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2020 Volume 36 Issue 6
2020, 36(6): 969-982
doi: 10.11862/CJIC.2020.122
Abstract:
As an emerging biotechnology optogenetics attracts tremendous attention in spatiotemporal control of biological functions, especially in neuronal excitability manipulation through channelrhodopsins (ChRs). However, it remains a major challenge for noninvasive deep-tissue applications due to current optogenetic tools are mainly visible light-sensitive. To address this issue, recent studies have utilized lanthanide-doped upconversion nanoparticles (UCNPs), as promising photo-nanotransducers that can convert near-infrared (NIR) light to visible emissions, thereby facilitating the optogenetic regulation in complex living systems. In this review, the development and advances in UCNPs-based optogentics are summarized in detail. In addition, future perspectives for advancing such a hybrid upconversion optogenetic technique into clinical research are proposed.
As an emerging biotechnology optogenetics attracts tremendous attention in spatiotemporal control of biological functions, especially in neuronal excitability manipulation through channelrhodopsins (ChRs). However, it remains a major challenge for noninvasive deep-tissue applications due to current optogenetic tools are mainly visible light-sensitive. To address this issue, recent studies have utilized lanthanide-doped upconversion nanoparticles (UCNPs), as promising photo-nanotransducers that can convert near-infrared (NIR) light to visible emissions, thereby facilitating the optogenetic regulation in complex living systems. In this review, the development and advances in UCNPs-based optogentics are summarized in detail. In addition, future perspectives for advancing such a hybrid upconversion optogenetic technique into clinical research are proposed.
2020, 36(6): 1001-1013
doi: 10.11862/CJIC.2020.142
Abstract:
Luminescent materials have been widely applied in the fields of lighting and display. It is significant to develop new luminescent materials with environmental compatibility, low cost and high efficiency. Phosphorescent manganese (Ⅱ) complexes have attracted much attention due to their excellent luminescent efficiency, low cost and low toxicity. The phosphorescence of manganese(Ⅱ) complexes originates from spin forbidden d-d transition and is mainly dependent on the type and strength of ligand field. Since the ligand field of manganese(Ⅱ) is sensitive to external stimuli and easy to change, which directly affects its photophysical properties, thus enabling the reversible conversion and regulation of luminous colors. Based on the research work in our group on the design of phosphorescent manganese(Ⅱ) complexes and their photoluminescence and electroluminescence properties, this article is aimed to review the recent progress of manganese(Ⅱ) halide complexes and various manganese(Ⅱ) complexes with stimulus-responsive luminescence and their applications in electroluminescent devices. The future development prospect and challenges in this field are prospected.
Luminescent materials have been widely applied in the fields of lighting and display. It is significant to develop new luminescent materials with environmental compatibility, low cost and high efficiency. Phosphorescent manganese (Ⅱ) complexes have attracted much attention due to their excellent luminescent efficiency, low cost and low toxicity. The phosphorescence of manganese(Ⅱ) complexes originates from spin forbidden d-d transition and is mainly dependent on the type and strength of ligand field. Since the ligand field of manganese(Ⅱ) is sensitive to external stimuli and easy to change, which directly affects its photophysical properties, thus enabling the reversible conversion and regulation of luminous colors. Based on the research work in our group on the design of phosphorescent manganese(Ⅱ) complexes and their photoluminescence and electroluminescence properties, this article is aimed to review the recent progress of manganese(Ⅱ) halide complexes and various manganese(Ⅱ) complexes with stimulus-responsive luminescence and their applications in electroluminescent devices. The future development prospect and challenges in this field are prospected.
2020, 36(6): 1014-1034
doi: 10.11862/CJIC.2020.134
Abstract:
Photocatalysis and electrochemical catalysis play an irreplaceable role in modern clean energy conversion. [60]Fullerene (C60) is widely used in novel catalysts designing because of its unique structures and properties, and has made satisfactory results. Herein, we have briefly introduced the basic properties and synthesis strategies for C60 (including C60 derivatives and C60 derived carbon materials) based catalysts. Providing a comprehensive overview of currently researches about the applications of C60 and C60 derives in photocatalysis and electrochemical catalysis. Furthermore, the functions, action mechanisms and the strategies of performance improvement for C60 based catalysts are systematically discussed. Some key issues and challenges in the development of C60 based catalysts are also proposed.
Photocatalysis and electrochemical catalysis play an irreplaceable role in modern clean energy conversion. [60]Fullerene (C60) is widely used in novel catalysts designing because of its unique structures and properties, and has made satisfactory results. Herein, we have briefly introduced the basic properties and synthesis strategies for C60 (including C60 derivatives and C60 derived carbon materials) based catalysts. Providing a comprehensive overview of currently researches about the applications of C60 and C60 derives in photocatalysis and electrochemical catalysis. Furthermore, the functions, action mechanisms and the strategies of performance improvement for C60 based catalysts are systematically discussed. Some key issues and challenges in the development of C60 based catalysts are also proposed.
2020, 36(6): 1035-1048
doi: 10.11862/CJIC.2020.143
Abstract:
Macrocyclic polyamines are intriguing electron donors for constructing fluorescent probes due to their characteristics of ring configuration and a few nitrogen atoms. For example, typical tetraazamacrocycle such as cyclen (1, 4, 7, 10-tetraazacyclododecane), cyclam (1, 4, 8, 11-tetraazacyclotetradecane) and pyclen (1, 4, 7, 10-tetraaza-2, 6-pyridinophane), and triazamacrocycle tacn (1, 4, 7-triazacyclononane) which are widely employed as receptors or functional groups in fluorescent probes for recognition of metal ions, onions, small molecules and biomacromolecules. In this review, we highlight the many different detection targets and summarize the latest prominent research achievements in the design, preparation and application of fluorescent probes based on macrocyclic polyamines. Additionally, the future research interests and perspectives in the field of fluorescence analysis are also addressed.
Macrocyclic polyamines are intriguing electron donors for constructing fluorescent probes due to their characteristics of ring configuration and a few nitrogen atoms. For example, typical tetraazamacrocycle such as cyclen (1, 4, 7, 10-tetraazacyclododecane), cyclam (1, 4, 8, 11-tetraazacyclotetradecane) and pyclen (1, 4, 7, 10-tetraaza-2, 6-pyridinophane), and triazamacrocycle tacn (1, 4, 7-triazacyclononane) which are widely employed as receptors or functional groups in fluorescent probes for recognition of metal ions, onions, small molecules and biomacromolecules. In this review, we highlight the many different detection targets and summarize the latest prominent research achievements in the design, preparation and application of fluorescent probes based on macrocyclic polyamines. Additionally, the future research interests and perspectives in the field of fluorescence analysis are also addressed.
2020, 36(6): 1049-1062
doi: 10.11862/CJIC.2020.121
Abstract:
Biomineralization is an importance process of hard tissues (such as mollusks shells, and vertebrates bones and teeth) formation, by which the precipitation of minerals are controlled in biological systems to enhance hard tissues functions. Its products, biominerals, have hierarchically ordered structures, super mechanical properties, and many important physiological functions. This inspired the designs and fabrications of organic-inorganic hybrid biomaterials for hard tissue repair via biomimetic mineralization (in vitro and in vivo). This review mainly summarizes the fundamental principles of biomineralization and the main biominerals, the principles and new findings of crystallization pathways, the mechanisms and recent advances in collagen mineralization that closely related to hard tissues repair, the hierarchical structures of hard tissues, and recent break-through of hard tissue repair via biomimetic mineralization and their perspectives.
Biomineralization is an importance process of hard tissues (such as mollusks shells, and vertebrates bones and teeth) formation, by which the precipitation of minerals are controlled in biological systems to enhance hard tissues functions. Its products, biominerals, have hierarchically ordered structures, super mechanical properties, and many important physiological functions. This inspired the designs and fabrications of organic-inorganic hybrid biomaterials for hard tissue repair via biomimetic mineralization (in vitro and in vivo). This review mainly summarizes the fundamental principles of biomineralization and the main biominerals, the principles and new findings of crystallization pathways, the mechanisms and recent advances in collagen mineralization that closely related to hard tissues repair, the hierarchical structures of hard tissues, and recent break-through of hard tissue repair via biomimetic mineralization and their perspectives.
2020, 36(6): 983-1000
doi: 10.11862/CJIC.2020.119
Abstract:
Metal-organic frameworks (MOFs) are a high-profile sort of multifunctional hybrid materials and display various luminescent behaviors due to the diversities of their architectures. Extraordinarily, the emergence of white-light-emitting (WLE) MOFs offers golden opportunities for designing and constructing new luminescent MOFs materials owing to their environmental friendliness, long service lives and high efficiencies. In this manuscript, we focus on recent developments of the WLE MOFs with particular emphases on their synthetic methods and properties, which mainly include co-doping of Ln3+ in multifarious MOFs materials, lanthanide encapsulation or organic molecules capture in MOF pores to obtain tunable WLE MOFs, and several potential sensing applications including temperature, molecular and metal ions sensors. In addition, imminent challenges and future developments of WLE MOFs materials are both proposed. This review may arouse the interest of researchers who will design and construct new luminescent MOFs.
Metal-organic frameworks (MOFs) are a high-profile sort of multifunctional hybrid materials and display various luminescent behaviors due to the diversities of their architectures. Extraordinarily, the emergence of white-light-emitting (WLE) MOFs offers golden opportunities for designing and constructing new luminescent MOFs materials owing to their environmental friendliness, long service lives and high efficiencies. In this manuscript, we focus on recent developments of the WLE MOFs with particular emphases on their synthetic methods and properties, which mainly include co-doping of Ln3+ in multifarious MOFs materials, lanthanide encapsulation or organic molecules capture in MOF pores to obtain tunable WLE MOFs, and several potential sensing applications including temperature, molecular and metal ions sensors. In addition, imminent challenges and future developments of WLE MOFs materials are both proposed. This review may arouse the interest of researchers who will design and construct new luminescent MOFs.
2020, 36(6): 1063-1071
doi: 10.11862/CJIC.2020.110
Abstract:
Reactions of the tri-olefinic tri-pyridyl ligand 1, 3, 5-tri-4-pyridyl-1, 2-ethenylbenzene (tpeb) with four metal nitrates M(NO3)2 (M=Co, Ni, Zn, Cd) and various carboxylic acids including 3, 5-dibromobenzoic acid (3, 5-HDBB), 2, 5-thiophenedicarboxylic acid (2, 5-H2TDC), 2, 5-furandicarboxylic acid (2, 5-H2FDC) and 2, 5-dibromoterephthalic acid (2, 5-H2DBTP) gave rise to six coordination polymers, namely [Zn(tpeb)(3, 5-DBB)2]n (1), [Co2(tpeb)2(2, 5-TDC)2]n (2), [Co2(tpeb)2(2, 5-FDC)2]n (3), [Co(tpeb)(2, 5-DBTP)]n (4), [Ni(tpeb)(2, 5-DBTP)]n (5) and [Cd(tpeb)0.5(2, 5-DBTP)]n (6). Complexes 1~6 were characterized by elemental analysis, infrared spectrum (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. Complexes 1~6 show rich structure varieties from one-dimensional (1D) to three-dimensional (3D). Compound 1 has a 1D zigzag chain structure in which the [Zn(3, 5-DBB)2] units are interconnected by tpeb ligands. Complexes 2 and 3 contain a similar two-dimensional (2D) double-layer network assembled from 1D ladder chains of [Co(tpeb)]n bridged by 2, 5-TDC or 2, 5-FDC. Complexes 4 and 5 hold a 3D framework constructed by bridging 1D chains of [M(2, 5-DBTP)]n (M=Co, Ni) with tpeb ligands. Compound 6 contains 2D [Cd(2, 5-DBTP)]n networks, which are interlinked by tpeb bridges, forming a unique 3D framework. Complexes 1~6 have good thermal stability, and exhibit various fluorescence emissions in the solid state.
Reactions of the tri-olefinic tri-pyridyl ligand 1, 3, 5-tri-4-pyridyl-1, 2-ethenylbenzene (tpeb) with four metal nitrates M(NO3)2 (M=Co, Ni, Zn, Cd) and various carboxylic acids including 3, 5-dibromobenzoic acid (3, 5-HDBB), 2, 5-thiophenedicarboxylic acid (2, 5-H2TDC), 2, 5-furandicarboxylic acid (2, 5-H2FDC) and 2, 5-dibromoterephthalic acid (2, 5-H2DBTP) gave rise to six coordination polymers, namely [Zn(tpeb)(3, 5-DBB)2]n (1), [Co2(tpeb)2(2, 5-TDC)2]n (2), [Co2(tpeb)2(2, 5-FDC)2]n (3), [Co(tpeb)(2, 5-DBTP)]n (4), [Ni(tpeb)(2, 5-DBTP)]n (5) and [Cd(tpeb)0.5(2, 5-DBTP)]n (6). Complexes 1~6 were characterized by elemental analysis, infrared spectrum (IR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single crystal X-ray diffraction. Complexes 1~6 show rich structure varieties from one-dimensional (1D) to three-dimensional (3D). Compound 1 has a 1D zigzag chain structure in which the [Zn(3, 5-DBB)2] units are interconnected by tpeb ligands. Complexes 2 and 3 contain a similar two-dimensional (2D) double-layer network assembled from 1D ladder chains of [Co(tpeb)]n bridged by 2, 5-TDC or 2, 5-FDC. Complexes 4 and 5 hold a 3D framework constructed by bridging 1D chains of [M(2, 5-DBTP)]n (M=Co, Ni) with tpeb ligands. Compound 6 contains 2D [Cd(2, 5-DBTP)]n networks, which are interlinked by tpeb bridges, forming a unique 3D framework. Complexes 1~6 have good thermal stability, and exhibit various fluorescence emissions in the solid state.
2020, 36(6): 1072-1078
doi: 10.11862/CJIC.2020.133
Abstract:
Herein, we report a complex manganese(Ⅱ) 3, 12-bis(2-oxo-2-((2, 2, 2-trifluoroethyl)amino)ethyl), 9-dioxa-3, 12-diazatetradecanediate (Mn(Ⅱ)-L, 1) as a Ca2+-responsive 1H/19F magnetic resonance imaging (MRI) molecular probe. Transversal relaxation time T2 of 19F nuclei is shortened dramatically by the paramagnetic relaxation enhancement (PRE) effect imposed by paramagnetic Mn2+ ions, resulting in significantly decreased 19F MRI signals. Mn2+ ions can be specifically replaced by Ca2+ ions via competitive coordination, leading to the increased distance between Mn2+ ions and 19F nuclei and the recovery of 19F MRI signals. At the same time, the higher longitudinal relaxivity r1 of free Mn2+ ions also brings about brighter 1H MRI signals. As demonstrated by our experiments, this complex is a Ca2+-responsive molecular probe for 1H/19F MRI.
Herein, we report a complex manganese(Ⅱ) 3, 12-bis(2-oxo-2-((2, 2, 2-trifluoroethyl)amino)ethyl), 9-dioxa-3, 12-diazatetradecanediate (Mn(Ⅱ)-L, 1) as a Ca2+-responsive 1H/19F magnetic resonance imaging (MRI) molecular probe. Transversal relaxation time T2 of 19F nuclei is shortened dramatically by the paramagnetic relaxation enhancement (PRE) effect imposed by paramagnetic Mn2+ ions, resulting in significantly decreased 19F MRI signals. Mn2+ ions can be specifically replaced by Ca2+ ions via competitive coordination, leading to the increased distance between Mn2+ ions and 19F nuclei and the recovery of 19F MRI signals. At the same time, the higher longitudinal relaxivity r1 of free Mn2+ ions also brings about brighter 1H MRI signals. As demonstrated by our experiments, this complex is a Ca2+-responsive molecular probe for 1H/19F MRI.
2020, 36(6): 1079-1084
doi: 10.11862/CJIC.2020.127
Abstract:
ZIF-65 was used as a precursor, and doped with nickel by a simple chemical precipitation method. The results of X-ray diffraction and scanning electron microscope showed that nickel-doped ZIF-65 with uniform morphology was synthesized successfully. Here, we examined the catalytic activity of the electrocatalytic oxygen evolution reaction (OER) of ZIF-65 and Ni-doped ZIF-65 in a three-electrode system. The results show that the doping of Ni improves the electrocatalytic activity of ZIF-65 and is superior to the electrocatalytic performance of the traditional precious metal catalyst ruthenium dioxide.
ZIF-65 was used as a precursor, and doped with nickel by a simple chemical precipitation method. The results of X-ray diffraction and scanning electron microscope showed that nickel-doped ZIF-65 with uniform morphology was synthesized successfully. Here, we examined the catalytic activity of the electrocatalytic oxygen evolution reaction (OER) of ZIF-65 and Ni-doped ZIF-65 in a three-electrode system. The results show that the doping of Ni improves the electrocatalytic activity of ZIF-65 and is superior to the electrocatalytic performance of the traditional precious metal catalyst ruthenium dioxide.
2020, 36(6): 1085-1092
doi: 10.11862/CJIC.2020.125
Abstract:
This work reports a platelet-like Ru-doped Ni2P nanosheet catalyst which was prepared by a simple one-pot method. The introduction of Ru not only significantly enhances the electron transport property of the catalyst, but also contributes to platelet-like morphology which causes a large number of step and dislocation defects on the catalyst surface; in addition, electrochemical tests reveal that both Ru and Ni2P are effective active components for electrocatalysis. These factors jointly enhance the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances of the Ru-doped Ni2P catalyst. For HER, the Ru-doped Ni2P catalyst shows superior onset potential (35 mV), Tafel slope (34 mV·dec-1) and long-term cycling stability (3 000 cycles), superior than that of the individual Ni2P, Ru and close to the commercial 20%Pt/C catalyst. For OER, the Ru-doped Ni2P catalyst displays a small onset potential of 1.54 V and overpotential (η10) of 0.49 V, superior to the Ni2P, Ru, 20%Pt/C, and close to the commercial IrO2 catalyst.
This work reports a platelet-like Ru-doped Ni2P nanosheet catalyst which was prepared by a simple one-pot method. The introduction of Ru not only significantly enhances the electron transport property of the catalyst, but also contributes to platelet-like morphology which causes a large number of step and dislocation defects on the catalyst surface; in addition, electrochemical tests reveal that both Ru and Ni2P are effective active components for electrocatalysis. These factors jointly enhance the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances of the Ru-doped Ni2P catalyst. For HER, the Ru-doped Ni2P catalyst shows superior onset potential (35 mV), Tafel slope (34 mV·dec-1) and long-term cycling stability (3 000 cycles), superior than that of the individual Ni2P, Ru and close to the commercial 20%Pt/C catalyst. For OER, the Ru-doped Ni2P catalyst displays a small onset potential of 1.54 V and overpotential (η10) of 0.49 V, superior to the Ni2P, Ru, 20%Pt/C, and close to the commercial IrO2 catalyst.
2020, 36(6): 1093-1097
doi: 10.11862/CJIC.2020.152
Abstract:
A high-nuclearity transition metal derivative based on the trivacant Keggin-type polyoxotungstate {GeW9O34}, K10.5Cs4H1.5{[Co8(OH)6(H2O)2](CO3)3(GeW9O34)2}·12H2O (1), has been successfully synthesized by the reaction of K8Na2 [A-α-GeW9O34]·25H2O, Co(NO3)2·6H2O and K2CO3 in a conventional aqueous solution method. It was structurally characterized by elemental analysis, IR spectrum, TG analysis and X-ray single crystal diffraction, etc. The results show that compound 1 contains a V-type polyoxoanion {[Co8(OH)6(H2O)2](CO3)3(GeW9O34)2}16-, and further forms a two-dimensional structure through K+ and Cs+ connections. In addition, magnetic properties show that compound 1 mainly represents the antiferromagnetic exchange interactions among Co2+ centers.
A high-nuclearity transition metal derivative based on the trivacant Keggin-type polyoxotungstate {GeW9O34}, K10.5Cs4H1.5{[Co8(OH)6(H2O)2](CO3)3(GeW9O34)2}·12H2O (1), has been successfully synthesized by the reaction of K8Na2 [A-α-GeW9O34]·25H2O, Co(NO3)2·6H2O and K2CO3 in a conventional aqueous solution method. It was structurally characterized by elemental analysis, IR spectrum, TG analysis and X-ray single crystal diffraction, etc. The results show that compound 1 contains a V-type polyoxoanion {[Co8(OH)6(H2O)2](CO3)3(GeW9O34)2}16-, and further forms a two-dimensional structure through K+ and Cs+ connections. In addition, magnetic properties show that compound 1 mainly represents the antiferromagnetic exchange interactions among Co2+ centers.
2020, 36(6): 1098-1104
doi: 10.11862/CJIC.2020.120
Abstract:
Based upon a new ligand of 5-(3-amino-pyridin-4-yl)-isophthalic acid (NH2-H2L1), the NH2-functionalized pillar-layer rtl-MOF, SNNU-Bai65, has been successfully designed and synthesized. With the polar amino group decorating the pore surface and partitioning the pore channel, activated SNNU-Bai65 exhibits more highly selective CO2 adsorption over N2 and CH4 than the parent MOF, SYSU.
Based upon a new ligand of 5-(3-amino-pyridin-4-yl)-isophthalic acid (NH2-H2L1), the NH2-functionalized pillar-layer rtl-MOF, SNNU-Bai65, has been successfully designed and synthesized. With the polar amino group decorating the pore surface and partitioning the pore channel, activated SNNU-Bai65 exhibits more highly selective CO2 adsorption over N2 and CH4 than the parent MOF, SYSU.
2020, 36(6): 1105-1112
doi: 10.11862/CJIC.2020.109
Abstract:
Two new 3d-4f tetranuclear cluster complexes, [Zn2Ln2(salen)2(CO2PyCH2O)2(MeOH)2](ClO4)2·2MeOH (Ln=Dy (1), Tb (2); H2salen=N, N'-bis(3-methoxysalicylidene)-1, 3-diaminopropane; HCO2PyCH2OH=6-(hydroxymethyl)pyridine-2-carboxylic acid), have been prepared solvothermally using Zn(salen) as the building block and CO2PyCH2O2- as the co-ligand. They are Zn-Ln2-Zn cluster complexes. Magnetic measurements indicate ferro-magnetic interactions between lanthanide(Ⅲ) ions. The Zn2Dy2 complex 1 shows magnet relaxation under a 2 000 Oe dc field, while the Zn2Tb2 complex 2 displays both field-induced magnet relaxation and fluorescence properties.
Two new 3d-4f tetranuclear cluster complexes, [Zn2Ln2(salen)2(CO2PyCH2O)2(MeOH)2](ClO4)2·2MeOH (Ln=Dy (1), Tb (2); H2salen=N, N'-bis(3-methoxysalicylidene)-1, 3-diaminopropane; HCO2PyCH2OH=6-(hydroxymethyl)pyridine-2-carboxylic acid), have been prepared solvothermally using Zn(salen) as the building block and CO2PyCH2O2- as the co-ligand. They are Zn-Ln2-Zn cluster complexes. Magnetic measurements indicate ferro-magnetic interactions between lanthanide(Ⅲ) ions. The Zn2Dy2 complex 1 shows magnet relaxation under a 2 000 Oe dc field, while the Zn2Tb2 complex 2 displays both field-induced magnet relaxation and fluorescence properties.
2020, 36(6): 1113-1122
doi: 10.11862/CJIC.2020.124
Abstract:
Exposure to high doses of sulfur dioxide (SO2) derivatives (SO32-and HSO3-) are associated with many cardiovascular diseases and lung cancer. Benefiting from the advantages of two-photon phosphorescence imaging microscopy (TPPIM) even two-photon phosphorescence lifetime imaging microscopy (TPPLIM), including excellent spatial and temporal resolutions, anti-photobleaching, anti-autofluorescence, and strong penetration, could be promising features for real-time detection of biological bisulfite derivatives in living tissues. Herein, we firstly report the probe (named as Ir-EA) for SO2 derivatives based on TPPLIM technology. Ir-EA was developed with an iridium complex according to its long phosphorescence lifetime (~110 ns) and the mitochondrial targeting properties. More importantly, Ir-EA displayed a significant luminescence enhancement (69-fold, 10 eq.) and a low detection limit (65 nmol·L-1) for bisulfite in an aqueous solution. Additionally, Ir-EA can selectively lighting-up mitochondria bisulfite derivatives in living cells as well as zebrafish.
Exposure to high doses of sulfur dioxide (SO2) derivatives (SO32-and HSO3-) are associated with many cardiovascular diseases and lung cancer. Benefiting from the advantages of two-photon phosphorescence imaging microscopy (TPPIM) even two-photon phosphorescence lifetime imaging microscopy (TPPLIM), including excellent spatial and temporal resolutions, anti-photobleaching, anti-autofluorescence, and strong penetration, could be promising features for real-time detection of biological bisulfite derivatives in living tissues. Herein, we firstly report the probe (named as Ir-EA) for SO2 derivatives based on TPPLIM technology. Ir-EA was developed with an iridium complex according to its long phosphorescence lifetime (~110 ns) and the mitochondrial targeting properties. More importantly, Ir-EA displayed a significant luminescence enhancement (69-fold, 10 eq.) and a low detection limit (65 nmol·L-1) for bisulfite in an aqueous solution. Additionally, Ir-EA can selectively lighting-up mitochondria bisulfite derivatives in living cells as well as zebrafish.
2020, 36(6): 1123-1130
doi: 10.11862/CJIC.2020.117
Abstract:
The dielectric and magnetic properties of a dinuclear Co(Ⅱ) double-stranded helicate containing hydrogen bridging bond have been investigated. Magnetic properties, HF-EPR spectra and dielectric properties all indicate that this intramolecular hydrogen bond plays an important role in the magnetic exchange interactions and dielectric properties. Ab initio calculations provide further support for above conclusions.
The dielectric and magnetic properties of a dinuclear Co(Ⅱ) double-stranded helicate containing hydrogen bridging bond have been investigated. Magnetic properties, HF-EPR spectra and dielectric properties all indicate that this intramolecular hydrogen bond plays an important role in the magnetic exchange interactions and dielectric properties. Ab initio calculations provide further support for above conclusions.
2020, 36(6): 1131-1136
doi: 10.11862/CJIC.2020.115
Abstract:
The dinuclear iron hydride radical cation salt cis-[Fe2Cp2(μ-H)(μ-PPh2)(CO)2]·+[Al(OC(CF3)3)4]-(cis-1·+[Al(OC(CF3)3)4]-) was isolated as a crystalline solid. It has been characterized by single crystal X-ray crystallography, electron paramagnetic resonance (EPR), infrared, and UV-Vis spectroscopy, in conjunction with density functional theory (DFT) calculations. EPR and DFT calculation studies reveal that the spin density of the radical is mainly equally located at both of the iron atoms.
The dinuclear iron hydride radical cation salt cis-[Fe2Cp2(μ-H)(μ-PPh2)(CO)2]·+[Al(OC(CF3)3)4]-(cis-1·+[Al(OC(CF3)3)4]-) was isolated as a crystalline solid. It has been characterized by single crystal X-ray crystallography, electron paramagnetic resonance (EPR), infrared, and UV-Vis spectroscopy, in conjunction with density functional theory (DFT) calculations. EPR and DFT calculation studies reveal that the spin density of the radical is mainly equally located at both of the iron atoms.
2020, 36(6): 1137-1142
doi: 10.11862/CJIC.2020.118
Abstract:
Reactions of N, N-dimethyl-1, 5-diazabicyclo [3.2.1]octane iodide ([3.2.1-Me2dabco]I2) and 1-amino-1, 4-diazabicyclo [2.2.2]octane iodide ([2.2.2-NH2dabco]I) with anhydrous copper chloride in concentrated HCl aqueous solution afforded two organicinorganic hybrid compounds [3.2.1-Me2dabco] [CuCl4] (1) and [2.2.2-NH2dabco] [CuCl4] (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compounds 1 and 2 was a distorted tetrahedral geometry [CuCl4]2-. Compounds 1 and 2 showed an intriguing reversible thermochromism with color change from yellow to red which may be derived from the deformation of [CuCl4]2- tetrahedron.
Reactions of N, N-dimethyl-1, 5-diazabicyclo [3.2.1]octane iodide ([3.2.1-Me2dabco]I2) and 1-amino-1, 4-diazabicyclo [2.2.2]octane iodide ([2.2.2-NH2dabco]I) with anhydrous copper chloride in concentrated HCl aqueous solution afforded two organicinorganic hybrid compounds [3.2.1-Me2dabco] [CuCl4] (1) and [2.2.2-NH2dabco] [CuCl4] (2), respectively. The single-crystal X-ray diffraction revealed that the inorganic component in compounds 1 and 2 was a distorted tetrahedral geometry [CuCl4]2-. Compounds 1 and 2 showed an intriguing reversible thermochromism with color change from yellow to red which may be derived from the deformation of [CuCl4]2- tetrahedron.
2020, 36(6): 1143-1148
doi: 10.11862/CJIC.2020.123
Abstract:
A mononuclear Fe(Ⅲ) compound [FeⅢ(Him)2(4-MeOhapen)](CH3SO3) (1, Him=imidazole, H2(4-MeOhapen)=N, N'-bis(4-methoxy-2-hydroxyacetophenylidene)ethylenediamine) was synthesized and characterized structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that the CH3SO3- anions bridge the [FeⅢ(Him)2(4-MeOhapen)]+ cations by moderate hydrogen bonds to form one-dimensional chain structures. Magnetic suscepti-bility measurements revealed that compound 1 exhibits an abrupt spin crossover (SCO) with transition temperatures T1/2↓=163 K and T1/2↑=167 K. These results indicate that hydrogen bonds formed between the cationic and anionic centers play an important role in improving the SCO properties.
A mononuclear Fe(Ⅲ) compound [FeⅢ(Him)2(4-MeOhapen)](CH3SO3) (1, Him=imidazole, H2(4-MeOhapen)=N, N'-bis(4-methoxy-2-hydroxyacetophenylidene)ethylenediamine) was synthesized and characterized structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that the CH3SO3- anions bridge the [FeⅢ(Him)2(4-MeOhapen)]+ cations by moderate hydrogen bonds to form one-dimensional chain structures. Magnetic suscepti-bility measurements revealed that compound 1 exhibits an abrupt spin crossover (SCO) with transition temperatures T1/2↓=163 K and T1/2↑=167 K. These results indicate that hydrogen bonds formed between the cationic and anionic centers play an important role in improving the SCO properties.
2020, 36(6): 1149-1156
doi: 10.11862/CJIC.2020.126
Abstract:
Trigonal bipyramidal Ni(Ⅱ) complex [Ni(Me6tren)Cl](ClO4) (1, Me6tren=tris(2-(dimethylamino)ethyl)amine) has recently been shown by Ruamps and coworkers to possess large, uniaxial magnetic anisotropy (J. Am. Chem. Soc., 2013, 135:3017-3026). Their HF-EPR studies gave rhombic zero-field-splitting (ZFS) parameter E=1.56(5) cm-1 for 1. However, the axial ZFS parameter D has not been determined. We have used far-IR magnetic spectroscopy (FIRMS) at 0~17.5 T and 5 K to probe the magnetic transitions between the MS=±1 and MS=0 states of the ground spin state S=1 in 1. Direct observation of the transitions between Zeeman-split states in FIRMS gives axial ZFS parameter D=-110.7(3) cm-1. Hirshfeld surface analysis of the crystal structure of 1 has been performed, revealing the interactions between the cation and anion in a molecule of 1 as well as among the molecules of 1 in crystals.
Trigonal bipyramidal Ni(Ⅱ) complex [Ni(Me6tren)Cl](ClO4) (1, Me6tren=tris(2-(dimethylamino)ethyl)amine) has recently been shown by Ruamps and coworkers to possess large, uniaxial magnetic anisotropy (J. Am. Chem. Soc., 2013, 135:3017-3026). Their HF-EPR studies gave rhombic zero-field-splitting (ZFS) parameter E=1.56(5) cm-1 for 1. However, the axial ZFS parameter D has not been determined. We have used far-IR magnetic spectroscopy (FIRMS) at 0~17.5 T and 5 K to probe the magnetic transitions between the MS=±1 and MS=0 states of the ground spin state S=1 in 1. Direct observation of the transitions between Zeeman-split states in FIRMS gives axial ZFS parameter D=-110.7(3) cm-1. Hirshfeld surface analysis of the crystal structure of 1 has been performed, revealing the interactions between the cation and anion in a molecule of 1 as well as among the molecules of 1 in crystals.
2020, 36(6): 1157-1162
doi: 10.11862/CJIC.2020.129
Abstract:
Reaction of CCl4 with zirconium amide guanidinate Zr(NMe2)2 [iPrNC(NMe2)NiPr]2 (1) has been found to give ZrCl(NMe2) [iPrNC(NMe2)NiPr]2 (2) as an intermediate and later ZrCl2 [iPrNC(NMe2)NiPr]2 (3). The reaction is likely radical in nature. Complex 2 has been independently prepared from the reaction of ZrCl(NMe2)3 with diisopropylcarbodiimide, iPr-N=C=N-iPr, and characterized by nuclear magnetic resonance (NMR) and elemental analysis.
Reaction of CCl4 with zirconium amide guanidinate Zr(NMe2)2 [iPrNC(NMe2)NiPr]2 (1) has been found to give ZrCl(NMe2) [iPrNC(NMe2)NiPr]2 (2) as an intermediate and later ZrCl2 [iPrNC(NMe2)NiPr]2 (3). The reaction is likely radical in nature. Complex 2 has been independently prepared from the reaction of ZrCl(NMe2)3 with diisopropylcarbodiimide, iPr-N=C=N-iPr, and characterized by nuclear magnetic resonance (NMR) and elemental analysis.
2020, 36(6): 1163-1168
doi: 10.11862/CJIC.2020.128
Abstract:
Here, we report a successful method to fabricate a 2D bis(benzylammonium) lead tetrachloride (A2PbCl4) flake with a thickness of 3.6 nm by a combination of mechanical exfoliation and an Ar+ plasma thinning process. Piezoresponse force microscopy (PFM) measurements reveal that the ferroelectricity of the A2PbCl4 flakes with single-unit-cell thickness persists after Ar+ plasma etching.
Here, we report a successful method to fabricate a 2D bis(benzylammonium) lead tetrachloride (A2PbCl4) flake with a thickness of 3.6 nm by a combination of mechanical exfoliation and an Ar+ plasma thinning process. Piezoresponse force microscopy (PFM) measurements reveal that the ferroelectricity of the A2PbCl4 flakes with single-unit-cell thickness persists after Ar+ plasma etching.
2020, 36(6): 1169-1175
doi: 10.11862/CJIC.2020.100
Abstract:
Two new copper(Ⅱ) complexes, trans-[Cu(L1)2(NO3)(H2O)]NO3·H2O (1) and trans-[Cu(L2)2(NO3)(H2O)]NO3·H2O (2) (L1=3-(2-pyridyl)-4-(p-methylphenyl)-5-(2-quinolyl)-1, 2, 4-triazole, L2=3-(2-pyridyl)-4-(p-fluorophenyl)-5-(2-quinolyl)-1, 2, 4-triazole), were synthesized and characterized by FT-IR, elemental analyses and single-crystal X-ray crystallography. Both 1 and 2 crystallize in triclinic system with space group P1. X-ray crystallography analysis reveals that the copper ion in 1 and 2 lies in a distorted octahedral environment [CuN4O2] with one nitrate and one water molecule, respectively in the trans-position. The L1 or L2 ligand coordinates with Cu(Ⅱ) via one pyridine N atom and one triazole N atom, while the quinolyl group does not take part in coordination. In 1 and 2 there are some intermolecular O-H…O, C-H…O and C-H…N hydrogen bonds and C-H…π interactions, connecting the mononuclear complexes to form a 3D framework.
Two new copper(Ⅱ) complexes, trans-[Cu(L1)2(NO3)(H2O)]NO3·H2O (1) and trans-[Cu(L2)2(NO3)(H2O)]NO3·H2O (2) (L1=3-(2-pyridyl)-4-(p-methylphenyl)-5-(2-quinolyl)-1, 2, 4-triazole, L2=3-(2-pyridyl)-4-(p-fluorophenyl)-5-(2-quinolyl)-1, 2, 4-triazole), were synthesized and characterized by FT-IR, elemental analyses and single-crystal X-ray crystallography. Both 1 and 2 crystallize in triclinic system with space group P1. X-ray crystallography analysis reveals that the copper ion in 1 and 2 lies in a distorted octahedral environment [CuN4O2] with one nitrate and one water molecule, respectively in the trans-position. The L1 or L2 ligand coordinates with Cu(Ⅱ) via one pyridine N atom and one triazole N atom, while the quinolyl group does not take part in coordination. In 1 and 2 there are some intermolecular O-H…O, C-H…O and C-H…N hydrogen bonds and C-H…π interactions, connecting the mononuclear complexes to form a 3D framework.
2020, 36(6): 1176-1184
doi: 10.11862/CJIC.2020.131
Abstract:
Two new metal-organic frameworks (MOFs) [Cd3(tib)2(BPT)2(H2O)2]·DMA·6H2O (1) and [Zn2(tib)(HBTB)2(H2O)]·2H2O (2) (tib=1, 3, 5-tris(1-imidazolyl)benzene, H3BPT=biphenyl-3, 4', 5-tricarboxylic acid, H3BTB=4, 4', 4″-benzene-1, 3, 5-triyl-tribenzoic acid, DMA=N, N-dimethylacetamide) were synthesized and characterized. Complex 1 is a 4-nodal three-dimensional (3D) framework with point symbol {83}4{85·12}{86}2, while 2 is a two-dimensional (2D) network to be joined together by hydrogen bonds to generate a 3D supramolecular structure. Gas/vapor adsorption and luminescence behavior of the two complexes were studied. It is meaningful that 1 and 2 can selectively adsorb CO2 over N2, and MeOH over EtOH. Furthermore, 1 can selectively detect acetone through a fluorescence quenching mechanism in the organic solvents including MeOH, EtOH, 2-PA, CH3CN, DMF, DMA, THF, CHCl3, CH2Cl2 and acetone.
Two new metal-organic frameworks (MOFs) [Cd3(tib)2(BPT)2(H2O)2]·DMA·6H2O (1) and [Zn2(tib)(HBTB)2(H2O)]·2H2O (2) (tib=1, 3, 5-tris(1-imidazolyl)benzene, H3BPT=biphenyl-3, 4', 5-tricarboxylic acid, H3BTB=4, 4', 4″-benzene-1, 3, 5-triyl-tribenzoic acid, DMA=N, N-dimethylacetamide) were synthesized and characterized. Complex 1 is a 4-nodal three-dimensional (3D) framework with point symbol {83}4{85·12}{86}2, while 2 is a two-dimensional (2D) network to be joined together by hydrogen bonds to generate a 3D supramolecular structure. Gas/vapor adsorption and luminescence behavior of the two complexes were studied. It is meaningful that 1 and 2 can selectively adsorb CO2 over N2, and MeOH over EtOH. Furthermore, 1 can selectively detect acetone through a fluorescence quenching mechanism in the organic solvents including MeOH, EtOH, 2-PA, CH3CN, DMF, DMA, THF, CHCl3, CH2Cl2 and acetone.
2020, 36(6): 1185-1194
doi: 10.11862/CJIC.2020.132
Abstract:
Reactions of (4-carboxynaphthalen-1-yl)phosphonic acid (4-cnappH3) with manganese chloride under solvo/hydrothermal conditions resulted in four new coordination polymers, formulated as Mn(4-cnappH2)2 (1), Mn(4-cnappH2)2(H2O)2 (2), α-Mn(4-cnappH)(H2O) (3) and β-Mn(4-cnappH)(H2O) (4). Compound 1 shows a 3D framework structure, where chains made up of corner-sharing {MnO6} octahedra and {PO3C} tetrahedra are cross-linked by the organic groups of the phosphonate ligands. Compounds 2~4 exhibit 2D layered structures with interlayer hydrogen bonds through the pendent carboxylic acid groups. However, the layer topologies are different in the three cases. In 2, the {MnO6} octahedra and {PO3C} tetrahedra are corner-shared with each other alternatively, forming an inorganic layer containing rectangular-shaped 12-membered rings. In 3, edge-sharing dimers of {Mn2O2} are connected by {PO3C} tetrahedra through corner-sharing, forming an inorganic layer containing 4-membered rings. In 4, chains of corner-sharing {MnO5} are connected by {PO3C} tetrahedra into an inorganic layer containing 3-and 4-membered rings. Magnetic studies reveal that antiferromagnetic interactions are dominant in all four compounds.
Reactions of (4-carboxynaphthalen-1-yl)phosphonic acid (4-cnappH3) with manganese chloride under solvo/hydrothermal conditions resulted in four new coordination polymers, formulated as Mn(4-cnappH2)2 (1), Mn(4-cnappH2)2(H2O)2 (2), α-Mn(4-cnappH)(H2O) (3) and β-Mn(4-cnappH)(H2O) (4). Compound 1 shows a 3D framework structure, where chains made up of corner-sharing {MnO6} octahedra and {PO3C} tetrahedra are cross-linked by the organic groups of the phosphonate ligands. Compounds 2~4 exhibit 2D layered structures with interlayer hydrogen bonds through the pendent carboxylic acid groups. However, the layer topologies are different in the three cases. In 2, the {MnO6} octahedra and {PO3C} tetrahedra are corner-shared with each other alternatively, forming an inorganic layer containing rectangular-shaped 12-membered rings. In 3, edge-sharing dimers of {Mn2O2} are connected by {PO3C} tetrahedra through corner-sharing, forming an inorganic layer containing 4-membered rings. In 4, chains of corner-sharing {MnO5} are connected by {PO3C} tetrahedra into an inorganic layer containing 3-and 4-membered rings. Magnetic studies reveal that antiferromagnetic interactions are dominant in all four compounds.
2020, 36(6): 1195-1203
doi: 10.11862/CJIC.2020.130
Abstract:
This work probes the aggregation-induced emission enhancement (AIEE) property of a 2-(2-thienyl)imidazo [4, 5-f]-[1, 10]-phenanthroline (TIP) based rhenium(Ⅰ) tricarbonyl compound. Herein, N-alkylation reactions between 2-(5-bromo-4-methylthiophen-2-yl)-imidazo [4, 5-f]-[1, 10]-phenanthroline (1) and different alkyl bromides were carried out and three N-alkylated TIP derivatives (2a~2c) have been prepared successfully. The implantation of an N-alkyl group into the imidazole ring of TIP core can obviously increase the solubility in common organic solutions and affect the dihedral angles between imidazo [4, 5-f] [1, 10]phenanthroline and its neighbouring thiophene ring to different extents. The AIEE active rhenium(Ⅰ) tricarbonyl 3 was prepared via the reaction between 2a and Re(CO)5Cl. X-ray single-crystal analysis of 3 indicates that the loose packing mode and the multiple intermolecular hydrogen-bonding interactions are suggested to be responsible for the AIEE activity.
This work probes the aggregation-induced emission enhancement (AIEE) property of a 2-(2-thienyl)imidazo [4, 5-f]-[1, 10]-phenanthroline (TIP) based rhenium(Ⅰ) tricarbonyl compound. Herein, N-alkylation reactions between 2-(5-bromo-4-methylthiophen-2-yl)-imidazo [4, 5-f]-[1, 10]-phenanthroline (1) and different alkyl bromides were carried out and three N-alkylated TIP derivatives (2a~2c) have been prepared successfully. The implantation of an N-alkyl group into the imidazole ring of TIP core can obviously increase the solubility in common organic solutions and affect the dihedral angles between imidazo [4, 5-f] [1, 10]phenanthroline and its neighbouring thiophene ring to different extents. The AIEE active rhenium(Ⅰ) tricarbonyl 3 was prepared via the reaction between 2a and Re(CO)5Cl. X-ray single-crystal analysis of 3 indicates that the loose packing mode and the multiple intermolecular hydrogen-bonding interactions are suggested to be responsible for the AIEE activity.
