Chemical Research in Chinese Universities

Chemical Research in Chinese Universities Vol.40 No.5 June 2024

2024, 40(5): 1-4.

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CO₂/NO_x-involved Electrochemical C-N Coupling Reactions

SUI Xiqing, WU Limin, JIA Shunhan, JIN Xiangyuan, SUN Xiaofu, HAN Buxing

2024, 40(5): 764-775. doi:10.1007/s40242-024-4118-1

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With the excessive use of fossil fuels leading to significant CO₂ emissions, and the continuous increase of NO_x in water bodies and soils, the use of electrochemical methods for the conversion of CO₂ and NO_x has garnered widespread attention as a green chemical approach due to its advantages of being environmentally friendly, low-carbon, and straightforward. C—N bonds are widely present in many value-added chemicals, such as urea, amides, and oximes. However, traditional methods for constructing C—N bonds typically involve thermochemical processes. Therefore, using electrochemical methods to catalyze the reduction of CO₂ and NO_x for C—N bond formation has emerged as a green and sustainable alternative. This paper summarizes the research progress of electrochemical C—N bond construction involving CO₂ and NO_x from the perspectives of reaction mechanisms and catalytic system construction, reviews the electrochemical synthesis of urea, amines, amides, and oximes through electrochemical C—N bond construction, and finally analyzes the current problems and challenges in the field, providing prospects for its future development.

Recent Progress on Water-based Liquid Embolic Agents in Endovascular Treatment

QI Yi, FAN Hailong

2024, 40(5): 776-785. doi:10.1007/s40242-024-4060-2

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Vascular embolization treatment, a minimally invasive surgery for various blood vessel-related conditions, has emerged as a crucial method in treating such as hemorrhage, arteriovenous malformation, aneurysms, and hypervascular tumors. Liquid embolic agents are gaining prominence due to their distinct advantage in infiltrating distal regions, expanding the scope of embolization beyond the reach of solid agents. Recent strides in biomaterials and technologies have spurred the development of novel liquid embolic agents, addressing challenges posed by traditional options. This mini-review provides a concise overview of the recent progress in water-based liquid embolic agents, highlighting their potential to overcome limitations associated with current embolic materials. By presenting selected research outcomes, we illuminate advancements that enhance the efficacy of liquid embolic agents. Furthermore, the review outlines essential properties for effective liquid embolic agents, offering insights for future developments in this field.

Sponge as Scaffolds in Bone and Cartilage Tissue Engineering

LUO Lei, GONG Yining, YAN Liang, BU Yazhong

2024, 40(5): 786-797. doi:10.1007/s40242-024-4135-0

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In recent years, tissue scaffolds have emerged as a new therapeutic method for bone and cartilage regeneration, with sponge scaffolds gaining increasing attention. Sponge scaffolds possess several favorable characteristics, including appropriate biodegradability, excellent biocompatibility, good processability, powerful osteogenic ability, a unique porous structure, and adjustable pore size and connectivity. These attributes make sponge scaffolds a promising option for bone and cartilage regeneration. However, to date, there is a lack of comprehensive reviews summarizing the use of sponge scaffolds in this field. In this review, our objective is to provide a comprehensive overview of the research progress and development trends of sponge scaffolds. Firstly, we introduce the various materials used for sponge scaffolds. Secondly, we summarize the different preparation methods employed for creating sponge scaffolds. Subsequently, we discuss the functional additives that can be incorporated into the scaffolds. Finally, we present some special structures that can be achieved in sponge scaffolds. Our aim is for this review to offer valuable insights and serve as a comprehensive resource for the design of sponge scaffolds in cartilage and bone regeneration.

Advancements and Prospects in Continuous Wave Time-resolved Electron Paramagnetic Resonance

ZHANG Shixue, ZHOU Shengqi, WU Hao, GUO Xingwei

2024, 40(5): 798-805. doi:10.1007/s40242-024-4144-z

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This brief review highlights the techniques and diverse applications of time-resolved electron paramagnetic resonance (TREPR) spectroscopy, underscoring its essential role in elucidating the structures, spin dynamics, and reactivities of open-shell systems. Furthermore, we discuss the limitations of traditional TREPR methodologies, particularly their challenges in directly observing reactive radical intermediates under real-world reaction conditions. Lastly, we present the latest advancements in TREPR technology developed in our laboratory, specifically ultrawide single-sideband phase-sensitive detection (U-PSD) TREPR, highlighting its significant impact and tremendous potential in advancing free radical chemistry research. We envision promising future applications of TREPR and its pivotal role in enhancing our understanding of mechanisms involved in complex radical processes and photocatalysis.

Near-infrared Emissive 1,2-Dioxetane-based Chemiluminescent Probes

CHEN Yingqi, BUDIANTA Richard, NING Yingying

2024, 40(5): 806-823. doi:10.1007/s40242-024-4166-6

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Chemiluminescence, a phenomenon emitting light from chemical reactions rather than photon absorption, has gained significant interest for applications in bioimaging and biosensing due to its high sensitivity and low background interference. Now there is a growing interest in near-infrared (NIR) chemiluminescent probes for improved tissue penetration and reduced autofluorescence. This review summarizes NIR emissive chemiluminescent probes based on 1,2-dioxetane and discusses their chemical structures and applications. Structure modification strategies for red-shifting wavelength and enhancing brightness include incorporating electron-withdrawing groups, designing chemiluminophore-fluorophore cassettes, and exploring alternative chemiluminescent scaffolds. This review aims to inspire the exploration of NIR chemiluminescent probes in disease detection and treatment.

Non-invasive Healthcare Analytical Platform Based on Organic Electrochemical Transistors

HU Xingyu, MAO Ning, YAN Xinwen, HUANG Ling, LIU Xu, YANG Huige, SUN Qingqing, LIU Xuying, JIA Hanyu

2024, 40(5): 824-841. doi:10.1007/s40242-024-4176-4

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Non-invasive bioelectronics, especially organic electrochemical transistors (OECTs), have drawn extensive attentions of academical and medical communities by virtue of their efficient bio-electronic interfacing, water-involved ionic transport, excellent ionic-electronic coupling, ultralow power consumption, wide detectable range, and outstanding detection sensitivity. Designable structure diversity, low-temperature solution processability, facile bio/chemical functionalization, and excellent biocompatibility of organic mixed ionic-electronic conductors (OMIECs) render OECTs particularly suitable for non-invasive or minimally invasive healthcare analytical platform. Here, we comprehensively review recent advances of the non-invasive analytical healthcare applications based on OECTs, especially on the detection of biomarkers or metabolites in the excretory biofluids, as well as the recording of electrophysiological signals. A brief introduction of OECT and its comparison with other organic thin-film transistors upon device configuration and working mechanism are firstly discussed. State-of-the-art non-invasive OECT-based biosensors are summarized on their detection of ionic and molecular biomarkers, following with circuit design strategies of OECTs for real-time and in-situ electrophysiological recording from skin surface. In conclusion, remaining barriers and future challenges of non-invasive OECT-based bioelectronics towards lower detection limit, more accurate quantitative relationship between analyte concentrations and measured parameters, more intimate device-tissue interface, and long-term operation stability are deeply analyzed with a critical outlook.

Stereo-control on Lanthanide Triple-stranded Helicates Toward Enhanced Enantioselective Sensing

GUO Xiaoqing, ZHANG Xinyuan, HU Shaojun, ZHOU Lipeng, SUN Qingfu

2024, 40(5): 842-848. doi:10.1007/s40242-024-3287-2

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Chiral metal-organic cages (MOCs) serve as a representative model for enzyme simulation, offering a robust platform for reproducing and expanding enzyme functions at the molecular level. In this study, we present a family of lanthanide triple-stranded helicates with finely-tuned stereoconfigurations, self-assembled from ligands featuring both point and axial chiral centers. Circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy demonstrated that peripheral point chirality induces the stereoconfiguration (Δ/Λ) of the metal center, while bridging axial chirality defines the cavity chiral microenvironment, resulting in the formation of both homochiral and mesomeric helicates. In comparison to mesocate, the homochiral helicates exhibited heightened enantioselectivity in the luminescent detection of D/L-leucinol.

Reaction Mechanism of Actin ATP Hydrolysis Studied by QM/MM Calculations

WANG Yiwen, LIN Lirui, XU Li-Yan, LI En-Min, DONG Geng

2024, 40(5): 849-855. doi:10.1007/s40242-024-4089-2

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Actin fibers are an important part of the cytoskeleton, providing vital support for the plasma membrane. This function is driven by its ATPase (ATP: adenosine triphosphate) activity, i.e., ATP+H₂O→ADP+P_i. This seemingly simple reaction has attracted much attention because the hydrolysis of ATP provides energy to support life processes. However, the reaction mechanism of ATP hydrolysis in actin is not clear. In order to gain deep insights into the functions of actin, it is essential to elucidate the reaction mechanism of the actin ATP hydrolysis. In this paper, we have studied the reaction mechanism of the ATP hydrolysis in actin by the combined quantum mechanical and molecular mechanics (QM/MM) calculations. Our results show that 1) bond cleavage of the P_γ—OS of ATP and bond formation between oxygen of the lytic water and P_γ atoms take place simultaneously, and this is the rate-limiting step of the hydrolysis; 2) the proton on the lytic water transfers to the phosphate to form H₂P_γO₄^- via one bridge water. The energy barrier of the complete reaction is 17.6 kcal/mol (1 kcal=4.184 kJ), which is in high agreement with the experimental value.

Well-controlled Organocatalytic Ring-opening Polymerization of Seven-membered Cyclic Carbonates with Cyclohexyl Fusion

ZHANG Wei, SHAN Si-Yi, DAI Jiang, CAI Zhongzheng, ZHU Jian-Bo

2024, 40(5): 856-862. doi:10.1007/s40242-024-4094-5

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Developing green and well-controlled polymerization methods is of great significance for the preparation of biomedical polymer materials. In this contribution, an efficient organocatalytic ring-opening polymerization (ROP) of a class of seven-membered cyclic carbonates (T6DO, T6HDO, C6DO, C6HDO) containing cis- or trans-cyclohexane structure was established. Organic catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) promoted living polymerization of these cyclic carbonates to deliver polycarbonate and block copolymer products with predictable molecular weights and narrow dispersity. The robust TBD-mediated ROP at 90 ℃ showcased turnover frequency (TOF) up to 10³ h^-1. The resulting amorphous polycarbonates displayed good thermal stability.

Visible-light-induced Synthesis of Organic Peroxides via Decarboxylative Couplings of Carboxylic Acids, Alkenes and tert-Butyl Hydroperoxide

HUANG Qiuwei, LOU Chenhao, LV Leiyang, LI Zhiping

2024, 40(5): 863-873. doi:10.1007/s40242-024-0095-4

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Herein, we present a photoinduced, CeCl₃-catalyzed three-component decarboxylative reaction that couples carboxylic acids, alkenes and tert-butyl hydroperoxide for the formation of various organic peroxides. The ligand-to-metal charge transfer (LMCT) excitation mode allows the decarboxylative alkylation-peroxidation reaction to occur under mild conditions, and is well applicable to primary, secondary and tertiary carboxylic acids and styrene derivatives.

Sandpaper-templated Stretchable Immunosensing Electrodes for Sub-picomolar Progesterone Detection

LI Zhaoxian, MENG Xingyu, FANG Chuyao, YI Zhenkai, WU Yaoyao, LIU Xuanxuan, ZHONG Wei, ZHANG Limei, XIE Zhuang

2024, 40(5): 874-880. doi:10.1007/s40242-024-4111-8

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Female hormone detection, particularly non-invasive monitoring progesterone (P4) levels in body fluids, plays a critical role in female health management and disease diagnosis. However, the challenge still exists because of the ultralow abundance of P4 (<100 pmol/L) in sweat and saliva, necessitating highly sensitive methods for wearable detection. Herein, we present a simple sandpaper-templated stretchable immunosensing electrode designed for ultra-sensitive detection of P4 at sub-picomolar level. A molding technique is employed to replicate the sandpaper textures to provide a microstructured elastomeric substrate for electrode preparation. Such microstructured surface coated with poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/LiTFSI [LiTFSI=lithium bis(trifluoromethanesulfonyl) imide] provided a stretchable polymer electrode with high conductivity, and further decoration with gold nanoparticles (AuNPs) enabled the immunosensing for P4 by electrochemical impedance spectroscopy (EIS) measurements. Through adjusting the AuNPs deposition conditions, ultrasensitive detection of P4 is realized with a low limit of detection (LOD) of ca. 10 fmol/L and a tunable dynamic range up to μmol/L. Notably, the stretchable electrode exhibits stable electrochemical performance, enabling the detection of P4 at sub-picomolar levels even under mechanical strain of 30%. This innovative electrochemical sensor holds significant promise for non-invasive, on-site monitoring of P4 levels in healthcare, as well as hormone detection in food safety and environment surveillance.

Synthesis and Properties of Ferrocene Conjugated Macrocycles with Illusory Topology of the Penrose Stairs

XU Jindong, LAN Bin, ZHU Lingyun, XU Hui, CHEN Xinyu, LI Wenjuan, YUAN Yaofeng, YAN Jianfeng, LI Yuanming

2024, 40(5): 881-886. doi:10.1007/s40242-024-4134-1

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Polyferrocene macrocycles hold immense potential in the fields of molecular electronics and electrochemistry, primarily due to their multiple metal centers. However, developing highly efficient synthetic strategies for constructing these rings remains a significant challenge. In this study, we successfully synthesized tri-ferrocenyl macrocycles using Pt-mediated coupling strategy and determined their configuration using single-crystal X-ray diffraction analysis, revealing a structure reminiscent of the Penrose Stair. We comprehensively investigated the macrocycle's structure, photophysical properties, and employed density functional theory (DFT) calculations to gain further insights. Notably, this macrocycle exhibits several advantageous features, including a flexible structure, good solubility, and a highly efficient synthetic pathway.

Copper(I) Cluster of Aggregation-induced Emission and X-Ray Scintillator Characteristic

XIONG Jiayu, WU Minjian, YAO Liao-Yuan

2024, 40(5): 887-893. doi:10.1007/s40242-024-4137-y

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Due to their precise atomic structures, photoluminescent copper nanoclusters (Cu NCs) have promising applications in basic research and technical applications, such as bioimaging, cell labeling, phototherapy, and photoactivation catalysis. In this work, we report a simple strategy for synthesizing novel CuNCs co-protected by alkynyl and phosphine ligands with the molecular formula [Cu₇(PPh₃)₁₀(PE)₃(CH₃O)] (Cu₄@Cu₃). Single-crystal X-ray crystallography reveals that the NC core exhibits an open square structure and an overall pyramid shape. Two Cu₄@Cu₃ units are connected through weak interactions to form dimers in crystals, creating a molecular cage that looks like two tightly closed bowls. Cu₄@Cu₃ exhibits dual emission in the visible region. It is also an aggregation-induced emission (AIE)-active luminescent substance, which exhibits strong emission in the visible light region when aggregated. Besides, it has the properties of radioluminescent (RL) and could be a potential scintillator material. This study not only enriches the types of atomically accurate AIE clusters, but also holds significant importance for the development of a new generation of high-performance and environmentally friendly X-ray scintillators.

Filterless Photosensors with Intrinsic Color Perception and Flexibility

ZHOU Hongtao, XU Beihang, ZHENG Xinjia, GONG Jinchao, ZHANG Kaitong, HE Yonglin

2024, 40(5): 894-900. doi:10.1007/s40242-024-4139-9

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Sensing materials possessing intrinsic color perception are indispensable prerequisites for the development of filterless photosensors, which could eliminate the need for complex device designs and avoid color distortion in post-processing. Traditional materials are constrained by complex processing methods and limited stability. Herein, a color-photosensitive array based on ionic liquid with selective photothermal conversion (ILSPC) has been developed for intrinsic color perception. Relying on the selective absorption, photothermal conversion, and thermosensitivity of ILSPC, a photo-thermo-electric sensing system has been constructed. Besides, the versatility of the two algorithms has been validated in color reconstruction and electrical signal prediction. As an exploration, the photosensitive array showcases promising color recognition capabilities, potentially propelling the evolution of flexible photosensors.

Waterproof Perovskite Quantum Dots for In-vivo Photoluminescence Bioimaging

JIAO Ziyue, WANG Xinli, GAO Jie, HUANG Xiao, WANG Yi

2024, 40(5): 901-906. doi:10.1007/s40242-024-4152-z

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Perovskite quantum dots (PQDs) have demonstrated great promise in bioimaging applications owing to their outstanding photophysical properties. Nonetheless, their practicality is seriously limited by the instability of PQDs against moisture. Here we develop a post-synthetic ligand exchange strategy to construct silica-coated PQD (PQD@SiO₂) nanocrystals, which results in the simultaneous improvement of photoluminescence efficiency and moisture stability. More importantly, compared to the classical in-situ ligand exchange method of fabricating PQD@SiO₂, the issues of chemical etching and resultant photoluminescence degradation are judiciously overcome. Employing the proposed PQD@SiO₂, we showcase their robust usefulness in labeling chlorella, paving the way for PQD-based in-vivo photoluminescence bioimaging methodology.

Photoinduced Bending and Curling Motions in Molecular Microcrystals of Naphthyl Meldrum's Acid Derivative Based on E-to-Z Photoisomerization

ZHANG Xiaowen, XU Tianyi, ZHANG Chenchen, TONG Fei

2024, 40(5): 907-913. doi:10.1007/s40242-024-4153-y

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Dynamic photoresponsive molecular crystals are promising candidates for making intelligent devices and materials in the future. Here, we synthesized a new photoactive molecule (E)-2,2-dimethyl-5-[3-(naphthalen-1-yl) allylide]-1,3-dioxane-4,6-dione [(E)-DNADD] that undergoes an E-to-Z photoisomerization in both liquid solution and solids when exposed to visible light (405 nm). Compared to the bulk crystals, the photoresponsive behavior in microcrystals was profoundly improved. Highly crystalline (E)-DNADD microplate crystals exhibit robust motions, including bending, curling, and coiling under light irradiation. The photoproduct conversion of the photochemical reaction in the microplate is no more than 20%, while the large bending curvature of the coiled illuminated samples was estimated at approximately 150—300 mm^-1, comparable to some photoactive nanowires. Our results indicate that shrinking crystal dimensions can boost the photoresponses in molecular crystals and provide a facile strategy for developing dynamic molecular crystals at the microscopic scale.

Promoted Non-enzymatic Glucose Sensor Based on Synergistic Effect of Hydrothermal Synthesized Ni(OH)₂-Graphene Nanocomposite

CAI Yuqing, CUI Qingyan, ZHANG Huanrong, MA Xinlei, XUE Mianqi

2024, 40(5): 914-921. doi:10.1007/s40242-024-4170-x

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Although glucose electrochemical sensors based on enzymes play a dominant role in market, their stability remains a problem due to the inherent nature of enzymes. Therefore, glucose sensors that are independent on enzymes have attracted more attention for the development of stable detection devices. Here we present an enzyme-free glucose sensor based on Ni(OH)₂ and reduced graphene oxide (rGO). The as-fabricated sensor still exhibits excellent electrocatalytic activity for detecting glucose under enzyme independent conditions. The enhanced catalytic performance may due to synergistic effect as follows: (i) the interaction between the Ni²⁺ and π electron of graphene induces the formation of the β-phase Ni(OH)₂ with higher catalytic activity; (ii) the frozen dry process works as a secondary filtration, getting rid of poorly formed Ni(OH)₂ particles with low catalytic activity; (iii) the rGO network with good conductivity provides a good electronic pathway for promoting electron transfer to reduce the response time. Based on the synergistic effect, the sensor exhibits a wide linear detection range from 0.2 μmol/L to 1.0 μmol/L and a low detection limit (0.1 μmol/L, S/N=3). The excellent detection performance, as well as the easy and low-cost preparation method, suggests the promising applicability of the sensor in the glucose detection market.

Low Temperature Tetragonal Tungsten Bronze Oxides for Li-ion Storage

XU Chengxin, ZHANG Wenda, LOU Chenjie, LI Chengyu, XU Ligang, SHI Yongchao, LIU Jie, LUO Huajie, FU Jipeng, KUANG Xiaojun, TANG Mingxue

2024, 40(5): 922-926. doi:10.1007/s40242-024-4173-7

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Nb-based tungsten bronze oxides have emerged as attractive materials in various fields, owing to the structural openings and simple synthesis method. In this work, the tetragonal tungsten bronze (TTB) NaWNbO₆ was prepared by solid state reaction at a relatively low temperature of 775 ℃. The local structure was systematically studied by solid state nuclear magnetic resonance (SSNMR) with the aid of transition electronic microscopy (TEM). The analysis indicates that NaWNbO₆ has pentagonal, square, and triangular tunnels. Notably, square tunnels were partly occupied (50%) by Na, which creates the ability for the Li-ion storage with a volumetric capacity of 210 A·h·L^-1 at 0.2 C. The 2D ²³Na-²³Na EXSY results further suggest the ability of ions to fast exchange between the tetragonal and pentagonal tunnels, resulting in a high-rate performance 20 C.

Chemical Activation of S/Li₂S in Li-S Batteries by a Bidirectional Organic Redox Mediator

LI Chengqiu, ZHOU Chaoyong, MEI Shilin, YAO Changjiang

2024, 40(5): 927-934. doi:10.1007/s40242-024-4177-3

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The energy density and lifespan of prototype Li-S batteries under high sulfur loading and lean electrolyte have been mainly restricted by the incomplete interconversion between insulating S₈ and Li₂S. The introduction of an electrocatalyst has been preserved as an effective way to breakthrough the bottleneck of the interconversion rate. Herein, we demonstrate a novel bidirectional redox mediator, insoluble dithiobisphthalimide (DTPI), as the electrocatalyst for both S₈ reduction and Li₂S oxidation. Due to the dual-functional role of both electron/Li⁺ donor and acceptor, DTPI can efficiently accelerate the redox reactions during charge/discharge and significantly alleviate the incomplete conversion of sulfur species. Consequently, the Li-S batteries with DTPI deliver superior specific capacity and cycling stability in comparison with those without DTPI. Especially, the redox mediator is scalable for synthesis and the DTPI-based 5 A·h pouch cell delivers a specific discharge capacity of around 870 mA·h·g^-1 at 0.1 C (1 C=1675 mA/g) without capacity fading over 80 cycles. The bidirectional catalysis mechanism has been studied through theoretical calculation and ex-situ characterization of the cathode materials. This work approves the effectiveness of bidirectional organic redox mediator in the construction of practical Li-S batteries.

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