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2020 Volume 83 Issue 3
2020, 83(3): 195-208
Abstract:
Serum albumin has a long circulatory half-life in blood, and can be actively internalized by tumor cells through albumin receptor-mediated pathways. Consequently, this natural biomacromolecule has been recognized as one of the most promising carriers for building theranostic agents. Multifunctional albumin carriers have been used for conjugation with a variety of imaging agents and therapeutic agents towards cancer theranostics. Both covalent and non-covalent strategies have been developed for albumin functionalization. In this review, we summarize the recent progress and propose future perspectives in regard to the exploitation of albumin carriers for precision cancer theranostics.
Serum albumin has a long circulatory half-life in blood, and can be actively internalized by tumor cells through albumin receptor-mediated pathways. Consequently, this natural biomacromolecule has been recognized as one of the most promising carriers for building theranostic agents. Multifunctional albumin carriers have been used for conjugation with a variety of imaging agents and therapeutic agents towards cancer theranostics. Both covalent and non-covalent strategies have been developed for albumin functionalization. In this review, we summarize the recent progress and propose future perspectives in regard to the exploitation of albumin carriers for precision cancer theranostics.
2020, 83(3): 209-217
Abstract:
This review summarized the recent works on in-situ generated magnesium catalysts, especially for the systematic induction and category of in-situ magnesium catalysts generated from mono-active hydrogen containing ligands. We try to introduce the design and development of chiral ligands with mono-nitrogen-hydrogen bond, mono-phenol and mono-alcohol, and the related applications in in-situ generated magnesium catalysts, for realizing multi-types of asymmetric catalyzed transformations and the ways of chemical bonds formation. Further exploration of the strategy of in-situ generated magnesium catalysis would be beneficial to study and expand more types of chemical transformations mediated by cheap and low pollution metal resources.
This review summarized the recent works on in-situ generated magnesium catalysts, especially for the systematic induction and category of in-situ magnesium catalysts generated from mono-active hydrogen containing ligands. We try to introduce the design and development of chiral ligands with mono-nitrogen-hydrogen bond, mono-phenol and mono-alcohol, and the related applications in in-situ generated magnesium catalysts, for realizing multi-types of asymmetric catalyzed transformations and the ways of chemical bonds formation. Further exploration of the strategy of in-situ generated magnesium catalysis would be beneficial to study and expand more types of chemical transformations mediated by cheap and low pollution metal resources.
2020, 83(3): 218-225, 264
Abstract:
Graphitic carbon nitride (g-C3N4) is the most popular research direction by virtue of its stable physicochemical properties and good biocompatibility. Graphitic carbon nitride quantum dots (g-CNQDs), a kind of metal-free analogue for carbon-based QDs, have good biocompatibility, stable fluorescence, high quantum yield, and nontoxicity. Similar to carbon-based QDs, the g-CNQDs have the advantages of small size distribution, good water solubility, easy functionalization, excellent biocompatibility and chemical inertness. Compared with bulk g-C3N4, g-CNQDs have smaller size, higher fluorescence and quantum confinement effect, so they have better photocatalytic and physicochemical properties. In this paper, we aimed to provide a comprehensive review on the synthesis of g-CNQDs and their applications in multiple areas. The recent progress in the synthesis of g-CNQDs by microwave-assisted method, low temperature solid-phase method, thermochemical tailoring method and electrochemical etching method, as well as the current applications of g-CNQDs in catalysts, ion detections, biosensors, diagnosis and treatments were reviewed. The morphology and structure of the g-CNQDs prepared using different methods and precursors will be described, and it is necessary to continuously improve the synthesis method. Finally, the challenges, future trends and prospects of g-CNQDs were briefly pointed out.
Graphitic carbon nitride (g-C3N4) is the most popular research direction by virtue of its stable physicochemical properties and good biocompatibility. Graphitic carbon nitride quantum dots (g-CNQDs), a kind of metal-free analogue for carbon-based QDs, have good biocompatibility, stable fluorescence, high quantum yield, and nontoxicity. Similar to carbon-based QDs, the g-CNQDs have the advantages of small size distribution, good water solubility, easy functionalization, excellent biocompatibility and chemical inertness. Compared with bulk g-C3N4, g-CNQDs have smaller size, higher fluorescence and quantum confinement effect, so they have better photocatalytic and physicochemical properties. In this paper, we aimed to provide a comprehensive review on the synthesis of g-CNQDs and their applications in multiple areas. The recent progress in the synthesis of g-CNQDs by microwave-assisted method, low temperature solid-phase method, thermochemical tailoring method and electrochemical etching method, as well as the current applications of g-CNQDs in catalysts, ion detections, biosensors, diagnosis and treatments were reviewed. The morphology and structure of the g-CNQDs prepared using different methods and precursors will be described, and it is necessary to continuously improve the synthesis method. Finally, the challenges, future trends and prospects of g-CNQDs were briefly pointed out.
2020, 83(3): 226-231
Abstract:
The retired ternary power battery contains a large amount of high-value metal elements such as cobalt, lithium, nickel and manganese. Recycling retired ternary power battery from electric vehicles can alleviate the recovery and environmental pollution pressure caused by retired batteries, and effectively improve resource utilization and economic benefits. This paper expounds the status quo of domestic and foreign technology research, especially focusing on the hydrometallurgy, including pretreatment and secondary treatment techniques such leaching, chemical precipitation, and solvent. Compared with pyrometallurgy, the advantages and disadvantages of the methods are introduced in detail. It is expected that this research could provide a guideline for improving retired ternary power battery recycling, and this topic can further promote the realization of industrialization.
The retired ternary power battery contains a large amount of high-value metal elements such as cobalt, lithium, nickel and manganese. Recycling retired ternary power battery from electric vehicles can alleviate the recovery and environmental pollution pressure caused by retired batteries, and effectively improve resource utilization and economic benefits. This paper expounds the status quo of domestic and foreign technology research, especially focusing on the hydrometallurgy, including pretreatment and secondary treatment techniques such leaching, chemical precipitation, and solvent. Compared with pyrometallurgy, the advantages and disadvantages of the methods are introduced in detail. It is expected that this research could provide a guideline for improving retired ternary power battery recycling, and this topic can further promote the realization of industrialization.
2020, 83(3): 232-239
Abstract:
The positive effects of oxygen vacancy defects on the performance of semiconductor materials are attracting increasing attention. Herein, blue TiO2 nanosheet with rich oxygen vacancies was successfully synthesized via a one-step molten salt method using the hydrolysis product of TiCl4 in trifluoroacetic acid as a precursor. Due to the low oxygen partial pressure of the molten salt, the lattice oxygen of TiO2 was consumed during calcination, leading to a large amount of oxygen vacancies and Ti3+. UV-Visible diffuse reflectance spectroscopy showed that the band gap of blue TiO2 nanosheets was reduced to 2.69 eV, and the light adsorption range was extended from the ultraviolet region to the visible region. The as-prepared blue TiO2 nanosheets exhibits excellent photocatalytic activity, and the photodegradation rate of rhodamine B is 47.3 times that of pure TiO2 under full-spectrum light irradiation. At the same time, the formed lattice fluorine doping can effectively stabilize the oxygen vacancies and greatly improve the separation efficiency of the photogenerated carriers. This work provides a new insight for constructing oxygen vacancies in semiconductor oxide materials.
The positive effects of oxygen vacancy defects on the performance of semiconductor materials are attracting increasing attention. Herein, blue TiO2 nanosheet with rich oxygen vacancies was successfully synthesized via a one-step molten salt method using the hydrolysis product of TiCl4 in trifluoroacetic acid as a precursor. Due to the low oxygen partial pressure of the molten salt, the lattice oxygen of TiO2 was consumed during calcination, leading to a large amount of oxygen vacancies and Ti3+. UV-Visible diffuse reflectance spectroscopy showed that the band gap of blue TiO2 nanosheets was reduced to 2.69 eV, and the light adsorption range was extended from the ultraviolet region to the visible region. The as-prepared blue TiO2 nanosheets exhibits excellent photocatalytic activity, and the photodegradation rate of rhodamine B is 47.3 times that of pure TiO2 under full-spectrum light irradiation. At the same time, the formed lattice fluorine doping can effectively stabilize the oxygen vacancies and greatly improve the separation efficiency of the photogenerated carriers. This work provides a new insight for constructing oxygen vacancies in semiconductor oxide materials.
2020, 83(3): 246-252
Abstract:
Two new tripodal receptors 1 and 2 containing benzoyl thiourea units were synthesized and characterized by conventional technical methods. Studies have shown that this type of receptor compound exhibits good UV-Vis recognition ability for F-, Ac- and CN-. Since the receptor compound 1 has a strong intramolecular charge transfer effect, it exhibits naked eye recognition performance for anions. UV titration indicated that this class of compounds had better binding ability to F- and CN-. Nuclear magnetic titration showed that the anion formed a host-guest complex through the intermolecular hydrogen bond with the host, and the proton detonation behavior occurred at the high concentration of F-. In addition, this class of subjects had a certain ability to selectively recognize Hg2+.
Two new tripodal receptors 1 and 2 containing benzoyl thiourea units were synthesized and characterized by conventional technical methods. Studies have shown that this type of receptor compound exhibits good UV-Vis recognition ability for F-, Ac- and CN-. Since the receptor compound 1 has a strong intramolecular charge transfer effect, it exhibits naked eye recognition performance for anions. UV titration indicated that this class of compounds had better binding ability to F- and CN-. Nuclear magnetic titration showed that the anion formed a host-guest complex through the intermolecular hydrogen bond with the host, and the proton detonation behavior occurred at the high concentration of F-. In addition, this class of subjects had a certain ability to selectively recognize Hg2+.
2020, 83(3): 253-257
Abstract:
Two metal complexes, named C1 and C2, were synthesized by reaction of Schiff base synthesized from 2-amino-5-chlorophenol and 2-quinoline formaldehyde with nickel chloride and copper chloride respectively. Their structures were characterized by single crystal X-ray diffraction. The inhibitory activities of complexes C1 and C2 on the proliferation of different human hepatoma cell lines and normal hepatoma cell lines HL-7702 were tested by MTT method. The results showed that the inhibitory activities of C1 and C2 on human hepatoma cell lines are better than that of cisplatin, C1 and C2 are less toxic to normal hepatoma cell lines HL-7702 than cisplatin. Through the experiments of reactive oxygen species and cell cycle, it can be concluded that the anti-tumor mechanism of complexes C1 and C2 is the oxidative damage of tumor cells caused by the production of living oxygen and the arrest of cell cycle in G0/G1 phase.
Two metal complexes, named C1 and C2, were synthesized by reaction of Schiff base synthesized from 2-amino-5-chlorophenol and 2-quinoline formaldehyde with nickel chloride and copper chloride respectively. Their structures were characterized by single crystal X-ray diffraction. The inhibitory activities of complexes C1 and C2 on the proliferation of different human hepatoma cell lines and normal hepatoma cell lines HL-7702 were tested by MTT method. The results showed that the inhibitory activities of C1 and C2 on human hepatoma cell lines are better than that of cisplatin, C1 and C2 are less toxic to normal hepatoma cell lines HL-7702 than cisplatin. Through the experiments of reactive oxygen species and cell cycle, it can be concluded that the anti-tumor mechanism of complexes C1 and C2 is the oxidative damage of tumor cells caused by the production of living oxygen and the arrest of cell cycle in G0/G1 phase.
2020, 83(3): 258-264
Abstract:
Three kinds of structure-symmetric thiourea catalysts with multi-chiral center and multi-hydrogen bond with axial chiral amphiyl skeleton were synthesized and applied to the synthesis of 3, 4-dihydropyrimidine thioneone by Biginelli reaction. The results show that the synthesized axial chiral thioureas all show good catalytic activity, which can effectively improve the yield and enantioselectivity of the Biginelli reaction.
Three kinds of structure-symmetric thiourea catalysts with multi-chiral center and multi-hydrogen bond with axial chiral amphiyl skeleton were synthesized and applied to the synthesis of 3, 4-dihydropyrimidine thioneone by Biginelli reaction. The results show that the synthesized axial chiral thioureas all show good catalytic activity, which can effectively improve the yield and enantioselectivity of the Biginelli reaction.
2020, 83(3): 265-271
Abstract:
N6, N6-Dimethyladenine (DMAP) is component of biomolecules and plays important roles in determining the activity and conformational properties of biomolecules. Hydroxyl radical (·OH) can react with DMAP to change its structure and influence its biological function. It is necessary to understand how DMAP reacts with·OH. In this paper, reaction mechanisms of DMAP and·OH have been investigated using theoretical calculations. Based on the stability of reaction energy barrier and product, the most likely reaction of DMAP and·OH is N(6) methyl H abstraction, N(9)H abstraction and C(8) addition. Methylation on N(6) improves the reactivity of adenine, and affects its reaction mechanism with·OH.
N6, N6-Dimethyladenine (DMAP) is component of biomolecules and plays important roles in determining the activity and conformational properties of biomolecules. Hydroxyl radical (·OH) can react with DMAP to change its structure and influence its biological function. It is necessary to understand how DMAP reacts with·OH. In this paper, reaction mechanisms of DMAP and·OH have been investigated using theoretical calculations. Based on the stability of reaction energy barrier and product, the most likely reaction of DMAP and·OH is N(6) methyl H abstraction, N(9)H abstraction and C(8) addition. Methylation on N(6) improves the reactivity of adenine, and affects its reaction mechanism with·OH.
2020, 83(3): 272-276
Abstract:
In the solution polymerization system, the grafted microparticles PDAC/PSA were prepared by grafting functional monomer acryloyloxyethyltrimethylammonium chloride (DAC) onto the surface of polystyrene primary amine microspheres (PSA) through a free radical polymerization method. The main influence factors on graft polymerization were investigated, and its adsorption characteristics for L-glutamic acid were preliminarily explored. The results showed that at the temperature of 25℃, the mass fraction of the monomer is 6% of the total solution, and the initiator is 1.2% of the mass of the monomer, the grafted particles with a grafting degree of 431mg·g-1 can be obtained. Its adsorption capacity for L-glutamic acid reaches 140mg·g-1.
In the solution polymerization system, the grafted microparticles PDAC/PSA were prepared by grafting functional monomer acryloyloxyethyltrimethylammonium chloride (DAC) onto the surface of polystyrene primary amine microspheres (PSA) through a free radical polymerization method. The main influence factors on graft polymerization were investigated, and its adsorption characteristics for L-glutamic acid were preliminarily explored. The results showed that at the temperature of 25℃, the mass fraction of the monomer is 6% of the total solution, and the initiator is 1.2% of the mass of the monomer, the grafted particles with a grafting degree of 431mg·g-1 can be obtained. Its adsorption capacity for L-glutamic acid reaches 140mg·g-1.
2020, 83(3): 240-245, 252
Abstract:
Two fluorescent probes, (N1'E, N3'E)-N1', N3'-bis((7-N, N-diethylaminocoumarin-3-yl)methylene) malonohydrazide and (N1'E, N4'E)-N1', N4'-bis((7-N, N-diethylaminocoumarin-3-yl)methylene) succinohydrazide, bearing acylhydrazone group as binding site and coumarin group as the fluorescence signal group were synthesized and characterized by conventional techniques. These probes showed notable fluorescence turn-off response for Cu2+ over other metals ions. The probes and Cu2+ formed 1:2 coordination complexes according to spectroscopy data and Job's plots. Further study demonstrated that the detection limit of Cu2+ for the probes was as low as 10-9 mol/L.
Two fluorescent probes, (N1'E, N3'E)-N1', N3'-bis((7-N, N-diethylaminocoumarin-3-yl)methylene) malonohydrazide and (N1'E, N4'E)-N1', N4'-bis((7-N, N-diethylaminocoumarin-3-yl)methylene) succinohydrazide, bearing acylhydrazone group as binding site and coumarin group as the fluorescence signal group were synthesized and characterized by conventional techniques. These probes showed notable fluorescence turn-off response for Cu2+ over other metals ions. The probes and Cu2+ formed 1:2 coordination complexes according to spectroscopy data and Job's plots. Further study demonstrated that the detection limit of Cu2+ for the probes was as low as 10-9 mol/L.
2020, 83(3): 277-281
Abstract:
Oxidation number is an important property of elements and widely applied in inorganic chemistry. The assignment of oxidation number was traditionally based on a set of rules founded by Ryōichi Kiriyama and Linus Pauling. These rules play important roles in the popularization of oxidation numbers in inorganic chemistry. But these initial rules would not work when dealing the compounds with complicated and unknown structures. According to the definition of oxidation number by IUPAC, a new method for determining the oxidation number based on the oxidation number depending entirely on the electron supply and demand relationship between the bonding two atoms is proposed here. The highest positive oxidation number of an element is limited by the number of electrons in its valence layer, and the lowest negative oxidation number of the element is limited by the difference between the number of electrons around the rare gas element and the number of valence layers in the same period. This method requires no information about molecule structure or initial rules of oxidation number. Furthermore, it is simple with few exceptions and can be used in high school and college chemistry teaching.
Oxidation number is an important property of elements and widely applied in inorganic chemistry. The assignment of oxidation number was traditionally based on a set of rules founded by Ryōichi Kiriyama and Linus Pauling. These rules play important roles in the popularization of oxidation numbers in inorganic chemistry. But these initial rules would not work when dealing the compounds with complicated and unknown structures. According to the definition of oxidation number by IUPAC, a new method for determining the oxidation number based on the oxidation number depending entirely on the electron supply and demand relationship between the bonding two atoms is proposed here. The highest positive oxidation number of an element is limited by the number of electrons in its valence layer, and the lowest negative oxidation number of the element is limited by the difference between the number of electrons around the rare gas element and the number of valence layers in the same period. This method requires no information about molecule structure or initial rules of oxidation number. Furthermore, it is simple with few exceptions and can be used in high school and college chemistry teaching.
2020, 83(3): 282-287
Abstract:
Boyle's corpuscular philosophy and Dalton's atomism are two representative theories in the development of atomic thought. By comparing the ideological basis and motivation of the times, the methodological basis as well as the reasons for the origin, material level and chemical change of all substances and so on, it can be found that the ideological basis determines the way forward for the development of scientific theory to a certain extent, scientific progress also shows the development of The Times.
Boyle's corpuscular philosophy and Dalton's atomism are two representative theories in the development of atomic thought. By comparing the ideological basis and motivation of the times, the methodological basis as well as the reasons for the origin, material level and chemical change of all substances and so on, it can be found that the ideological basis determines the way forward for the development of scientific theory to a certain extent, scientific progress also shows the development of The Times.
