Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valua...Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valuable in numerous applications owing to their unique chemical and biological characteristics.This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications.The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms,such as iron depletion,metallo-β-lactamases inhibitors,intracellular ATP depletion,non-viral gene vector,DNA/RNA syntheses inhibitors and theranostics agent.Of interest are the metal complex of macrocyclic polyamines,which is usually a double-edged sword as dealing with endogenous macromolecular targets,especially DNA.These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines,and achieve actual applications in medicine.展开更多
New water-soluble fluorescent tetracationic imidazolium-based macrocycles are synthesized via a modular SN2 nucleophilic substitution reaction.The positive charge and acidic C-H sites of these macrocycles enable them ...New water-soluble fluorescent tetracationic imidazolium-based macrocycles are synthesized via a modular SN2 nucleophilic substitution reaction.The positive charge and acidic C-H sites of these macrocycles enable them to bind with nucleotides in water,driven by hydrogen bonds and electrostatic interactions.The binding is high affinity for suitable nucleotides.These properties position them as promising candidates for the selective sensing of nucleotides.展开更多
Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis（3-aminopropoxy）butane with metal nitrate and 1,3-bis（2-formylphenyl）propane or 1,4-bis（2-formylphenyl）butane and their structures ...Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis（3-aminopropoxy）butane with metal nitrate and 1,3-bis（2-formylphenyl）propane or 1,4-bis（2-formylphenyl）butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, ^1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1： 1. The complexes are 1：2 electrolytes for Pb（II）, Zn（II） and Cd（II） complexes and 1：3 electrolytes for La（III） as shown by their molar conductivities （Am） in DMSO at 10^-3 mol L^-1. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of La（III） and Pb（II） were proposed to probably octahedral and Zn（II） and Cd（II） complexes were proposed to probably tetrahedral.展开更多
The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
A new macrocyclic diterpenoid,named kansuinine J（1）,was isolated from the roots of Euphorbia kansui.Its structure was characterized on the basis of spectroscopic analysis.
Imitating the signal transduction and transmembrane transport co ntrolled by biological channels in the cell membra ne,artificial nanochannels with a similar capability of sensing and transport are constructed as bion...Imitating the signal transduction and transmembrane transport co ntrolled by biological channels in the cell membra ne,artificial nanochannels with a similar capability of sensing and transport are constructed as bionic nanochannels.To accomplish selective sensing and transport of biological analyte(as "vip"),the bionic nanochannels are modified with the artificial receptor(as "host"),Based on selective recognition between host and vip,bionic nanochannels translate the stimulus of the vip to electrochemical signal as sensors,and further regulate the transmission of vip as transporters.Howeve r,throughout all kinds of vips,the selective sensing and transpo rt of ions and chiral molecules is a challenging problem.And throughout all hosts of ions and chiral molecules,the macrocyclic hosts with multisite of recognition show better selectivity,such as crown ethers,cyclodextrins,calixarenes,and pillararenes.In this article,we highlight recent advances in the macrocyclic host-based nanochannels for the selective sensing and transport of ionic and chiral vips,summarize the similarities and differences of different kinds of macrocyclic host-based nanochannels,and expect the research direction and application prospect.展开更多
The activities of the catalytic hydrolysis of phosphate diester （BNPP） [bis（p-nitrophenyl）phosphate diester] and plasmid DNA （pUC 18） by mononuclear macrocyclic polyamine metal complexes have been investigated i...The activities of the catalytic hydrolysis of phosphate diester （BNPP） [bis（p-nitrophenyl）phosphate diester] and plasmid DNA （pUC 18） by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn（II） complex （composed of lipophilic group） as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA （pUC18） at physiological conditions.展开更多
Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien,...Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.展开更多
The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distribut...The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.展开更多
Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [Z...Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by vip water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.展开更多
A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesi...A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.展开更多
The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]...The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.展开更多
Protein-protein interactions(PPIs) are recognized as attractive therapeutic targets. However targeting PPIs especially intracellular ones has been proven extremely difficult for conventional drug-like small molecules,...Protein-protein interactions(PPIs) are recognized as attractive therapeutic targets. However targeting PPIs especially intracellular ones has been proven extremely difficult for conventional drug-like small molecules, and biological drugs such as monoclonal antibodies have difficulty in reaching intracellular targets. Macrocyclic peptides are promising candidates of PPI regulators for their potential in combining high potency and biological stability together. Cell permeability of macrocyclic peptides may also be achieved by structural modifications or conjugation to a cell-penetrating sequence. Significant progress has been made in this research area in recent years. Important technology progress and recent examples of macrocyclic peptide PPI modulators are reviewed.展开更多
On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to ...On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.展开更多
Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloai...Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloaikylsulfonates（1）in total yields of 45 and 57%,respectively.展开更多
A series of novel aromatic-linked polyamine macrocyclic derivatives have been synthesized. Their structures were confirmed by MS and ^1H NMR. These compounds exhibited potent anti-HIV-1 activities.
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金National Natural Science Foundation of China(Nos.22177011,21977012,and 21672021)the Joint Project of BRCBC(Biomedical Translational Engineering Research Center of BUCT-CJFH)(No.XK2020-06).
文摘Macrocyclic polyamines are excellent chelating agents with the advantage of forming highly stable complexes.They offer the flexibility to adjust the coordination environment through functionalization.making them valuable in numerous applications owing to their unique chemical and biological characteristics.This review summarizes the use of macrocyclic polyamines as carriers and molecular platforms of targeted drugs for medical applications.The significance and innovative design of these original approaches are dissected from the unique perspective of diverse mechanisms,such as iron depletion,metallo-β-lactamases inhibitors,intracellular ATP depletion,non-viral gene vector,DNA/RNA syntheses inhibitors and theranostics agent.Of interest are the metal complex of macrocyclic polyamines,which is usually a double-edged sword as dealing with endogenous macromolecular targets,especially DNA.These excellent cases will help to understand the typical mechanism in drug design based on macrocyclic polyamines,and achieve actual applications in medicine.
基金Zhejiang Provincial Natural Science Foundation of China(Nos.LR24B020003 and LQ24B020003)Science and Technology Project of Taizhou City(No.24gyb17)for financial support。
文摘New water-soluble fluorescent tetracationic imidazolium-based macrocycles are synthesized via a modular SN2 nucleophilic substitution reaction.The positive charge and acidic C-H sites of these macrocycles enable them to bind with nucleotides in water,driven by hydrogen bonds and electrostatic interactions.The binding is high affinity for suitable nucleotides.These properties position them as promising candidates for the selective sensing of nucleotides.
文摘Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis（3-aminopropoxy）butane with metal nitrate and 1,3-bis（2-formylphenyl）propane or 1,4-bis（2-formylphenyl）butane and their structures were proposed on the basis of elemental analysis, FTIR, UV-vis, molar conductivity measurements, ^1H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1： 1. The complexes are 1：2 electrolytes for Pb（II）, Zn（II） and Cd（II） complexes and 1：3 electrolytes for La（III） as shown by their molar conductivities （Am） in DMSO at 10^-3 mol L^-1. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of La（III） and Pb（II） were proposed to probably octahedral and Zn（II） and Cd（II） complexes were proposed to probably tetrahedral.
文摘The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
基金supported by grants from the Ministry of Science and Technology(Nos.2009CB940900 and 2009CB522300)
文摘A new macrocyclic diterpenoid,named kansuinine J（1）,was isolated from the roots of Euphorbia kansui.Its structure was characterized on the basis of spectroscopic analysis.
基金financially supported by the National Key Research and Development Program of China (No.2018YFD0200102)the National Natural Science Foundation of China (Nos.21911530178 and 21772055)+1 种基金the 111 Project (No.B17019)Self-determined research funds of CCNU from the colleges’ basic research and operation of MOE。
文摘Imitating the signal transduction and transmembrane transport co ntrolled by biological channels in the cell membra ne,artificial nanochannels with a similar capability of sensing and transport are constructed as bionic nanochannels.To accomplish selective sensing and transport of biological analyte(as "vip"),the bionic nanochannels are modified with the artificial receptor(as "host"),Based on selective recognition between host and vip,bionic nanochannels translate the stimulus of the vip to electrochemical signal as sensors,and further regulate the transmission of vip as transporters.Howeve r,throughout all kinds of vips,the selective sensing and transpo rt of ions and chiral molecules is a challenging problem.And throughout all hosts of ions and chiral molecules,the macrocyclic hosts with multisite of recognition show better selectivity,such as crown ethers,cyclodextrins,calixarenes,and pillararenes.In this article,we highlight recent advances in the macrocyclic host-based nanochannels for the selective sensing and transport of ionic and chiral vips,summarize the similarities and differences of different kinds of macrocyclic host-based nanochannels,and expect the research direction and application prospect.
基金supported by the Science and Technology Department(No.04JY029-018)Education Department of Sichuan Province(No.2006ZD049).
文摘The activities of the catalytic hydrolysis of phosphate diester （BNPP） [bis（p-nitrophenyl）phosphate diester] and plasmid DNA （pUC 18） by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn（II） complex （composed of lipophilic group） as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA （pUC18） at physiological conditions.
基金supported by the National Natural Science Foundation of China(No.20771083)
文摘Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.
文摘The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
基金the Robert A. Welch Foundation (A-0259) in the U.S and China Scholarship Council is gratefully acknowledged.
文摘The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.
基金supported by the Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2013-191)National Undergraduate Training Programs for Innovation and Entrepreneurship(201310551158)+4 种基金the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030)the Key Laboratory of Functional Organometallic Materials of Hunan Province College(13K09,13K10)the Program for Excellent Talents in Hunan University of Science and Engineeringthe Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)
文摘Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by vip water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.
文摘A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.
基金Supported by the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030,13CY029)the Program for Excellent Talents in Hunan University of Science and Engineering(2013)+2 种基金the Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)NSF of Hunan(11JJ2009)
文摘The reactions of chiral four-coordinated nickel（Ⅱ） complex [Ni（RR-L）]（ClO4）2/[Ni（SS- L）]（ClO4）2 with β-dl-phenylalanine in acetonitrile/water gave a six-coordinated enantiomer of [Ni（RR-L）（β-d-HPhe）]（ClO4）2（1） and [Ni（SS-L）（β-l-HPhe）]（ClO4）2（2）, respectively（L = 5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, HPhe = phenylalanine）. Single-crystal X-ray diffraction analyses revealed that the nickel（Ⅱ） atom displays a distorted octahedral coordination geometry by coordinating with four nitrogen atoms of L in a folded configuration, and two carboxylate oxygen atoms of β-d/l-HPhe in cis-position in both complexes. The monomers of [Ni（RR-L）（β-d-HPhe）]2＋ and [Ni（SS-L）（β-l-HPhe）]2＋ are connected through intermolecular hydrogen bonds to generate one-dimensional zigzag chains, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.
基金supported by Principle Training Program of Education Department of Sichuan Province (No. 18CZ0042)Fundamental Research Fund of Chengdu University (No. 2081916027)Undergraduate Innovation Programm of Chengdu University (Nos. CDU_CX_2018250, CDU_CX_2018251)
文摘Protein-protein interactions(PPIs) are recognized as attractive therapeutic targets. However targeting PPIs especially intracellular ones has been proven extremely difficult for conventional drug-like small molecules, and biological drugs such as monoclonal antibodies have difficulty in reaching intracellular targets. Macrocyclic peptides are promising candidates of PPI regulators for their potential in combining high potency and biological stability together. Cell permeability of macrocyclic peptides may also be achieved by structural modifications or conjugation to a cell-penetrating sequence. Significant progress has been made in this research area in recent years. Important technology progress and recent examples of macrocyclic peptide PPI modulators are reviewed.
基金Project supported by the National Natural Science Foundation of China(22131011,22071274,21821003)the Pearl River Talent Plan of Guangdong(2017BT01C161)。
文摘On account of the complicated magnetic exchange interactions between lanthanide ions,binuclear lanthanide complexes have broad application prospect in the field of single-molecule magnets.Therefore,it is necessary to develop reasonable bridging ligands to manipulate the directional assembly of binuclear lanthanide complexes.Herein,we selected the macrocyclic ligand L^(N_(8)O_(2))to build up two new dilanthanide complexes[Ln_(2)(LN_(8)O_(2))(OpyO)_(2)(H_(2)O)2](NO_(3))_(2)(1-Ln,Ln=Dy,Tb;LN_(8)O_(2)=hexamethyl-tetraaza-dioxe-dipyrazolacycloicosaphane-2,9,12,19-tetraene;OpyOH=2-pyridinol-1-oxide).Dynamic magnetic studies show that 1-Dy exhibits slow relaxation behavior under a 1 kOe applied field.Further fitting analysis of relaxation times gives the effective energy barrier of 38.2 cm^(−1),and reveals that the slow magnetic relaxation behavior is dominated by the Orbach and Raman processes.High-resolution luminescence emission spectrum indicates the energy gap of 36.8 cm^(−1)between the ground state and the first excited state,consistent with the magnetic measurement results.1-Tb exhibits brilliant characteristic green light emission under UV light excitation.The absolute quantum yield of 1-Tb is 44.8%,and its first-order fitted decay lifetime is 779.21μs at room temperature.This study provides the way for directional construction of high-performance molecular materials with magnetic and optical dual-function.
文摘Two representative macrocyclic lactones with methoxysulfonyl side chain（5a and 5b）were synthesized employing Michael addition with acrolein and ring enlargement as the key steps,starting from potassium,α-oxocycloaikylsulfonates（1）in total yields of 45 and 57%,respectively.
基金supported by the National Basic Research Program of China(973 project:No.2004CB518908)the National Natural Science Foundation of China(No.30472093)to SLthe 0utstanding 0verseas Chinese Scholars Fund of Chinese Academy of Sciences(No.2005-2-6)to S.J.
文摘A series of novel aromatic-linked polyamine macrocyclic derivatives have been synthesized. Their structures were confirmed by MS and ^1H NMR. These compounds exhibited potent anti-HIV-1 activities.
