



Anti-fouling Hydrophobic Coatings via Single-step Silane Hydrolysis

LI Saiya, HOU Qinwen, CHEN Huiping, JIA Yule, ZHANG Dongyang, LIU Yunge, ZHANG Jing, SU Yuan, WANG Dianyu

2025, 41(1):  106-112.  doi:10.1007/s40242-024-4188-0

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Superhydrophobic coatings have tremendous potential for cotton fabric applications in antifouling and antibacterial. Despite great scientific and industrial interest in waterproof cellulosic cotton, its application in cotton fibres has been hindered by complicated processes, templates requirement, and limitations in scale-up production. Herein, we prepared a hydrophobic coating using one-step hydrolysis of siloxane. Through the reaction of long-chain organosilanes with acid, micro/nanostructures with low surface energy were constructed on the cotton fabric surface. Notably, the coating not only imparts self-cleaning and anti-bacterial adhesion properties to cotton fabrics, but also maintains a contact angle of over 140° after treatment with acid, alkali, organic solvents and extreme temperatures. In addition, the coating can be applied to a wide range of metals, plastics and paper to provide antifouling properties. This study believes that these excellent overall properties possess enormous potential for various applications involving anti-fouling.



Direct Synthesis of UOS Zeolite Using a Simple and Commercially Available Organic Structure-directing Agent

HU Chao, FU Wenhua, YUAN Zhiqing, LIU Chuang, WANG Zhendong, YANG Weimin

2025, 41(1):  113-120.  doi:10.1007/s40242-024-4196-0

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The preparation of zeolite utilizing commercially available organic compounds instead of complex and expensive ones is of practical significance. Herein, we report the synthesis of germanosilicate zeolite with UOS framework by utilizing a simple and commercially available compound 3-diethylamino-1-propanol (DEAP) as organic structure-directing agent (OSDA) under fluoride condition. The synthesis has been optimized by rational modification of the variables, including the Si/Ge molar ratios, the amount of DEAP and F^- anions, the concentration of the synthesis gel and crystallization temperature. UOS zeolite materials were prepared with Si/Ge ratio in the range of 1—4. The physicochemical properties, including crystallinity, crystal morphology, chemical environment of framework elements, textural properties and acidity were characterized by multiple techniques. Ge atoms are proved to preferentially occupy the T sites in the double-four-ring (D4Rs) units. Compared to the isostructural IM-16 zeolite, the UOS zeolites prepared herein are of similar textural properties, such as specific surface area and micropore volume. The simple structure and commercial availability of DEAP endow this synthesis with a cost advantage over the conventional preparation of UOS zeolite, where an expensive imidazolium derivative is employed.



Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO₂ Cycloaddition

YAN Shengrong, ZHANG Lan, SHI Songhu, REN Yanyan, LIU Wenhao, LI Yujie, DUAN Fang, LU Shuanglong, DU Mingliang, CHEN Mingqing

2025, 41(1):  121-130.  doi:10.1007/s40242-025-4202-1

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The photocatalytic CO₂ cycloaddition to prepare high value-added chemicals, such as cyclic carbonates (CCs) under mild conditions is an effective strategy to realize carbon neutrality. Herein, through a three-step reaction, the porphyrin-based covalent organic polymer with bimetallic active sites (Fe-COP-Zr) is successfully obtained by coordinating Fe²⁺ and Zr⁴⁺ with porphyrin and bipyridine (Bpy), respectively. Owing to excellent photosensitivity of porphyrin moieties, Fe-COP-Zr exhibits outstanding visible light absorption, which is very important for the production of photogenerated carriers. Consequently, Fe-COP-Zr shows high photocatalytic performance towards CO₂ cycloaddition with a yield of 12.1 mmol/h, which is 6 times higher than that of pure covalent organic polymer (COP) and 3 times higher than that of monometallic Fe-COP. The reason for this excellent photocatalytic CO₂ cycloaddition performance may be ascribed to the synergistic effect of Fe and Zr sites. The photogenerated electrons are easily injected into epichlorohydrin (ECH) through Fe—O bonds to form affluent electron transition state, and interact with Zr⁴⁺ as Lewis acid sites for the ring-opening of ECH, which is the rate-determining step for the visible light boosted chemical fixation of CO₂ into CCs. This work might provide some insights for design and preparation of COPs with multiple active sites to modulate their photocatalytic activities.



Protein@AuNPs Synthesized by Microfluidic Droplet System and Application in Cu(II) and L-Cysteine Sensing

ZHU Xiaotong, LI Xinyu, QI Li, ZHANG Rongyue, LI Nan, HE Xiaonan, QIAO Juan

2025, 41(1):  131-137.  doi:10.1007/s40242-025-4203-0

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In this study, Pepsin@AuNPs (Pep@AuNPs) and Trypsin@AuNPs (Try@AuNPs) were synthesized by a microfluidic droplet system using Pepsin and Trypsin as protection reagents and NaOH as reducing reagents. Compared to the synthesis method in a flask, the AuNPs synthesized by the microfluidic droplet system demonstrated uniform nucleation, superior ultraviolet absorption performance, high stability and short preparation cycles (15 min). The detection range of Cu(II) by Pep@AuNPs was 1.0—100.0 μmol/L and the detection limit was 0.3 μmol/L. The detection range of L-Cysteine by Try@AuNPs was 0.3—250.0 mmol/L and the detection limit was 0.1 mmol/L. This universal method provides an effective strategy for the detection of bioactive molecules, such as metal ions and amino acids by AuNPs with protein as a protective agent.



High Efficiency Mixed Amine Adsorbents for Directly Capturing Carbon Dioxide from Air

WU Yilu, ZHENG Haolong, XIA Zihan, FU Chengmin, XU Feng, YAN Jian

2025, 41(1):  138-145.  doi:10.1007/s40242-024-4206-2

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The development of effective adsorbents with high amine efficiency and CO₂ adsorption almost unaffected by humidity is extremely challenging. In this study, we introduce an innovative solid amine adsorbent, TETA/DEA@FS, composed of triethylenetetramine (TETA) and diethanolamine (DEA) functionalized fumed silica (FS), which exhibits exceptional capability in selectively capturing trace CO₂ from N₂. TETA/DEA@FS shows an exceptionally high capacity of CO₂ adsorption of 1.13 mmol/g at the temperature of 298 K and the pressure of 0.0004 bar (1 bar=100 kPa), and achieves an unprecedented CO₂/N₂ IAST selectivity of 1.70×10¹². TETA/DEA@FS exhibits high amine efficiency, with breakthrough experiments demonstrating that CO₂ adsorption remains nearly unaffected by humidity. Meanwhile, TETA/DEA@FS demonstrates rapid CO₂ adsorption kinetics and outstanding cyclic stability.



Computational Insights into the Interactions of Farnesoid X Receptor with Fargesone A, a Natural Product from Magnolia fargesii

ZHANG Li, CHEN Yaqiong, LI Weihua

2025, 41(1):  146-154.  doi:10.1007/s40242-024-4210-6

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Farnesoid X receptor (FXR) is a ligand-activated nuclear receptor and plays important roles in the regulation of metabolism and homeostasis of several important physiological substances, such as bile acids, glucose, and lipids. As such, FXR has become a promising therapeutic target for the treatment of several metabolic diseases and liver disorders. Recently, fargesone A (FA), a natural product from Magnolia fargesii was identified to be a novel, potent FXR agonist that demonstrated good in vitro and in vivo activities. However, the detailed interaction mechanism of FA with FXR remains unclear. In this study, we employed multiple computational approaches including molecular docking, molecular dynamics simulation, and binding free energy calculation to address the issue. By comparisons of the structural dynamics and binding free energies, an optimal binding mode was identified, in which FA interacts with FXR via a direct hydrogen bond with His447 and hydrophobic interactions with multiple residues, such as Leu287, Met290, Met328, Ile352, and Trp454. Two mutants, namely, H447F and L287N, were further constructed to validate the importance of the identified residues. We anticipate that these findings could be helpful for future rational design of new FA analogues targeting FXR.



3D Printed Chitosan Bioink Loaded with Chrysin for Repairing Bone Defects

ZHANG Hao, TANG Wenshuo, SUI Xin, LI Lingfeng, ZHANG Hongpu, LI Yuran, ZHANG Xueyi, LIU Zhihui, WANG Bowei

2025, 41(1):  155-164.  doi:10.1007/s40242-024-4216-0

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This study aimed to investigate the potential of chrysin (C) to induce osteogenic differentiation of rat bone marrow mesenchymal stem cells (BMSCs) in vitro. Chitosan (CS) was dissolved by repeated freeze-thawing of alkali/urea solutions, followed by co-printing of nano-hydroxyapatite (HAP) powders with different concentrations of C solutions (5, 10, and 20 μmol/L) compounded into CS solution. Its rheological properties were modified with acetic acid/gelatin solution to construct C-CS-HAP (C-CS-H) composite scaffolds by extrusion printing technology. Physicochemical characterization showed that the four groups of scaffolds had regularly interconnected porous structures with pore diameters of about 450—600 μm, and the novel bioink exhibited shear-thinning properties, with the viscosity of the material decreasing in the shear rates range of 0.01—1000 s^-1 and thus good printability. The osteogenic differentiation ability of BMSCs was confirmed by the CCK-8 test, alkaline phosphatase (ALP) test, Alizarin Red staining (ARS) test, osteogenesis-related genes OCN, ALP, Runx 2, and bone morphogenetic protein-2 (BMP-2) test, which showed a significant promotion of the osteogenic differentiation ability of BMSCs with the increase of the content of C. The above results indicate the potential of C-CS-H composite scaffolds in osteogenesis.