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2020 Volume 36 Issue 7
2020, 36(7): 1205-1222
doi: 10.11862/CJIC.2020.136
Abstract:
The issues of climate change and fossil fuel depletion will promote the development and use of new green energy sources. Therefore, the energy storage system with high efficiency, low cost and safety has received more and more attention and research. Among various types of energy storage systems, secondary batteries are the best choice for storing electric energy and powering electronic devices. Currently, lithium-ion batteries (LIBs) are the most widely used. However, due to the high cost caused by the shortage and uneven distribution of lithium resources on earth, research and development of other high-performance new secondary batteries are urgently needed. Sodium element has the advantages of abundant reserves in the crust, uniformity and similar chemical properties with lithium, so sodium ion batteries (SIBs) is one of the most promising alternative secondary batteries to replace LIBs. However, problems such as larger volume of sodium ions, slower ion conduction kinetics and worse conductivity limit the realization of high performance of SIBs, which is the difficulty and focus of current research. In addition, iron is rich in reserves and environmentally friendly, and its application in SIBs has attracted extensive attention from researchers in the field of batteries. Therefore, finding good iron-based cathode materials has become an important research direction for the development of high-performance electrode materials of SIBs. This review summarizes the recent progress in the research of iron-based cathode materials for SIBs, and systematically describes and analyzes the classification of polyanionic compounds, transition metal oxides, Prussian blue and its analogues, and fluorides.
The issues of climate change and fossil fuel depletion will promote the development and use of new green energy sources. Therefore, the energy storage system with high efficiency, low cost and safety has received more and more attention and research. Among various types of energy storage systems, secondary batteries are the best choice for storing electric energy and powering electronic devices. Currently, lithium-ion batteries (LIBs) are the most widely used. However, due to the high cost caused by the shortage and uneven distribution of lithium resources on earth, research and development of other high-performance new secondary batteries are urgently needed. Sodium element has the advantages of abundant reserves in the crust, uniformity and similar chemical properties with lithium, so sodium ion batteries (SIBs) is one of the most promising alternative secondary batteries to replace LIBs. However, problems such as larger volume of sodium ions, slower ion conduction kinetics and worse conductivity limit the realization of high performance of SIBs, which is the difficulty and focus of current research. In addition, iron is rich in reserves and environmentally friendly, and its application in SIBs has attracted extensive attention from researchers in the field of batteries. Therefore, finding good iron-based cathode materials has become an important research direction for the development of high-performance electrode materials of SIBs. This review summarizes the recent progress in the research of iron-based cathode materials for SIBs, and systematically describes and analyzes the classification of polyanionic compounds, transition metal oxides, Prussian blue and its analogues, and fluorides.
2020, 36(7): 1223-1232
doi: 10.11862/CJIC.2020.159
Abstract:
As one of the few natural products that is useful both in the prevention and treatment of cancers, perillol has been used as a clinical drug for the treatment of cancer. However, perillol has low bioavailability and large dosage by oral administration, which limits its clinical application. In this work, perillol was chemically modified and introduced into the metal-arene complex as a ligand, thus a novel ruthenium-arene complex Ru-L was synthesized and characterized by NMR, ESI-MS and elemental analysis. The complex exhibited high cytotoxic activity against several tumor cells A2780, A2780/DDP and MCF-7, while it was none toxic to the normal cell lines (IC50>200 μmol·L-1). Absorbance and fluorescence spectra suggested that the complex had a fast hydrolysis rate, could bind to CTDNA with a high affinity through intercalation mode and interact with BSA/HSA by static quenching. Flow cytometry also revealed that the complex induced tumor cell cycle arrest in the G0/G1 phase, which led to apoptosis of tumor cells. The above results indicate that the ruthenium-arene complex Ru-L based on perillol can overcome the disadvantages of perillyl alcohol, such as its high doses and severe toxicity.
As one of the few natural products that is useful both in the prevention and treatment of cancers, perillol has been used as a clinical drug for the treatment of cancer. However, perillol has low bioavailability and large dosage by oral administration, which limits its clinical application. In this work, perillol was chemically modified and introduced into the metal-arene complex as a ligand, thus a novel ruthenium-arene complex Ru-L was synthesized and characterized by NMR, ESI-MS and elemental analysis. The complex exhibited high cytotoxic activity against several tumor cells A2780, A2780/DDP and MCF-7, while it was none toxic to the normal cell lines (IC50>200 μmol·L-1). Absorbance and fluorescence spectra suggested that the complex had a fast hydrolysis rate, could bind to CTDNA with a high affinity through intercalation mode and interact with BSA/HSA by static quenching. Flow cytometry also revealed that the complex induced tumor cell cycle arrest in the G0/G1 phase, which led to apoptosis of tumor cells. The above results indicate that the ruthenium-arene complex Ru-L based on perillol can overcome the disadvantages of perillyl alcohol, such as its high doses and severe toxicity.
2020, 36(7): 1233-1240
doi: 10.11862/CJIC.2020.148
Abstract:
Magnetic hollow carbon nanospheres (MHCNS) with uniform particle size were prepared by high temperature calcination using acorn as carbon source. MHCNS-1 can be obtained by HCl soaking treatment, and then treated with HNO3 and NH3·H2O to obtain MHCNS-2. MHCNS-2 had a uniform particle size with a diameter of 20~40 nm and a wall thickness of 3~5 nm. The size of MHCNS can be adjusted by changing the amount and ratio of Ni2+ and KOH. The prepared products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer and transmission electron microscopy (TEM). The growth mechanism of MHCNS was analyzed. The results of the adsorption performance of MHCNS-2 on the organic dye methylene blue (MB) show that MHCNS-2 has strong adsorption performance. When the concentration of MB solution was 100 mg·L-1, the adsorption amount could reach 185 mg·g-1. The results of MHCNS-2 on drug-loaded drug release of ibuprofen showed that the drug-loading rate of MHCNS-2 was up to 44% and the drug release rate was 70%, which means that it has good drug-loading and drug-releasing ability.
Magnetic hollow carbon nanospheres (MHCNS) with uniform particle size were prepared by high temperature calcination using acorn as carbon source. MHCNS-1 can be obtained by HCl soaking treatment, and then treated with HNO3 and NH3·H2O to obtain MHCNS-2. MHCNS-2 had a uniform particle size with a diameter of 20~40 nm and a wall thickness of 3~5 nm. The size of MHCNS can be adjusted by changing the amount and ratio of Ni2+ and KOH. The prepared products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer and transmission electron microscopy (TEM). The growth mechanism of MHCNS was analyzed. The results of the adsorption performance of MHCNS-2 on the organic dye methylene blue (MB) show that MHCNS-2 has strong adsorption performance. When the concentration of MB solution was 100 mg·L-1, the adsorption amount could reach 185 mg·g-1. The results of MHCNS-2 on drug-loaded drug release of ibuprofen showed that the drug-loading rate of MHCNS-2 was up to 44% and the drug release rate was 70%, which means that it has good drug-loading and drug-releasing ability.
2020, 36(7): 1241-1248
doi: 10.11862/CJIC.2020.171
Abstract:
Three novel cucurbit[n]uril-based (Q[n]-based) supramolecular frameworks(QSFs) have been successfully prepared by using the planar configuration[PdnClm]2- anion as the structure-directing agent, namely {Na2(H2O)6TMeQ[6]}[Pd2Cl6]·3H2O (1), (H3O)2{CyH5Q[5]}[Pd2Cl6]·3H2O (2) and (H3O)2{Q[5]}[PdCl4]·23H2O (3), respectively. Structural analysis reveals that using the[PdnClm]2- anion as the structure-directing agent in different Q[n] systems that can promote the orderly arrangement of Q[n]s, and contribute to the formation of QSFs with different frame structures. For 1, the carbonyl groups of TMeQ[6] bind directly to the Na(Ⅰ) ions to form 1D coordination chains, which can be further built into 3D supramolecular architecture by outer surface interactions between TMeQ[6] and the[Pd2Cl6]2- anions. For 2, under the guidance of[Pd2Cl6]2- anions, CyH5Q[5] molecules can be orderly arranged to construct a 3D structure with pores which are filled with[Pd2Cl6]2- anions, while it can be found in 3 that Q[5] molecules can also be orderly arranged by[PdCl4]2- anions to form a 3D frameworks with a 1D channel. The driving force to result in the formation of such frameworks is attributed to the outer surface interaction of Q[n]s, which is ion-dipole between the electrostatic potential positive outer surface of Q[n]s and the[PdnClm]2- anions.CCDC: 1956589, 1; 1956591, 2; 1956590, 3.
Three novel cucurbit[n]uril-based (Q[n]-based) supramolecular frameworks(QSFs) have been successfully prepared by using the planar configuration[PdnClm]2- anion as the structure-directing agent, namely {Na2(H2O)6TMeQ[6]}[Pd2Cl6]·3H2O (1), (H3O)2{CyH5Q[5]}[Pd2Cl6]·3H2O (2) and (H3O)2{Q[5]}[PdCl4]·23H2O (3), respectively. Structural analysis reveals that using the[PdnClm]2- anion as the structure-directing agent in different Q[n] systems that can promote the orderly arrangement of Q[n]s, and contribute to the formation of QSFs with different frame structures. For 1, the carbonyl groups of TMeQ[6] bind directly to the Na(Ⅰ) ions to form 1D coordination chains, which can be further built into 3D supramolecular architecture by outer surface interactions between TMeQ[6] and the[Pd2Cl6]2- anions. For 2, under the guidance of[Pd2Cl6]2- anions, CyH5Q[5] molecules can be orderly arranged to construct a 3D structure with pores which are filled with[Pd2Cl6]2- anions, while it can be found in 3 that Q[5] molecules can also be orderly arranged by[PdCl4]2- anions to form a 3D frameworks with a 1D channel. The driving force to result in the formation of such frameworks is attributed to the outer surface interaction of Q[n]s, which is ion-dipole between the electrostatic potential positive outer surface of Q[n]s and the[PdnClm]2- anions.CCDC: 1956589, 1; 1956591, 2; 1956590, 3.
2020, 36(7): 1249-1258
doi: 10.11862/CJIC.2020.091
Abstract:
The magnetic carbon-based material (Fe3O4@C) was prepared by using ferrocene, and chitosan (CS) modified Fe3O4@C composite adsorbent (Fe3O4@C-CS) was prepared. The characterization of Fe3O4@C-CS by nfrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS), and the adsorption performance for Cr (Ⅲ)-EDTA in water was systematically studied by initial concentrations, adsorption temperature, time, solution pH and cations. The results show that Fe3O4@C has been successfully functionalized by CS. Adsorption isotherm was in accordance with the Langmuir model and the theoretical maximum adsorption capacity was 12.63 mg·g-1 at 25℃, pH=4.0 and dosage of 0.4 g·L-1. The adsorption kinetics can be fitted well with the pseudo-second kinetic model, and adsorption behavior is a spontaneous endothermic process. Based on the XPS analysis and adsorption experiments, the electrostatic interaction and surface complexation was the main mechanism of Cr(Ⅲ)-EDTA adsorption on Fe3O4@CCS adsorbent. After four adsorption and desorption cycles, Fe3O4@C-CS still had high adsorption efficiency for Cr(Ⅲ)EDTA in water.
The magnetic carbon-based material (Fe3O4@C) was prepared by using ferrocene, and chitosan (CS) modified Fe3O4@C composite adsorbent (Fe3O4@C-CS) was prepared. The characterization of Fe3O4@C-CS by nfrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS), and the adsorption performance for Cr (Ⅲ)-EDTA in water was systematically studied by initial concentrations, adsorption temperature, time, solution pH and cations. The results show that Fe3O4@C has been successfully functionalized by CS. Adsorption isotherm was in accordance with the Langmuir model and the theoretical maximum adsorption capacity was 12.63 mg·g-1 at 25℃, pH=4.0 and dosage of 0.4 g·L-1. The adsorption kinetics can be fitted well with the pseudo-second kinetic model, and adsorption behavior is a spontaneous endothermic process. Based on the XPS analysis and adsorption experiments, the electrostatic interaction and surface complexation was the main mechanism of Cr(Ⅲ)-EDTA adsorption on Fe3O4@CCS adsorbent. After four adsorption and desorption cycles, Fe3O4@C-CS still had high adsorption efficiency for Cr(Ⅲ)EDTA in water.
2020, 36(7): 1259-1266
doi: 10.11862/CJIC.2020.172
Abstract:
A series of 4, 5, 9, 10-tetraaryl-quinazinoquinoline derivatives were synthesized and applied to hydrogen evolution in water splitting as photosensitizers. In this photocatalytic water reduction system, PdCl2 is the most suitable water reduction catalyst and the reduction quenching is the main quench way for the excited photosensitizers. The substituent effect could explain the structure-activity relationship in photocatalytic water reduction system. The methoxy group as an electron donating substituent was found to increase the turnover number for hydrogen production (TON) of the derivatives up to 341. Photophysical and electronic chemical characterization of quinazinoquinoline derivatives showed that the methoxy group could increase the fluorescence quantum efficiency of the derivatives up to 0.48.
A series of 4, 5, 9, 10-tetraaryl-quinazinoquinoline derivatives were synthesized and applied to hydrogen evolution in water splitting as photosensitizers. In this photocatalytic water reduction system, PdCl2 is the most suitable water reduction catalyst and the reduction quenching is the main quench way for the excited photosensitizers. The substituent effect could explain the structure-activity relationship in photocatalytic water reduction system. The methoxy group as an electron donating substituent was found to increase the turnover number for hydrogen production (TON) of the derivatives up to 341. Photophysical and electronic chemical characterization of quinazinoquinoline derivatives showed that the methoxy group could increase the fluorescence quantum efficiency of the derivatives up to 0.48.
2020, 36(7): 1267-1274
doi: 10.11862/CJIC.2020.165
Abstract:
This work reports the synthesis and properties of three iridium(（Ⅲ）) complexes ((tfmppy)2Ir(F-tpip), (tfmppy)2Ir (MeO-tpip) and (tfmppy)2Ir(tnin)) with 2-(4-(trifluoromethyl)phenyl)pyridine (tfmppy) as main ligand and tetra(4-fluoropheny) imidodiphosphinate (F-tpip), tetra(4-methoxypheny)imidodiphosphinate (MeO-tpip), tetra(naphthalen-1-yl) imidodiphosphinate (tnin) as ancillary ligands, respectively. Their structures were confirmed by 1H NMR, MS (MALDI-TOF), elemental and single crystal analysis. Both (tfmppy)2Ir(F-tpip) and (tfmppy)2Ir(MeO-tpip) complexes belong to P1 space group of triclinic crystal system. The complex (tfmppy)2Ir(tnin) belongs to R3c space group of trigonal crystal system. All the complexes are green materials with similar emission color and photoluminescence quantum efficiency ((tfmppy)2Ir(F-tpip):λem=526 nm, Φ=0.52; (tfmppy)2Ir(MeO-tpip):λem=523 nm, Φ=0.44; (tfmppy)2Ir (tnin):λem=522 nm, Φ=0.48). In addition, the excited state lifetimes of (tfmppy)2Ir(F-tpip), (tfmppy)2Ir(MeO -tpip) and (tfmppy)2Ir(tnin) were 2.51, 2.00 and 3.88 μs, respectively. Furthermore, they all showed good reversible redox peaks in the cyclic voltammetry curves, and their energy levels were also calculated ((tfmppy)2Ir(F-tpip):EHOMO=-5.67 eV, ELUMO=-3.29 eV; (tfmppy)2Ir(MeO-tpip):EHOMO=-6.08 eV, ELUMO=-3.61 eV; (tfmppy)2Ir(tnin):EHOMO=-5.69 eV, ELUMO=-3.22 eV).
This work reports the synthesis and properties of three iridium(（Ⅲ）) complexes ((tfmppy)2Ir(F-tpip), (tfmppy)2Ir (MeO-tpip) and (tfmppy)2Ir(tnin)) with 2-(4-(trifluoromethyl)phenyl)pyridine (tfmppy) as main ligand and tetra(4-fluoropheny) imidodiphosphinate (F-tpip), tetra(4-methoxypheny)imidodiphosphinate (MeO-tpip), tetra(naphthalen-1-yl) imidodiphosphinate (tnin) as ancillary ligands, respectively. Their structures were confirmed by 1H NMR, MS (MALDI-TOF), elemental and single crystal analysis. Both (tfmppy)2Ir(F-tpip) and (tfmppy)2Ir(MeO-tpip) complexes belong to P1 space group of triclinic crystal system. The complex (tfmppy)2Ir(tnin) belongs to R3c space group of trigonal crystal system. All the complexes are green materials with similar emission color and photoluminescence quantum efficiency ((tfmppy)2Ir(F-tpip):λem=526 nm, Φ=0.52; (tfmppy)2Ir(MeO-tpip):λem=523 nm, Φ=0.44; (tfmppy)2Ir (tnin):λem=522 nm, Φ=0.48). In addition, the excited state lifetimes of (tfmppy)2Ir(F-tpip), (tfmppy)2Ir(MeO -tpip) and (tfmppy)2Ir(tnin) were 2.51, 2.00 and 3.88 μs, respectively. Furthermore, they all showed good reversible redox peaks in the cyclic voltammetry curves, and their energy levels were also calculated ((tfmppy)2Ir(F-tpip):EHOMO=-5.67 eV, ELUMO=-3.29 eV; (tfmppy)2Ir(MeO-tpip):EHOMO=-6.08 eV, ELUMO=-3.61 eV; (tfmppy)2Ir(tnin):EHOMO=-5.69 eV, ELUMO=-3.22 eV).
2020, 36(7): 1275-1282
doi: 10.11862/CJIC.2020.158
Abstract:
Two benzothiazole modified metal chelators (N, N'-bis (salicylaldehyde)-2, 2'-(3-(benzo[d]-thiozol-2-yl)-1, 2 -phenylene-dioxyethyldiamine (L1), N, N'-bis (salicylaldehyde)-2, 2'-(4-(benzo[d]thiozol-2-yl)-1, 2-phenylene dioxyethyldiamine (L2) were designed and synthesized. The biological activities of chelators were determined by Turbidity Assay, BCA Protein Assay, HRP/Amplex Red Assay and MTT Assay. The results show that these two chelators could effectively prevent aggregation of Aβ1~40 induced by metal ion (such as Zn2+, Cu2+), dramatically reduce the product of H2O2 which caused by Cu2+-Aβ species, and inhibit Aβ aggregation mediated cytotoxicity on PC12 cells. The same assays were carried out for non-benzothiozole functionalized analogue. The non-specific chelator also has above bioactivities, however, its effect was far less than that of the benzothiozole functionalized varieties.
Two benzothiazole modified metal chelators (N, N'-bis (salicylaldehyde)-2, 2'-(3-(benzo[d]-thiozol-2-yl)-1, 2 -phenylene-dioxyethyldiamine (L1), N, N'-bis (salicylaldehyde)-2, 2'-(4-(benzo[d]thiozol-2-yl)-1, 2-phenylene dioxyethyldiamine (L2) were designed and synthesized. The biological activities of chelators were determined by Turbidity Assay, BCA Protein Assay, HRP/Amplex Red Assay and MTT Assay. The results show that these two chelators could effectively prevent aggregation of Aβ1~40 induced by metal ion (such as Zn2+, Cu2+), dramatically reduce the product of H2O2 which caused by Cu2+-Aβ species, and inhibit Aβ aggregation mediated cytotoxicity on PC12 cells. The same assays were carried out for non-benzothiozole functionalized analogue. The non-specific chelator also has above bioactivities, however, its effect was far less than that of the benzothiozole functionalized varieties.
2020, 36(7): 1283-1290
doi: 10.11862/CJIC.2020.137
Abstract:
Two new zinc porphyrin with different donor units based Mn(Ⅱ) ion coordination polymers (CPsx, x=1, 2) have been designed, synthesized, and well-characterized. Two coordination polymers and anchor porphyrin (ZnPA) self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. The assembled processes of CPsx-ZnPA on TiO2 surface were as follows:a porphyrin molecule (ZnPA) as anchoring group was immobilized on the TiO2 electrode surface through carboxylic groups, then the desired dye of CPsx was bound to the anchoring group through axially coordination bonded from porphyrin central Zn(Ⅱ) ions of CPsx and the N atom of ZnPA. Our results reveal that the self-assemblies devices show significantly improved photocurrent conversion efficiency. Particularly, CPs2 based solar cell displayed a PCE (power conversion efficiency) of 1.89%, and the Jsc was 4.82 mA·cm-2. This indicates that the supramolecular coordination polymers self-assembly strategy has been successfully applied in dye-sensitized solar cells (DSSC). Their optical performance and electrochemical impedance spectroscopy were also investigated to further understand the photoelectrochemical results. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy (TEM).
Two new zinc porphyrin with different donor units based Mn(Ⅱ) ion coordination polymers (CPsx, x=1, 2) have been designed, synthesized, and well-characterized. Two coordination polymers and anchor porphyrin (ZnPA) self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. The assembled processes of CPsx-ZnPA on TiO2 surface were as follows:a porphyrin molecule (ZnPA) as anchoring group was immobilized on the TiO2 electrode surface through carboxylic groups, then the desired dye of CPsx was bound to the anchoring group through axially coordination bonded from porphyrin central Zn(Ⅱ) ions of CPsx and the N atom of ZnPA. Our results reveal that the self-assemblies devices show significantly improved photocurrent conversion efficiency. Particularly, CPs2 based solar cell displayed a PCE (power conversion efficiency) of 1.89%, and the Jsc was 4.82 mA·cm-2. This indicates that the supramolecular coordination polymers self-assembly strategy has been successfully applied in dye-sensitized solar cells (DSSC). Their optical performance and electrochemical impedance spectroscopy were also investigated to further understand the photoelectrochemical results. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy (TEM).
2020, 36(7): 1291-1297
doi: 10.11862/CJIC.2020.156
Abstract:
To investigate the effect of strong magnetic field on the chemical reactions and properties of biological important molecules, as a part of this research, tetra-phenyl porphyrin and its metalloporphyrin coordination reaction were chosen to extended study. The TPP crystals, obtained at different magnetic field, were measured by X-ray powder diffraction. The yields of cobalt porphyrin (CoTPP) and zinc porphyrin (ZnTPP) at different magnetic field intensities were determined by UV -Vis spectrophotometer. The conversion rates of cobalt porphyrin (CoTPP) and zinc porphyrin (ZnTPP) in different magnetic fields, as well as the reaction kinetics of Co2+ and Zn2+ coordination with TPP were analyzed, respectively. The results show that the crystallinity of TPP increases with the intensity of magnetic field. The yield and reaction rate of CoTPP and ZnTPP decreased with the increase of magnetic field intensity, but the magnetic field intensity made no effect on the reaction kinetics. According to the research results, high magnetic field is beneficial to the crystallization of tetraphenyl porphyrin, and the orientation of tetraphenyl porphyrin perpendicular to the magnetic field in the solution is the main reason for the decrease of coordination reaction rate. With the increase of magnetic field intensity, the orientation degree of tetraphenyl porphyrin increases.
To investigate the effect of strong magnetic field on the chemical reactions and properties of biological important molecules, as a part of this research, tetra-phenyl porphyrin and its metalloporphyrin coordination reaction were chosen to extended study. The TPP crystals, obtained at different magnetic field, were measured by X-ray powder diffraction. The yields of cobalt porphyrin (CoTPP) and zinc porphyrin (ZnTPP) at different magnetic field intensities were determined by UV -Vis spectrophotometer. The conversion rates of cobalt porphyrin (CoTPP) and zinc porphyrin (ZnTPP) in different magnetic fields, as well as the reaction kinetics of Co2+ and Zn2+ coordination with TPP were analyzed, respectively. The results show that the crystallinity of TPP increases with the intensity of magnetic field. The yield and reaction rate of CoTPP and ZnTPP decreased with the increase of magnetic field intensity, but the magnetic field intensity made no effect on the reaction kinetics. According to the research results, high magnetic field is beneficial to the crystallization of tetraphenyl porphyrin, and the orientation of tetraphenyl porphyrin perpendicular to the magnetic field in the solution is the main reason for the decrease of coordination reaction rate. With the increase of magnetic field intensity, the orientation degree of tetraphenyl porphyrin increases.
2020, 36(7): 1298-1308
doi: 10.11862/CJIC.2020.139
Abstract:
Co-MOF two-dimensional nanosheets were first grown on a carbon cloth by solution method, and MOFderived porous carbon nanosheets were obtained after high temperature annealing and etching process. Co-MOF derived porous carbon nanosheets/carbon cloths (CNSs/CC) was used as the carbon-based framework, and highly active nitrogen-doped graphene quantum dots (N-GQDs) were loaded by electrochemical deposition to prepare hierarchical porous structures N-GQD/CNS/CC composite material as electrode material for supercapacitors. The N-GQD/CNS/CC electrode, as a self-supporting and adhesive-free electrode, delivered a specific capacitance of 423 F·g-1 at 1 A·g-1. According to the mechanism of energy storage and capacitance contribution, the N-GQD/CNS/CC composite is an ideal supercapacitor electrode material with high capacitance, due to synergetic effect between CNS grown in situ on carbon fiber with high double-layer capacitance and N-GQDs loaded on the surface with high pseudo-capacitance. The highly conductive, hierarchical porous structure of the electrode material is beneficial to the electron transport and the diffusion of electrolyte ions, which presents good kinetic performance, high rate performance and rapid charge-discharge capability. A symmetrical supercapacitor based on N -GQD/CNS/CC electrode exhibited a high energy density of 250 W·kg-1 at power density of 7.9 Wh·kg-1, while the capacitance retention after 10 000 cycles reached 91.2%, which indicates that the N-GQD/CNS/CC composite is an all-carbon electrode material with stable electrochemical performance and high capacitance performance.
Co-MOF two-dimensional nanosheets were first grown on a carbon cloth by solution method, and MOFderived porous carbon nanosheets were obtained after high temperature annealing and etching process. Co-MOF derived porous carbon nanosheets/carbon cloths (CNSs/CC) was used as the carbon-based framework, and highly active nitrogen-doped graphene quantum dots (N-GQDs) were loaded by electrochemical deposition to prepare hierarchical porous structures N-GQD/CNS/CC composite material as electrode material for supercapacitors. The N-GQD/CNS/CC electrode, as a self-supporting and adhesive-free electrode, delivered a specific capacitance of 423 F·g-1 at 1 A·g-1. According to the mechanism of energy storage and capacitance contribution, the N-GQD/CNS/CC composite is an ideal supercapacitor electrode material with high capacitance, due to synergetic effect between CNS grown in situ on carbon fiber with high double-layer capacitance and N-GQDs loaded on the surface with high pseudo-capacitance. The highly conductive, hierarchical porous structure of the electrode material is beneficial to the electron transport and the diffusion of electrolyte ions, which presents good kinetic performance, high rate performance and rapid charge-discharge capability. A symmetrical supercapacitor based on N -GQD/CNS/CC electrode exhibited a high energy density of 250 W·kg-1 at power density of 7.9 Wh·kg-1, while the capacitance retention after 10 000 cycles reached 91.2%, which indicates that the N-GQD/CNS/CC composite is an all-carbon electrode material with stable electrochemical performance and high capacitance performance.
2020, 36(7): 1309-1317
doi: 10.11862/CJIC.2020.151
Abstract:
The Fe3O4@C/rGO composite was synthesized using graphene oxide (GO) as the substrate, Fe(NO3)3·9H2O, isopropanol and glycerol as the raw materials by solvothermal method and subsequent heat treatment process, and it succeeded in realizing the in-situ growth of carbon-coated hierarchical Fe3O4 hollow spheres on graphene oxide sheets. The physicochemical properties and lithium storage properties of Fe3O4@C/rGO materials were analyzed by X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic discharge-charge, etc. The results showed that the composite still has the reversible capacity of 437.7 mAh·g-1 under the current density of 5.0 A·g-1, and the discharge specific capacity of 587.3 mAh·g-1 after 200 cycles at 1.0 A·g-1. This is mainly attributed to the introduction of reduced graphene oxide (rGO) which improves the overall structural stability and electrical conductivity of carbon-coated Fe3O4 hierarchical hollow spheres.
The Fe3O4@C/rGO composite was synthesized using graphene oxide (GO) as the substrate, Fe(NO3)3·9H2O, isopropanol and glycerol as the raw materials by solvothermal method and subsequent heat treatment process, and it succeeded in realizing the in-situ growth of carbon-coated hierarchical Fe3O4 hollow spheres on graphene oxide sheets. The physicochemical properties and lithium storage properties of Fe3O4@C/rGO materials were analyzed by X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic discharge-charge, etc. The results showed that the composite still has the reversible capacity of 437.7 mAh·g-1 under the current density of 5.0 A·g-1, and the discharge specific capacity of 587.3 mAh·g-1 after 200 cycles at 1.0 A·g-1. This is mainly attributed to the introduction of reduced graphene oxide (rGO) which improves the overall structural stability and electrical conductivity of carbon-coated Fe3O4 hierarchical hollow spheres.
2020, 36(7): 1366-1374
doi: 10.11862/CJIC.2020.140
Abstract:
High-silica SSZ-13 zeolite membranes were prepared on tubular mullite supports using a diluted organic template gel composition to investigate the hydrothermal growth process. Membranes and powders at the bottom of autoclave were characterized after secondary growth from 2 to 72 h at 433 K, and the XRD patterns show SSZ-13 characteristic peaks appeared in the membranes and powders simultaneously after 6 h. The size of zeolite crystals in the powder was almost the same when the synthesis time delayed. The SSZ-13 membrane synthesized at 433 K and 72 h had a CO2 permeance of 2.08×10-7 mol·m-2·s-1·Pa-1 with an ideal selectivity of CO2/CH4 of 24 at 298 K and 0.4 MPa. The possible growth process of SSZ-13 zeolite membrane was proposed with the seeds coated on supports dissolved and formed numerous orderly structure units in the gel firstly, inducing SSZ-13 zeolite crystals generated and grew rapidly, the crystals deposited on the supports, grew up and intergrew for limited space to from a defectfree layer.
High-silica SSZ-13 zeolite membranes were prepared on tubular mullite supports using a diluted organic template gel composition to investigate the hydrothermal growth process. Membranes and powders at the bottom of autoclave were characterized after secondary growth from 2 to 72 h at 433 K, and the XRD patterns show SSZ-13 characteristic peaks appeared in the membranes and powders simultaneously after 6 h. The size of zeolite crystals in the powder was almost the same when the synthesis time delayed. The SSZ-13 membrane synthesized at 433 K and 72 h had a CO2 permeance of 2.08×10-7 mol·m-2·s-1·Pa-1 with an ideal selectivity of CO2/CH4 of 24 at 298 K and 0.4 MPa. The possible growth process of SSZ-13 zeolite membrane was proposed with the seeds coated on supports dissolved and formed numerous orderly structure units in the gel firstly, inducing SSZ-13 zeolite crystals generated and grew rapidly, the crystals deposited on the supports, grew up and intergrew for limited space to from a defectfree layer.
2020, 36(7): 1375-1382
doi: 10.11862/CJIC.2020.146
Abstract:
A coumarin Schiff-base fluorescent sensor bearing 2-(5-(pyridine-3-yl)-4H-1, 2, 4-triazol-3-yl)acetohydrazide unit (CPTH) was designed, synthesized and characterized. CPTH exhibited strong yellow fluorescence and unique selectivity for Cu2+ ions. As a Cu2+ ion quencher, CPTH showed highly sensitive detection limit of 2 μmol·L-1.
A coumarin Schiff-base fluorescent sensor bearing 2-(5-(pyridine-3-yl)-4H-1, 2, 4-triazol-3-yl)acetohydrazide unit (CPTH) was designed, synthesized and characterized. CPTH exhibited strong yellow fluorescence and unique selectivity for Cu2+ ions. As a Cu2+ ion quencher, CPTH showed highly sensitive detection limit of 2 μmol·L-1.
2020, 36(7): 1383-1392
doi: 10.11862/CJIC.2020.161
Abstract:
Three new metal-organic complexes(MOCs), namely {[Pb2(HL)(phen)]·2H2O}n (1), {[Ni(H3L)(4, 4'-bipy)1.5 (H2O)4]·6H2O}n (2) and {[Ni2(HL)(1, 4-bibb)(H2O)]·(CH3CN)·H2O}n (3), have been synthesized by the V-pattern multicarboxylic acid ligand of H5L (H5L=3, 5-di(2', 5'-dicarboxylpyl)benozoic acid, phen=1, 10-phenanthroline, 4, 4'-bipy=4, 4'-bipyridine, 1, 4-bibb=1, 4-bis(benzimidazole)benzene) and Pb(Ⅱ)/Ni(Ⅱ) under solvothermal condition. 1 is a 1D chains structure with the binuclear[Pb2(μ2-COO)2(μ1-COO)4] SBUs. 2 shows 2D lamellar networks with the point symbol of {4.62}2{42.62.82}. 3 presents a 3D network structure with the point symbol of {62.84}{64.82}2. The fluorescence measurements show that 1 has highly sensitive detection for Fe3+ and Cr2O72- ions in aqueous solution by luminescence quenching effect. Meanwhile, the possible sensing mechanisms of 1 to Fe3+ and Cr2O72- were also investigated. Then, the variable-temperature magnetic susceptibility measurements reveal that 3 has antiferromagnetic interactions between the Ni(Ⅱ) ions.
Three new metal-organic complexes(MOCs), namely {[Pb2(HL)(phen)]·2H2O}n (1), {[Ni(H3L)(4, 4'-bipy)1.5 (H2O)4]·6H2O}n (2) and {[Ni2(HL)(1, 4-bibb)(H2O)]·(CH3CN)·H2O}n (3), have been synthesized by the V-pattern multicarboxylic acid ligand of H5L (H5L=3, 5-di(2', 5'-dicarboxylpyl)benozoic acid, phen=1, 10-phenanthroline, 4, 4'-bipy=4, 4'-bipyridine, 1, 4-bibb=1, 4-bis(benzimidazole)benzene) and Pb(Ⅱ)/Ni(Ⅱ) under solvothermal condition. 1 is a 1D chains structure with the binuclear[Pb2(μ2-COO)2(μ1-COO)4] SBUs. 2 shows 2D lamellar networks with the point symbol of {4.62}2{42.62.82}. 3 presents a 3D network structure with the point symbol of {62.84}{64.82}2. The fluorescence measurements show that 1 has highly sensitive detection for Fe3+ and Cr2O72- ions in aqueous solution by luminescence quenching effect. Meanwhile, the possible sensing mechanisms of 1 to Fe3+ and Cr2O72- were also investigated. Then, the variable-temperature magnetic susceptibility measurements reveal that 3 has antiferromagnetic interactions between the Ni(Ⅱ) ions.
2020, 36(7): 1393-1400
doi: 10.11862/CJIC.2020.138
Abstract:
This work adopts the colloidal nanoparticles as a model for research due to the prominent specific surface area of colloidal nanoparticles. There was a hypothesis that cations uniformly distributed in the conductive carbon and binder. Electrolyte ion can interact with cations to form reactive colloidal clusters in situ. Herein, the electrochemical method was adapted to synthesize different iron based electrode materials by the changes of electrolyte. Febased electrodes exhibited specific capacitances of 1 113, 927 and 755 F·g-1 in KOH, NaOH and LiOH aqueous electrolyte, respectively. A novel type of colloid systems with adjustable structure was built, achieving multiscale controllable regulation of colloid structure and material performance. By extending the colloid model, a novel method of in situ composition adjustment to cross-scale control of material properties was provided.
This work adopts the colloidal nanoparticles as a model for research due to the prominent specific surface area of colloidal nanoparticles. There was a hypothesis that cations uniformly distributed in the conductive carbon and binder. Electrolyte ion can interact with cations to form reactive colloidal clusters in situ. Herein, the electrochemical method was adapted to synthesize different iron based electrode materials by the changes of electrolyte. Febased electrodes exhibited specific capacitances of 1 113, 927 and 755 F·g-1 in KOH, NaOH and LiOH aqueous electrolyte, respectively. A novel type of colloid systems with adjustable structure was built, achieving multiscale controllable regulation of colloid structure and material performance. By extending the colloid model, a novel method of in situ composition adjustment to cross-scale control of material properties was provided.
2020, 36(7): 1401-1412
doi: 10.11862/CJIC.2020.135
Abstract:
In this work, metal organic framework materials (MOFs) photocatalysts with large specific surface area and easy structure modification are synthesized:MIL-101(Cr) and MIL-101(Cr)-2OH. The structures of MIL-101(Cr) and MIL-101(Cr)-2OH photocatalysts were characterized by FT-IR, X-ray powder diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS). The UV-visible diffuse reflectance spectroscopy (UV-Vis DRS), ζ potential, and electrospray ionization mass spectrometry (ESI-MS) were used to systematically analyze the effect of electron donating groups in the MOFs on photocatalytic degradation of methylene blue (MB). It was found that the two hydroxyl groups that do not participate in MIL-101(Cr)-2OH can affect the absorption of light through the action of ligandmetal charge transfer (LMCT), thereby regulating the photocatalytic degradation rate.
In this work, metal organic framework materials (MOFs) photocatalysts with large specific surface area and easy structure modification are synthesized:MIL-101(Cr) and MIL-101(Cr)-2OH. The structures of MIL-101(Cr) and MIL-101(Cr)-2OH photocatalysts were characterized by FT-IR, X-ray powder diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS). The UV-visible diffuse reflectance spectroscopy (UV-Vis DRS), ζ potential, and electrospray ionization mass spectrometry (ESI-MS) were used to systematically analyze the effect of electron donating groups in the MOFs on photocatalytic degradation of methylene blue (MB). It was found that the two hydroxyl groups that do not participate in MIL-101(Cr)-2OH can affect the absorption of light through the action of ligandmetal charge transfer (LMCT), thereby regulating the photocatalytic degradation rate.
2020, 36(7): 1318-1326
doi: 10.11862/CJIC.2020.147
Abstract:
Herein, Zn-doped Co9S8 nanoparticles were synthesized via an in situ solvothermal growth method. These particles have a pore size of 18 nm and specific surface area of 23 m2·g-1. A series of performance tests showed that microscale Zn doping significantly improved the catalytic activity and capacitor performance of Co9S8. In HER performance tests, Zn-doped Co9S8 exhibited a lower potential of -361 mV at the current density of 10 mA·cm-2 and the highest current density up to 38.26 mA·cm-2, excellent cycling stability as well. In capacitor performance tests, Zndoped Co9S8 showed pretty high specific capacitance with mass and area specific capacitances of 235.48 F·g-1 and 812.4 mF·cm-2 respectively at a current density of 1 A·g-1.
Herein, Zn-doped Co9S8 nanoparticles were synthesized via an in situ solvothermal growth method. These particles have a pore size of 18 nm and specific surface area of 23 m2·g-1. A series of performance tests showed that microscale Zn doping significantly improved the catalytic activity and capacitor performance of Co9S8. In HER performance tests, Zn-doped Co9S8 exhibited a lower potential of -361 mV at the current density of 10 mA·cm-2 and the highest current density up to 38.26 mA·cm-2, excellent cycling stability as well. In capacitor performance tests, Zndoped Co9S8 showed pretty high specific capacitance with mass and area specific capacitances of 235.48 F·g-1 and 812.4 mF·cm-2 respectively at a current density of 1 A·g-1.
2020, 36(7): 1327-1332
doi: 10.11862/CJIC.2020.150
Abstract:
One new coordination polymer, {[Cu2(OH)(btre)1.5(1, 2, 4-btc)]·13H2O}n (1·13H2O) (btre=1, 2-bis(4H-1, 2, 4-triazole)ethane, 1, 2, 4-btc=1, 2, 4-benzenetricarboxylate), was synthesized under room temperature condition and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy and powder X-ray diffraction. Sing-crystal X-ray structural analysis shows that compound 1 features a 3D framework based on the tetranuclear[Cu4 (μ2-OH)2N12]. The 3D coordination network of 1 is a 10-connected network with (312·428·55) topology based on the tetranuclear copper cluster nodes. The thermogravimetric (TG) analysis and photocatalytic degradation of methyl orange (MO) of 1·13H2O were studied.
One new coordination polymer, {[Cu2(OH)(btre)1.5(1, 2, 4-btc)]·13H2O}n (1·13H2O) (btre=1, 2-bis(4H-1, 2, 4-triazole)ethane, 1, 2, 4-btc=1, 2, 4-benzenetricarboxylate), was synthesized under room temperature condition and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy and powder X-ray diffraction. Sing-crystal X-ray structural analysis shows that compound 1 features a 3D framework based on the tetranuclear[Cu4 (μ2-OH)2N12]. The 3D coordination network of 1 is a 10-connected network with (312·428·55) topology based on the tetranuclear copper cluster nodes. The thermogravimetric (TG) analysis and photocatalytic degradation of methyl orange (MO) of 1·13H2O were studied.
2020, 36(7): 1333-1343
doi: 10.11862/CJIC.2020.149
Abstract:
Two new N, N, N-trimethylpropane-1-ammonium and N, N, N-trimethylpentane-1-ammonium conjugated acetophenone-(4-hydroxybenzohydrazone) ligands, (E)-3-(4-(1-(2-(4-hydroxybenzoyl)hydrazono)ethyl)phenoxy)-N, N, N-trimethylpropan-1-ammonium perchlorate (H2L1) and (E)-3-(4-(1-(2-(4-hydroxybenzoyl)hydrazono)ethyl)phenoxy)N, N, N-trimethylpentane-1-ammonium perchlorate (H2L2), and two new copper complexes with the formulation[Cu (HL1)2] and[Cu(HL2)2] were synthesized and their DNA binding and cleavage activities of the compounds were investigated. The mechanism of DNA cleavage and the effect of the compound concentration on the DNA cleavage reaction were also studied. UV-Vis spectroscopy results suggest that all compounds preferably bind to DNA via major groove binding mode. This is also supported that DNA cleavage activity was inhibited in the presence of methyl green, a major groove binder. According to the results of electrophoresis studies, the compounds exhibit significant cleavage activity on the plasmid DNA both in the presence and absence of an oxidative agent (H2O2), which strongly depends on the concentration of the compound. The compounds cleavage pBR322 DNA via hydrolytic pathway, which is also supported by the DNA cleavage experiments in the presence of different radical scavengers.
Two new N, N, N-trimethylpropane-1-ammonium and N, N, N-trimethylpentane-1-ammonium conjugated acetophenone-(4-hydroxybenzohydrazone) ligands, (E)-3-(4-(1-(2-(4-hydroxybenzoyl)hydrazono)ethyl)phenoxy)-N, N, N-trimethylpropan-1-ammonium perchlorate (H2L1) and (E)-3-(4-(1-(2-(4-hydroxybenzoyl)hydrazono)ethyl)phenoxy)N, N, N-trimethylpentane-1-ammonium perchlorate (H2L2), and two new copper complexes with the formulation[Cu (HL1)2] and[Cu(HL2)2] were synthesized and their DNA binding and cleavage activities of the compounds were investigated. The mechanism of DNA cleavage and the effect of the compound concentration on the DNA cleavage reaction were also studied. UV-Vis spectroscopy results suggest that all compounds preferably bind to DNA via major groove binding mode. This is also supported that DNA cleavage activity was inhibited in the presence of methyl green, a major groove binder. According to the results of electrophoresis studies, the compounds exhibit significant cleavage activity on the plasmid DNA both in the presence and absence of an oxidative agent (H2O2), which strongly depends on the concentration of the compound. The compounds cleavage pBR322 DNA via hydrolytic pathway, which is also supported by the DNA cleavage experiments in the presence of different radical scavengers.
2020, 36(7): 1344-1352
doi: 10.11862/CJIC.2020.157
Abstract:
Three 0D dinuclear zinc(Ⅱ) and cadmium(Ⅱ) coordination compounds, namely[Zn2(μ-dbda)2(phen)2(H2O)2] (1), [Zn2(μ-dbda)2(2, 2'-bipy)2] (2), and[Cd2(μ-dbda)2(2, 2'-bipy)2(H2O)2]·2H2O (3), have been constructed hydrothermally using H2dbda (H2dbda=4, 4'-dimethyl-2, 2'-biphenyldicarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2' -bipy (2, 2'-bipy=2, 2'-bipyridine), and zinc or cadmium chlorides. Single-crystal X-ray diffraction analyses reveal that three compounds crystallize in the triclinic or monoclinic systems, space groups P1 or P21/n. All compounds disclose a discrete dimer structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bonds. The luminescent and photocatalytic properties of three compounds were investigated, showing that compound 3 is a promising photocatalyst for the UV-light-driven degradation of methylene blue as a model organic dye pollutant.
Three 0D dinuclear zinc(Ⅱ) and cadmium(Ⅱ) coordination compounds, namely[Zn2(μ-dbda)2(phen)2(H2O)2] (1), [Zn2(μ-dbda)2(2, 2'-bipy)2] (2), and[Cd2(μ-dbda)2(2, 2'-bipy)2(H2O)2]·2H2O (3), have been constructed hydrothermally using H2dbda (H2dbda=4, 4'-dimethyl-2, 2'-biphenyldicarboxylic acid), phen (phen=1, 10-phenanthroline), 2, 2' -bipy (2, 2'-bipy=2, 2'-bipyridine), and zinc or cadmium chlorides. Single-crystal X-ray diffraction analyses reveal that three compounds crystallize in the triclinic or monoclinic systems, space groups P1 or P21/n. All compounds disclose a discrete dimer structure, which is assembled to a 3D supramolecular framework through O-H…O hydrogen bonds. The luminescent and photocatalytic properties of three compounds were investigated, showing that compound 3 is a promising photocatalyst for the UV-light-driven degradation of methylene blue as a model organic dye pollutant.
2020, 36(7): 1353-1365
doi: 10.11862/CJIC.2020.155
Abstract:
Mouse aortic smooth muscle cells (MOVAS) were cultured for 14 d under the conditions of high calcium and different concentrations of diethyl citrate (Et2Cit), sodium citrate (Na3Cit), and phosphonoformic acid (PFA). Alizarin red staining, immunofluorescence and annexin V staining were used to detect cell transdifferentiation, apoptosis, and cell calcium deposition. The inhibitory effects of Et2Cit, Na3Cit, and PFA on calcium-induced calcification of MOVAS cells and their possible mechanisms were studied. The results showed that Et2Cit, Na3Cit, and PFA can all reduce MOVAS calcification induced by high calcium and reduce extracellular calcified plaque and calcium deposition. These inhibitors can inhibit the transdifferentiation of MOVAS to osteoblast-like cells, resulting in a decrease in the activity of alkaline phosphatase (ALP), a marker transformed to osteogenic differentiation. Their inhibitory effects exhibited concentration dependence. The inhibitory effects of the inhibitors at the same concentration showed the following trend:PFA > Na3Cit > Et2Cit. Low concentrations of Na3Cit and Et2Cit inhibit calcification by reducing cell apoptosis, but high concentrations of Na3Cit, Et2Cit, and PFA increased cell apoptosis due to their own toxicity. Et2Cit and Na3Cit as blood anticoagulants can effectively inhibit MOVAS calcification induced by high calcium.
Mouse aortic smooth muscle cells (MOVAS) were cultured for 14 d under the conditions of high calcium and different concentrations of diethyl citrate (Et2Cit), sodium citrate (Na3Cit), and phosphonoformic acid (PFA). Alizarin red staining, immunofluorescence and annexin V staining were used to detect cell transdifferentiation, apoptosis, and cell calcium deposition. The inhibitory effects of Et2Cit, Na3Cit, and PFA on calcium-induced calcification of MOVAS cells and their possible mechanisms were studied. The results showed that Et2Cit, Na3Cit, and PFA can all reduce MOVAS calcification induced by high calcium and reduce extracellular calcified plaque and calcium deposition. These inhibitors can inhibit the transdifferentiation of MOVAS to osteoblast-like cells, resulting in a decrease in the activity of alkaline phosphatase (ALP), a marker transformed to osteogenic differentiation. Their inhibitory effects exhibited concentration dependence. The inhibitory effects of the inhibitors at the same concentration showed the following trend:PFA > Na3Cit > Et2Cit. Low concentrations of Na3Cit and Et2Cit inhibit calcification by reducing cell apoptosis, but high concentrations of Na3Cit, Et2Cit, and PFA increased cell apoptosis due to their own toxicity. Et2Cit and Na3Cit as blood anticoagulants can effectively inhibit MOVAS calcification induced by high calcium.
