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2024 Volume 40 Issue 12
2024, 40(12): 2259-2274
doi: 10.11862/CJIC.20240128
Abstract:
The review summarizes the recent research progress of pressure-temperature dual-functional flexible sensors, including the sensing mechanisms, the design of dual-functional sensors, and their applications in biomedicine. The sensing mechanisms of the sensors include electrical signal mechanisms (resistance, voltage, and capacitance mechanisms) and non-electrical signal mechanisms (optical and magnetic mechanisms). Then, the design strategies of pressure-temperature dual-functional flexible sensors are discussed, including the integration of different types of sensors and the design of single dual-functional sensors composed of multifunctional materials and microstructures. Finally, the applications of pressure-temperature dual-functional flexible sensors in human motion detection, health monitoring, artificial intelligence, and human-machine interaction are introduced. Based on this, the problems of dual-functional flexible sensors are summarized, and the future development prospects are discussed.
The review summarizes the recent research progress of pressure-temperature dual-functional flexible sensors, including the sensing mechanisms, the design of dual-functional sensors, and their applications in biomedicine. The sensing mechanisms of the sensors include electrical signal mechanisms (resistance, voltage, and capacitance mechanisms) and non-electrical signal mechanisms (optical and magnetic mechanisms). Then, the design strategies of pressure-temperature dual-functional flexible sensors are discussed, including the integration of different types of sensors and the design of single dual-functional sensors composed of multifunctional materials and microstructures. Finally, the applications of pressure-temperature dual-functional flexible sensors in human motion detection, health monitoring, artificial intelligence, and human-machine interaction are introduced. Based on this, the problems of dual-functional flexible sensors are summarized, and the future development prospects are discussed.
2024, 40(12): 2275-2285
doi: 10.11862/CJIC.20240229
Abstract:
Malignant tumors are one of the most serious threats to human health, and it has been a wildly discussed topic to establish efficient and accurate tumor treatment techniques. With the rapid development of nanomedicine technology, nanomaterial-mediated tumor treatment techniques have attracted more attention due to their low invasiveness, high specificity, and good therapeutic effects. As a new member of the nanomaterial family, atomically precise coinage metal nanoclusters show great potential in tumor treatment due to their excellent biocompatibility, surface modifiability, good optical properties, and efficient catalytic activity (generation of reactive oxygen species). This review mainly discusses the progress of research on atomically precise coinage metal nanoclusters in tumor treatment. Their antitumor mechanism is detailed in different therapies (radiation therapy, photothermal therapy, photodynamic therapy, chemodynamic therapy, drug delivery, and multimodal combination therapy). Moreover, the current challenges and prospects of metal nanoclusters in antitumors are summarized.
Malignant tumors are one of the most serious threats to human health, and it has been a wildly discussed topic to establish efficient and accurate tumor treatment techniques. With the rapid development of nanomedicine technology, nanomaterial-mediated tumor treatment techniques have attracted more attention due to their low invasiveness, high specificity, and good therapeutic effects. As a new member of the nanomaterial family, atomically precise coinage metal nanoclusters show great potential in tumor treatment due to their excellent biocompatibility, surface modifiability, good optical properties, and efficient catalytic activity (generation of reactive oxygen species). This review mainly discusses the progress of research on atomically precise coinage metal nanoclusters in tumor treatment. Their antitumor mechanism is detailed in different therapies (radiation therapy, photothermal therapy, photodynamic therapy, chemodynamic therapy, drug delivery, and multimodal combination therapy). Moreover, the current challenges and prospects of metal nanoclusters in antitumors are summarized.
2024, 40(12): 2286-2302
doi: 10.11862/CJIC.20240235
Abstract:
The bottom-up construction of artificial cell compartments, known as synthetic protocells, that can mimic the fundamental characteristics of living cells, is advancing at a rapid pace. This development not only bridges the gap between non-living and living entities but also provides crucial insights into the origin of life. Among them, inorganic protocells exhibit higher chemical and mechanical stability, biocompatibility, and flexibility in membrane design. Therefore, they hold great promise for research, particularly in the fields of cell biomimetics and biocatalysis. The article first introduces the basic characteristics of inorganic protocells, including compartmentalization, membrane selectivity, and cascade metabolic networks. Then, it provides an overview of the construction methods of inorganic protocells, with a focus on three main types of compartments: inorganic colloidosomes, magnetic nanoparticles, and polyoxometalates. Finally, it discusses their latest applications in cell biomimetics and biocatalysis, along with an analysis of current challenges and future development prospects.
The bottom-up construction of artificial cell compartments, known as synthetic protocells, that can mimic the fundamental characteristics of living cells, is advancing at a rapid pace. This development not only bridges the gap between non-living and living entities but also provides crucial insights into the origin of life. Among them, inorganic protocells exhibit higher chemical and mechanical stability, biocompatibility, and flexibility in membrane design. Therefore, they hold great promise for research, particularly in the fields of cell biomimetics and biocatalysis. The article first introduces the basic characteristics of inorganic protocells, including compartmentalization, membrane selectivity, and cascade metabolic networks. Then, it provides an overview of the construction methods of inorganic protocells, with a focus on three main types of compartments: inorganic colloidosomes, magnetic nanoparticles, and polyoxometalates. Finally, it discusses their latest applications in cell biomimetics and biocatalysis, along with an analysis of current challenges and future development prospects.
2024, 40(12): 2318-2334
doi: 10.11862/CJIC.20240247
Abstract:
In biological fluids, proteins bind to the surface of nanoparticles to form a coating named the protein corona, which can dramatically change their physicochemical properties and affect interactions with living systems. Understanding the formation mechanism and dynamic changes of protein corona can help optimize the design of nanoparticles, improve the targeting and effectiveness of nanomedicines, and reduce side effects. In this review, we first reviewed the progress of protein corona and highlighted the properties of protein corona, the factors influencing their formation, and the analytical techniques for probing the protein corona. Finally, we share our perspective on the challenges and opportunities of protein corona in characterization methods and controlling their formation and composition. This review will contribute to understanding protein corona for the development and application of nanomedicine and biotechnology.
In biological fluids, proteins bind to the surface of nanoparticles to form a coating named the protein corona, which can dramatically change their physicochemical properties and affect interactions with living systems. Understanding the formation mechanism and dynamic changes of protein corona can help optimize the design of nanoparticles, improve the targeting and effectiveness of nanomedicines, and reduce side effects. In this review, we first reviewed the progress of protein corona and highlighted the properties of protein corona, the factors influencing their formation, and the analytical techniques for probing the protein corona. Finally, we share our perspective on the challenges and opportunities of protein corona in characterization methods and controlling their formation and composition. This review will contribute to understanding protein corona for the development and application of nanomedicine and biotechnology.
2024, 40(12): 2335-2355
doi: 10.11862/CJIC.20240249
Abstract:
The responsive optical sensor demonstrates broad potential for specific detection and micro-quantitative analysis. Rare-earth-doped upconversion nanoparticle (UCNP), owing to their unique fluorescence properties, large anti-Stokes shift, good biocompatibility, and resistance to autofluorescence interference, can serve as emerging optical labels for achieving high-sensitivity biological detection at deeper tissue levels. This review focuses on the prospects and key applications of UCNP-based fluorescent nanoprobes in the field of biological detection, including specific detection of ions, reactive oxygen species, gases, and biomolecules. Additionally, this review discusses the sensing mechanisms of upconversion detection and the design principles of nanoprobes, evaluates the future challenges of upconversion nanoprobes in basic research and clinical applications, and aims to provide theoretical support and experimental guidance for the wide application of UCNP in biological detection and clinical diagnosis.
The responsive optical sensor demonstrates broad potential for specific detection and micro-quantitative analysis. Rare-earth-doped upconversion nanoparticle (UCNP), owing to their unique fluorescence properties, large anti-Stokes shift, good biocompatibility, and resistance to autofluorescence interference, can serve as emerging optical labels for achieving high-sensitivity biological detection at deeper tissue levels. This review focuses on the prospects and key applications of UCNP-based fluorescent nanoprobes in the field of biological detection, including specific detection of ions, reactive oxygen species, gases, and biomolecules. Additionally, this review discusses the sensing mechanisms of upconversion detection and the design principles of nanoprobes, evaluates the future challenges of upconversion nanoprobes in basic research and clinical applications, and aims to provide theoretical support and experimental guidance for the wide application of UCNP in biological detection and clinical diagnosis.
2024, 40(12): 2356-2372
doi: 10.11862/CJIC.20240254
Abstract:
Inorganic metal complex-based photothermal materials have garnered significant attention due to their advantages, such as ease of structural modification, tunable properties, high photothermal conversion efficiency, and good biocompatibility. In recent years, remarkable progress has been made in the development of photothermal agents for diagnostics and therapy. This review categorizes these complexes according to different organic ligands, including porphyrin, phthalocyanine, polyphenol, bis(disulfide), and azapyrrolidine, and examines how the coordination of various metal centers, ligand modifications, complex assembly, water solubility regulation, and targeting affect the photothermal properties and therapeutic performance. Additionally, we summarize the research advancements of the past decade in inorganic metal complex photothermal materials and offer insights into potential future directions to further advance their development and application.
Inorganic metal complex-based photothermal materials have garnered significant attention due to their advantages, such as ease of structural modification, tunable properties, high photothermal conversion efficiency, and good biocompatibility. In recent years, remarkable progress has been made in the development of photothermal agents for diagnostics and therapy. This review categorizes these complexes according to different organic ligands, including porphyrin, phthalocyanine, polyphenol, bis(disulfide), and azapyrrolidine, and examines how the coordination of various metal centers, ligand modifications, complex assembly, water solubility regulation, and targeting affect the photothermal properties and therapeutic performance. Additionally, we summarize the research advancements of the past decade in inorganic metal complex photothermal materials and offer insights into potential future directions to further advance their development and application.
2024, 40(12): 2373-2395
doi: 10.11862/CJIC.20240290
Abstract:
Small molecules, including inorganic compounds such as hydrogen, oxygen, ammonia, hydrocarbons, and hydrogen peroxide that can serve as energy sources, as well as organic compounds like urea and amino acids used in the biochemical industry, are assuming an increasingly pivotal role in daily life and production. The industrial synthesis of small molecule substances still faces challenges, such as the extensive utilization of precious metal catalysts and significant energy inefficiency. Electrochemical synthesis offers several advantages over traditional processes, including reduced catalyst costs, enhanced environmental sustainability, and superior performance. Porous material catalysts based on metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and porous coordination cages (PCCs) have attracted extensive attention due to their unique morphology, adjustable structure, high catalytic activity, and excellent chemical stability. Therefore, a key area of future research on the electrocatalytic synthesis of small molecules lies in advancing porous framework materials as electrocatalysts for synthesizing small molecule substances. This review provides a comprehensive overview of the utilization of these materials in electrocatalysis.
Small molecules, including inorganic compounds such as hydrogen, oxygen, ammonia, hydrocarbons, and hydrogen peroxide that can serve as energy sources, as well as organic compounds like urea and amino acids used in the biochemical industry, are assuming an increasingly pivotal role in daily life and production. The industrial synthesis of small molecule substances still faces challenges, such as the extensive utilization of precious metal catalysts and significant energy inefficiency. Electrochemical synthesis offers several advantages over traditional processes, including reduced catalyst costs, enhanced environmental sustainability, and superior performance. Porous material catalysts based on metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and porous coordination cages (PCCs) have attracted extensive attention due to their unique morphology, adjustable structure, high catalytic activity, and excellent chemical stability. Therefore, a key area of future research on the electrocatalytic synthesis of small molecules lies in advancing porous framework materials as electrocatalysts for synthesizing small molecule substances. This review provides a comprehensive overview of the utilization of these materials in electrocatalysis.
2024, 40(12): 2396-2414
doi: 10.11862/CJIC.20240106
Abstract:
In recent years, non-invasive photothermal therapy (PTT) and photodynamic therapy (PDT) have been booming in the field of treating cancer. They offer many advantages over chemotherapy and other traditional cancer treatments. Among various types of PTT and PDT agents for cancer, some inorganic nanomaterials with different properties can achieve highly effective cancer PTT or PDT, because compared with other materials, they have the advantage of strong absorption in the near-infrared (NIR) window. In addition to being used alone, inorganic nanomaterials can also be easily combined with other types of materials, chemical reagents, or drugs to construct multifunctional composite nano-therapeutic platforms. They are used to produce the synergistic effects of PTT, PDT, chemotherapy, and other therapies, enhance the therapeutic effect, and reduce toxicity and side effects to improve the cure rate of cancer patients. This review summarizes the latest research progress of common NIR inorganic nanomaterials in the field of cancer PTT and PDT, involving metal nanoparticles, carbon nanomaterials, MXenes, transition metal oxides and chalcogenides, black phosphorus nanosheets, and complex nanomaterials. The PTT and PDT therapeutic properties of these inorganic nanomaterials are mainly introduced. Finally, the research and development prospects of NIR inorganic nanosystems for cancer PTT and PDT in the future are put forward.
In recent years, non-invasive photothermal therapy (PTT) and photodynamic therapy (PDT) have been booming in the field of treating cancer. They offer many advantages over chemotherapy and other traditional cancer treatments. Among various types of PTT and PDT agents for cancer, some inorganic nanomaterials with different properties can achieve highly effective cancer PTT or PDT, because compared with other materials, they have the advantage of strong absorption in the near-infrared (NIR) window. In addition to being used alone, inorganic nanomaterials can also be easily combined with other types of materials, chemical reagents, or drugs to construct multifunctional composite nano-therapeutic platforms. They are used to produce the synergistic effects of PTT, PDT, chemotherapy, and other therapies, enhance the therapeutic effect, and reduce toxicity and side effects to improve the cure rate of cancer patients. This review summarizes the latest research progress of common NIR inorganic nanomaterials in the field of cancer PTT and PDT, involving metal nanoparticles, carbon nanomaterials, MXenes, transition metal oxides and chalcogenides, black phosphorus nanosheets, and complex nanomaterials. The PTT and PDT therapeutic properties of these inorganic nanomaterials are mainly introduced. Finally, the research and development prospects of NIR inorganic nanosystems for cancer PTT and PDT in the future are put forward.
2024, 40(12): 2303-2317
doi: 10.11862/CJIC.20240245
Abstract:
Corrole, a representative branch of porphyrin, has recently gained popularity. These molecules, viewed as ring-contracted porphyrinoids containing direct pyrrole-pyrrole linkages due to the absence of a meso-carbon atom, exhibit significant photo-physicochemical properties that make them attractive for various applications. Herein, this review comprehensively discusses the remarkable properties of corrole complexes, as well as related structures and chelation properties. It further explores the biological applications of corrole complexes for in vivo imaging and anticancer therapy. Additionally, it addresses common research bottlenecks and challenges, providing insights into future potential applications in disease diagnosis and treatment. Generally, this review aims to illuminate the significance of corrole complexes and their promising biological applications.
Corrole, a representative branch of porphyrin, has recently gained popularity. These molecules, viewed as ring-contracted porphyrinoids containing direct pyrrole-pyrrole linkages due to the absence of a meso-carbon atom, exhibit significant photo-physicochemical properties that make them attractive for various applications. Herein, this review comprehensively discusses the remarkable properties of corrole complexes, as well as related structures and chelation properties. It further explores the biological applications of corrole complexes for in vivo imaging and anticancer therapy. Additionally, it addresses common research bottlenecks and challenges, providing insights into future potential applications in disease diagnosis and treatment. Generally, this review aims to illuminate the significance of corrole complexes and their promising biological applications.
2024, 40(12): 2415-2421
doi: 10.11862/CJIC.20240304
Abstract:
A 1D Zn-based coordination polymer, {[Zn(L)(Phen)]·H2O}n (Zn-CP), was synthesized by the solvothermal method using 2, 2'-thiodiisonicotinic acid (H2L) and 1, 10-phenanthroline (Phen) as ligands. The structure of ZnCP was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared analysis, elemental analysis, and thermogravimetric analysis. The results of the fluorescence studies demonstrated that Zn-CP exhibited a fluorescence quenching response to the chlortetracycline (CTC). In addition, Zn-CP exhibited excellent sensitivity and a rapid response time of 30 s, while maintaining a high detection efficacy after five cycles. A strong linear relationship was observed within the detection range of 5.0-40.0 μmol·L-1, with a detection limit of 72.9 μmol·L-1. The fluorescence mechanism studies indicate that the quenching sensing effect of Zn-CP on CTC is a consequence of energy competition absorption.
A 1D Zn-based coordination polymer, {[Zn(L)(Phen)]·H2O}n (Zn-CP), was synthesized by the solvothermal method using 2, 2'-thiodiisonicotinic acid (H2L) and 1, 10-phenanthroline (Phen) as ligands. The structure of ZnCP was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared analysis, elemental analysis, and thermogravimetric analysis. The results of the fluorescence studies demonstrated that Zn-CP exhibited a fluorescence quenching response to the chlortetracycline (CTC). In addition, Zn-CP exhibited excellent sensitivity and a rapid response time of 30 s, while maintaining a high detection efficacy after five cycles. A strong linear relationship was observed within the detection range of 5.0-40.0 μmol·L-1, with a detection limit of 72.9 μmol·L-1. The fluorescence mechanism studies indicate that the quenching sensing effect of Zn-CP on CTC is a consequence of energy competition absorption.
2024, 40(12): 2422-2428
doi: 10.11862/CJIC.20240278
Abstract:
To study the synthesis and antitumor activities of the transition metal complexes incorporating a novel naphthol-aldehyde Schiff base ligand, three transition metal complexes [Cu(L)2(DMF)2] (1), [Ni(L)2(DMF)2] (2), and [Zn(L)2] (3) were synthesized using a Schiff base of N-[(2-hydroxy-1-naphthalenyl)methylene]-[(1H-indol-3-yl)ethyl] imine (HL) by liquid diffusion method. The complexes 1-3 were characterized by IR analysis, elemental analysis, and single-crystal X-ray diffraction. Moreover, their antitumor activities in vitro were screened through three human cancer cell lines (MGC-803, A549, MDA-MB-231) by the MTT assay. It revealed that complexes 1-3 showed high antitumor activities. Complex 1 showed much higher antitumor activities than complexes 2 and 3, and even than cisplatin. Among them, complex 1 had the highest inhibitory effects on tumor cells with its IC50 value (half-inhibitory concentration) being (4.8±0.2) μmol·L-1 against MGC-803 cells. These demonstrated a potential anti-cancer candidate for complex 1, which induced MGC-803 cancer cells' late apoptosis by flow cytometry. Subsequently, the cell scraper experiment showed that the killing effect of MGC-803 cells was enhanced with the increase in the concentration of complex 1.
To study the synthesis and antitumor activities of the transition metal complexes incorporating a novel naphthol-aldehyde Schiff base ligand, three transition metal complexes [Cu(L)2(DMF)2] (1), [Ni(L)2(DMF)2] (2), and [Zn(L)2] (3) were synthesized using a Schiff base of N-[(2-hydroxy-1-naphthalenyl)methylene]-[(1H-indol-3-yl)ethyl] imine (HL) by liquid diffusion method. The complexes 1-3 were characterized by IR analysis, elemental analysis, and single-crystal X-ray diffraction. Moreover, their antitumor activities in vitro were screened through three human cancer cell lines (MGC-803, A549, MDA-MB-231) by the MTT assay. It revealed that complexes 1-3 showed high antitumor activities. Complex 1 showed much higher antitumor activities than complexes 2 and 3, and even than cisplatin. Among them, complex 1 had the highest inhibitory effects on tumor cells with its IC50 value (half-inhibitory concentration) being (4.8±0.2) μmol·L-1 against MGC-803 cells. These demonstrated a potential anti-cancer candidate for complex 1, which induced MGC-803 cancer cells' late apoptosis by flow cytometry. Subsequently, the cell scraper experiment showed that the killing effect of MGC-803 cells was enhanced with the increase in the concentration of complex 1.
2024, 40(12): 2429-2437
doi: 10.11862/CJIC.20240275
Abstract:
A homobimetallic silver nitrogen heterocyclic carbene (NHC) complex NHC-Ag2 and a heterobimetallic silver/gold NHC complex NHC-Ag/Au were synthesized using phenanthroline functionalized imidazole salt ((HL)PF6, L=3-benzyl-1-(1, 10-phenanthrolin-2-yl)-imidazolylidene). NMR and elemental analysis characterized the NHC precursor and resultant NHC-metal complexes. Furthermore, X-ray diffraction analysis was conducted to examine the crystal structures of the two NHC-metal complexes. The results indicate that these two complexes share a similar structure wherein two phenanthrene-functionalized carbene ligands coordinate two metal center atoms. Within the homonuclear NHC-Ag2, the two central silver ions exhibit distinct coordination modes, with an Ag—Ag distance of 0.282 87 nm. One silver ion is bis-coordinated by two carbene carbon atoms in a linear fashion, with C— Ag—C bond angle of 172.5°. In contrast, the other silver ion is coordinated with four nitrogen atoms from two phenanthrolines in a tetrahedral configuration. In the heteronuclear NHC-Ag/Au, the gold ion is coordinated linearly by two carbene carbon atoms, forming a C—Au—C bond angle of 176.2°, and the silver ion is coordinated in a distorted tetrahedral fashion by four nitrogen atoms from two phenanthrolines. The in vitro cytotoxic studies revealed that both NHC-Ag2 and NHC-Ag/Au exhibited stronger antitumor activity compared to their NHC precursor and cisplatin. Specifically, in the case of LoVo cells, NHC-Ag2 and NHC-Ag/Au demonstrated potent cytotoxicity with half inhibitory concentration (IC50) values of (5.6±0.3) μmol·L-1 and (6.4±0.3) μmol·L-1, respectively, which were lower than that of cisplatin. Detailed mechanistic studies suggested that complexes NHC-Ag2 and NHC-Ag/Au provoked mitochondrial membrane depolarization and intracellular reactive oxygen species (ROS) overproduction, which eventually resulted in cell membrane permeability and cell death.
A homobimetallic silver nitrogen heterocyclic carbene (NHC) complex NHC-Ag2 and a heterobimetallic silver/gold NHC complex NHC-Ag/Au were synthesized using phenanthroline functionalized imidazole salt ((HL)PF6, L=3-benzyl-1-(1, 10-phenanthrolin-2-yl)-imidazolylidene). NMR and elemental analysis characterized the NHC precursor and resultant NHC-metal complexes. Furthermore, X-ray diffraction analysis was conducted to examine the crystal structures of the two NHC-metal complexes. The results indicate that these two complexes share a similar structure wherein two phenanthrene-functionalized carbene ligands coordinate two metal center atoms. Within the homonuclear NHC-Ag2, the two central silver ions exhibit distinct coordination modes, with an Ag—Ag distance of 0.282 87 nm. One silver ion is bis-coordinated by two carbene carbon atoms in a linear fashion, with C— Ag—C bond angle of 172.5°. In contrast, the other silver ion is coordinated with four nitrogen atoms from two phenanthrolines in a tetrahedral configuration. In the heteronuclear NHC-Ag/Au, the gold ion is coordinated linearly by two carbene carbon atoms, forming a C—Au—C bond angle of 176.2°, and the silver ion is coordinated in a distorted tetrahedral fashion by four nitrogen atoms from two phenanthrolines. The in vitro cytotoxic studies revealed that both NHC-Ag2 and NHC-Ag/Au exhibited stronger antitumor activity compared to their NHC precursor and cisplatin. Specifically, in the case of LoVo cells, NHC-Ag2 and NHC-Ag/Au demonstrated potent cytotoxicity with half inhibitory concentration (IC50) values of (5.6±0.3) μmol·L-1 and (6.4±0.3) μmol·L-1, respectively, which were lower than that of cisplatin. Detailed mechanistic studies suggested that complexes NHC-Ag2 and NHC-Ag/Au provoked mitochondrial membrane depolarization and intracellular reactive oxygen species (ROS) overproduction, which eventually resulted in cell membrane permeability and cell death.
2024, 40(12): 2438-2444
doi: 10.11862/CJIC.20240240
Abstract:
A novel europium metal-organic framework (Eu-MOF) with formula (H3O)6[Eu(BHC)(H2O)]2·H2O (1) has been synthesized successfully via the hydrothermal method by using a monoaromatic polycarboxylic acid ligand benzenehexacarboxylic acid (H6BHC) reacting with Eu(NO3)3·6H2O. Singlecrystal X-ray diffraction analysis reveals that in 1 the adjacent two Eu(Ⅲ) cations are bridged by the BHC6- ligands to form the Eu dinuclear unit as a node, and then the Eu dinuclear nodes join each other via the BHC6- as bridges plus the hydrogen bond interactions along a-, b- and c-axis to form a unique 3D network structure. Photoluminescence measurement indicates that 1 possesses the following advantages as the fluorescent probe: 1 displayed a very low limit of detection (LOD) for Pb2+ (0.42 μmol·L-1) in an aqueous system, and 1 demonstrated higher selectivity.
A novel europium metal-organic framework (Eu-MOF) with formula (H3O)6[Eu(BHC)(H2O)]2·H2O (1) has been synthesized successfully via the hydrothermal method by using a monoaromatic polycarboxylic acid ligand benzenehexacarboxylic acid (H6BHC) reacting with Eu(NO3)3·6H2O. Singlecrystal X-ray diffraction analysis reveals that in 1 the adjacent two Eu(Ⅲ) cations are bridged by the BHC6- ligands to form the Eu dinuclear unit as a node, and then the Eu dinuclear nodes join each other via the BHC6- as bridges plus the hydrogen bond interactions along a-, b- and c-axis to form a unique 3D network structure. Photoluminescence measurement indicates that 1 possesses the following advantages as the fluorescent probe: 1 displayed a very low limit of detection (LOD) for Pb2+ (0.42 μmol·L-1) in an aqueous system, and 1 demonstrated higher selectivity.
2024, 40(12): 2445-2454
doi: 10.11862/CJIC.20240194
Abstract:
A multifunctional nanomaterial CuO2/PB with H2O2 self-supply and photothermal-enhanced enzyme-like activity was obtained by introducing CuO2 into Prussian blue (PB). The simulated tumor microenvironment (TME) can produce H2O2 and consume glutathione (GSH), further enhancing the generation of ·OH and the consumption of GSH with near-infrared light irradiation. In addition, mouse experiments have shown that CuO2/PB can be used for T2 -magnetic resonance imagingguided tumor therapy. In the 14 d treatment cycle, combined with near-infrared light irradiation, it had a significant inhibitory effect on tumors, achieving photothermal therapy combined with H2O2 self-supply catalytic therapy, which provides a new idea for improving the efficiency of catalytic treatment.
A multifunctional nanomaterial CuO2/PB with H2O2 self-supply and photothermal-enhanced enzyme-like activity was obtained by introducing CuO2 into Prussian blue (PB). The simulated tumor microenvironment (TME) can produce H2O2 and consume glutathione (GSH), further enhancing the generation of ·OH and the consumption of GSH with near-infrared light irradiation. In addition, mouse experiments have shown that CuO2/PB can be used for T2 -magnetic resonance imagingguided tumor therapy. In the 14 d treatment cycle, combined with near-infrared light irradiation, it had a significant inhibitory effect on tumors, achieving photothermal therapy combined with H2O2 self-supply catalytic therapy, which provides a new idea for improving the efficiency of catalytic treatment.
2024, 40(12): 2455-2465
doi: 10.11862/CJIC.20240192
Abstract:
Three new tetranuclear lanthanide-based complexes, namely [Ln4(dbm)6(L)2(μ2-OCH3)2(CH3OH)2] · xCH3OH [Ln=Eu (1), Tb (2), and Tm (3); x=3 (1), 0 (2), and 0 (3); Hdbm=dibenzoylmethane], were successfully designed and constructed by using a polydentate Schiff base (E)-2-hydroxy-3-methoxy-N'-(6-methoxy-pyridine-2-methylene)benzoylhydrazine (H2L) reacting with Ln(dbm)3·6H2O via solvothermal method. Single crystal X-ray diffraction analysis shows that the coordination units of1-3 comprise four LnⅢ ions, six dbm- ligands, two L2- ligands, two μ2 -OCH3 ligands, and two coordinated CH3OH molecules. Four central LnⅢ ions are interlinked by six μ2-O atoms displaying a linear tetranuclear structure. Solid fluorescence tests show that1 and2 exhibited fluorescence emission peaks of Ln(Ⅲ) ions at room temperature. In addition, antibacterial studies indicate that1-3 had stronger antibacterial activity than ligand H2L and Ln(Ⅲ) ions. The interaction between1-3 and calf thymus DNA (CT-DNA) was studied by ultraviolet spectroscopy, cyclic voltammetry, and fluorescence spectrometry. The results indicate that1-3 are primarily intercalated with CT-DNA.
Three new tetranuclear lanthanide-based complexes, namely [Ln4(dbm)6(L)2(μ2-OCH3)2(CH3OH)2] · xCH3OH [Ln=Eu (1), Tb (2), and Tm (3); x=3 (1), 0 (2), and 0 (3); Hdbm=dibenzoylmethane], were successfully designed and constructed by using a polydentate Schiff base (E)-2-hydroxy-3-methoxy-N'-(6-methoxy-pyridine-2-methylene)benzoylhydrazine (H2L) reacting with Ln(dbm)3·6H2O via solvothermal method. Single crystal X-ray diffraction analysis shows that the coordination units of1-3 comprise four LnⅢ ions, six dbm- ligands, two L2- ligands, two μ2 -OCH3 ligands, and two coordinated CH3OH molecules. Four central LnⅢ ions are interlinked by six μ2-O atoms displaying a linear tetranuclear structure. Solid fluorescence tests show that1 and2 exhibited fluorescence emission peaks of Ln(Ⅲ) ions at room temperature. In addition, antibacterial studies indicate that1-3 had stronger antibacterial activity than ligand H2L and Ln(Ⅲ) ions. The interaction between1-3 and calf thymus DNA (CT-DNA) was studied by ultraviolet spectroscopy, cyclic voltammetry, and fluorescence spectrometry. The results indicate that1-3 are primarily intercalated with CT-DNA.
2024, 40(12): 2466-2474
doi: 10.11862/CJIC.20240266
Abstract:
Two coordination polymers were synthesized by hydrothermal reaction, namely, [Cd(H3cpbda)(2, 2'-bipy) (H2O)]n (1) and[Mn(H3cpbda)(phen)(H2O)]n (2), where H5cpbda=5, 5'-[(5-carboxy-1, 3-phenyl)bis(oxy)]triisophthalic acid, 2, 2'-bipy=2, 2'-bipyridine, phen=1, 10-phenanthroline. The two complexes were characterized by single-crystal X-ray diffraction, powder diffraction, infrared spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are "V"-shaped 1D chains, and the molecules form 2D (1) and 3D framework (2) structures through weak π…π stacking. Furthermore, complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability. Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10-8 mol·L-1.
Two coordination polymers were synthesized by hydrothermal reaction, namely, [Cd(H3cpbda)(2, 2'-bipy) (H2O)]n (1) and[Mn(H3cpbda)(phen)(H2O)]n (2), where H5cpbda=5, 5'-[(5-carboxy-1, 3-phenyl)bis(oxy)]triisophthalic acid, 2, 2'-bipy=2, 2'-bipyridine, phen=1, 10-phenanthroline. The two complexes were characterized by single-crystal X-ray diffraction, powder diffraction, infrared spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are "V"-shaped 1D chains, and the molecules form 2D (1) and 3D framework (2) structures through weak π…π stacking. Furthermore, complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability. Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10-8 mol·L-1.
2024, 40(12): 2475-2485
doi: 10.11862/CJIC.20240193
Abstract:
We used pentacarboxylic acid ligand 3, 5-di(2', 4'-dicarboxylphenyl) benzoic acid (H5L) to synthesize two structural similarity lanthanide-cobalt heteronuclear bimetallic organic frameworks (Ln-Co-MOFs) by hydrothermal method: (C2H6NH2)5{[Eu9Co(L)6(H2O)5(OH)4] ·5DMF}n (1), (C2H6NH2)2{[Sm9Co(L)6(H2O)3Cl] ·5DMF}n (2). The structures were characterized and the property was tested by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, infrared, fluorescence spectra, and magnetism. The results show that 1 and 2 both belong to the trigonal R3 space group and have novel 3D structures and good thermal stability. Among them, 1 has strong fluorescence properties, which can sensitively identify drug molecules sulfasalazine and organic molecules glutaraldehyde. The detection limits could reach 0.95 and 2.10 μmol·L-1, respectively. In addition, 1 and 2 were antiferromagnetic at 1 kOe.
We used pentacarboxylic acid ligand 3, 5-di(2', 4'-dicarboxylphenyl) benzoic acid (H5L) to synthesize two structural similarity lanthanide-cobalt heteronuclear bimetallic organic frameworks (Ln-Co-MOFs) by hydrothermal method: (C2H6NH2)5{[Eu9Co(L)6(H2O)5(OH)4] ·5DMF}n (1), (C2H6NH2)2{[Sm9Co(L)6(H2O)3Cl] ·5DMF}n (2). The structures were characterized and the property was tested by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, infrared, fluorescence spectra, and magnetism. The results show that 1 and 2 both belong to the trigonal R3 space group and have novel 3D structures and good thermal stability. Among them, 1 has strong fluorescence properties, which can sensitively identify drug molecules sulfasalazine and organic molecules glutaraldehyde. The detection limits could reach 0.95 and 2.10 μmol·L-1, respectively. In addition, 1 and 2 were antiferromagnetic at 1 kOe.
2024, 40(12): 2486-2496
doi: 10.11862/CJIC.20240122
Abstract:
Two new dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(dbm)2(HL)2(CH3OH)2]·4CH3OH [Ln=Tb (1) and Dy (2), Hdbm=dibenzoylmethane] have been synthesized using prepared multidentate Schiff base ligand H3L (hydroxy-acetic acid(4-diethylamino-2-hydroxy-benzylidene)-hydrazide) with good biological activity. Structure characterizations show that the complex comprises two Ln3+ ions, two dbm- ions, two HL2- ligands, two CH3OH molecules, and four free methanol molecules. Each Ln3+ ion is eight-coordinated. The two central Ln(Ⅲ) ions are bridged by two μ2-O atoms leading to a parallelogram [Ln2O2] core. The interaction between the compounds (H3L, 1, and 2) and the calf thymus DNA (CT-DNA) has been further confirmed by UV-Vis spectrometry, fluorescence titration, and cyclic voltammetry. The results showed that both 1 and 2 could undergo insertion with CT-DNA.
Two new dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(dbm)2(HL)2(CH3OH)2]·4CH3OH [Ln=Tb (1) and Dy (2), Hdbm=dibenzoylmethane] have been synthesized using prepared multidentate Schiff base ligand H3L (hydroxy-acetic acid(4-diethylamino-2-hydroxy-benzylidene)-hydrazide) with good biological activity. Structure characterizations show that the complex comprises two Ln3+ ions, two dbm- ions, two HL2- ligands, two CH3OH molecules, and four free methanol molecules. Each Ln3+ ion is eight-coordinated. The two central Ln(Ⅲ) ions are bridged by two μ2-O atoms leading to a parallelogram [Ln2O2] core. The interaction between the compounds (H3L, 1, and 2) and the calf thymus DNA (CT-DNA) has been further confirmed by UV-Vis spectrometry, fluorescence titration, and cyclic voltammetry. The results showed that both 1 and 2 could undergo insertion with CT-DNA.
2024, 40(12): 2497-2504
doi: 10.11862/CJIC.20240084
Abstract:
Herein, a layered chiral coordination polymer, [Cd2(D-cam)2(2, 2'-bipy)2]n (Cd-CP), was synthesized using a solvothermal method with camphoric acid (D-H2cam), 2, 2'-bipyridine (2, 2'-bipy) and Cd2+, and Tb3+@Cd-CP was in-situ synthesized introducing Tb3+ ions. The fluorescence experiments revealed that compared to Cd-CP, Tb3+@Cd-CP exhibited ultra-high fluorescence performance. The luminescence sensing performance demonstrated that Tb3+@Cd-CP could distinguish R/S-propylene glycol (R/S-PG) by fluorescence responses, with fluorescence quenching constant of 5.3×103 and 2.0×103 L·mol-1 respectively and the enantioselectivity factor (α) of 2.65. Moreover, Tb3+@Cd-CP demonstrated limits of detection of 9.3 and 19.0 μmol·L-1 for R-PG and S-PG, respectively, and showed good reproducibility.
Herein, a layered chiral coordination polymer, [Cd2(D-cam)2(2, 2'-bipy)2]n (Cd-CP), was synthesized using a solvothermal method with camphoric acid (D-H2cam), 2, 2'-bipyridine (2, 2'-bipy) and Cd2+, and Tb3+@Cd-CP was in-situ synthesized introducing Tb3+ ions. The fluorescence experiments revealed that compared to Cd-CP, Tb3+@Cd-CP exhibited ultra-high fluorescence performance. The luminescence sensing performance demonstrated that Tb3+@Cd-CP could distinguish R/S-propylene glycol (R/S-PG) by fluorescence responses, with fluorescence quenching constant of 5.3×103 and 2.0×103 L·mol-1 respectively and the enantioselectivity factor (α) of 2.65. Moreover, Tb3+@Cd-CP demonstrated limits of detection of 9.3 and 19.0 μmol·L-1 for R-PG and S-PG, respectively, and showed good reproducibility.
