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
Traditional Chinese medicine(TCM)has become an important treasure trove of natural resources for the development of new medicines due to their diverse compositions,significant therapeutic effects,and few side effects....Traditional Chinese medicine(TCM)has become an important treasure trove of natural resources for the development of new medicines due to their diverse compositions,significant therapeutic effects,and few side effects.The screening of active ingredients in TCM represents a crucial step in elucidating the material basis and mechanism of action of TCM.At present,efficient and precise molecular recognition techniques based on intermolecular interactions have been extensively employed for the identification of active ingredients in TCM.This paper presents a review of the fundamental principles underlying solution-phase/affinity ligand fishing,solid-phase/affinity ligand fishing,molecular imprinting and molecular docking techniques,with a particular focus on their applications in the screening of active ingredients in TCM.Furthermore,the paper compares the advantages and disadvantages of the various techniques and identifies the limitations of existing techniques.In conclusion,the paper identifies the prospective trajectory of molecular recognition techniques in the domain of TCM research.This paper not only provides theoretical references for the development of new methods of active ingredient screening but also helps to promote the modernization and internationalization of TCM.展开更多
Anion can be identified by pyromellitic imide-azacyclophane which is one of the host compounds.This article investigated the interaction between the host and organic pollution compounds.The host and other eight compou...Anion can be identified by pyromellitic imide-azacyclophane which is one of the host compounds.This article investigated the interaction between the host and organic pollution compounds.The host and other eight compounds were optimized by DFT（density functional theory） B3LYP/6-31G level and the energy of compounds was corrected using Boys-Bemardi method.On the basis of B3LYP/6-31G optimized geometries,the RDG function and sign（λ2（r））ρ（r） function values of space points were calculated,and color RDG isosurface map was drawn.3He chemical shift was calculated by the B3LYP/6-31G method.The results showed that the eight organic pollution molecules with the host one shaped stable configurations by hydrogen bonds,respectively.The stabilization energy of complexes 4 and 7 showed repulsion（steric effects） of cyclophane cage observably affecting the stability of the complexes.The location,intensity and the type of interaction in complex 1 were analyzed through color-filled RDG isosurface map.Aromaticity calculations showed that the weak interaction reduced the transverse induction ring current in the host rings,and deteriorated the aromaticity of compounds.展开更多
This study involves initial Hartree-Fock and Density Functional theory calculations onthe molecular recognition of the cyclodextrins. The α-cyclodextrin-acetophenone complexationsystem was investigated with PM3, HF/...This study involves initial Hartree-Fock and Density Functional theory calculations onthe molecular recognition of the cyclodextrins. The α-cyclodextrin-acetophenone complexationsystem was investigated with PM3, HF/3-21G* and B3LYP/3-21G* methods. The results indicatedthat the inclusion orientation in which the acetyl group of the acetophenone points towards thesecondary hydroxyls of the a-cyclodextrin was preferable in energy. The steric effect wassupposed as the physical reason of such a behavior Hence, the simple rule the anti-parallelarrangement of the dipoles of the host and vip molecules in the cyclodextrin complexqtion is notgenerally applicable.展开更多
Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar vips espec...Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar vips especially ionic vips and monosaccharides. Electronic spectra of coordinates are computed by the INDO/SCI method. The reason of the blue-shift for UV absorption of complexes relative to that of hosts is discussed and electronic transition is theoretic- cally assigned.展开更多
Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processe...Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processes at the molecular level.Over the past five decades,supramolecular chemists have developed a vast array of synthetic receptors with highly diverse structures and recognition properties.Among them,cyclophanes represent an important family of macrocyclic receptors that have been extensively explored.The aromatic moieties in cyclophanes not only facilitate chemical modifications to impart water solubility but also enable forming hydrophobic cavities for vip inclusion in aqueous environments.Pioneered by Koga et al.,who reported the first inclusion complex of cyclophanes in water and solid state,numerous water-soluble cyclophanes,including derivatives of blue box,calixarenes,resorcinarenes,pillararenes,octopusarenes,biphenarenes,coronarenes,and naphthotubes,etc.,have been synthesized and subjected to investigation of the recognition capabilities in aqueous solutions.This review provides an overview of cyclophane receptors designed to bind organic vips in water.We categorize them into two classes based on the modifications made to their hydrophobic cavities:those with“exo-functionalized hydrophobic cavities”and those with“endo-functionalized hydrophobic cavities”.We introduce their distinctive features and discuss strategies to enhance recognition affinity and selectivity.This review aims to inspire the development of novel synthetic receptors with intriguing properties and foster practical applications of cyclophanes.展开更多
β-Cyclodextrin (β-CD) and its cross-linked polymer (β-CDP) were known as the mimetic models. Metalloporphyrin had been widely used in the enzymatic method of analysis and molecular recognition. In present work, it ...β-Cyclodextrin (β-CD) and its cross-linked polymer (β-CDP) were known as the mimetic models. Metalloporphyrin had been widely used in the enzymatic method of analysis and molecular recognition. In present work, it was investigation that supramolecular recognition for halogenated phenols, three crosols, three nitrophenols and three aminophenols, served respectively as the substrate of the mimetic receptor, iron-5, 10, 15, 20-tetrakis (sulforphenyl)-21H, 23H-porphine (FeTPPS) or FeTPPS-β-CDP. Supramolecular complex, FeTPPS-β-CDP with function of mult i-recognition and induced-fit, was a advanced kind of mimetic peroxidase; Methyl phenol or polyphenol was the substitute of chlorophenic acid, while aminophenols and other phenols were suggested not to be utilized to enzymatic assay of H2O2. Being a mimetic enzyme mimicking the space structure of overall proteinase, beaimed by immobilized mimetic enzyme with a large number of β-CD interior cavities, chlorophenol was identified optimal substrate in the system tested.展开更多
Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments....Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments.By mimicking the cavity feature of bioreceptors,Prof.Wei Jiang proposed and clarified the concept of“endo-functionalized cavity”.Through situating polar binding sites into a deep hydrophobic cavity,we designed and synthesized several macrocyclic hosts,among which amide naphthotubes are the most representative.The hosts can selectively recognize various polar molecules including organic micropollutants,drug molecules,and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding.In addition,these biomimetic hosts have been applied in spectroscopic analysis,adsorptive separation and self-assembly.In this review,we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group.We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.展开更多
A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morpholo...A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM （transmission electron microscopy）. The UV-Vis spectroscopic behavior of PC/MTOAB/thymine （molar ratio = 5： 1： 1 ） and PC/MTOAB/TOTB （molar ratio = 5： 1： 1 ） of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.展开更多
Assembly of carbohydrates on nickel (Ⅱ) center by utilizing N-glycosidicbond formation with a branched amine: tris(2-aminoethyl)amine (tren), an unprecedentedchiral inversion around the metal center (Co or Mn) induce...Assembly of carbohydrates on nickel (Ⅱ) center by utilizing N-glycosidicbond formation with a branched amine: tris(2-aminoethyl)amine (tren), an unprecedentedchiral inversion around the metal center (Co or Mn) induced by an interaction betweensugars and sulfate anions, peroxo-bridged dinuclear cobalt (Ⅲ) complex containing N-glycoside ligands from tren and D-glucose and its reversible dioxygen binding property,and novel trimanganese complexes with a linear Mn_3 (Ⅱ, Ⅲ, Ⅱ) assemblage bridged bycarbohydrates are described.展开更多
Cerium （III） tetraphenylporphyrin nitrate Ce（TPP）NO3 was synthesized by using meso- tetraphenylporphyrin （TPP） and Ce（NO3）.6H20 in mixture solution of CHC13 and C2HsOH （V：V=1：1）. The complex was characteri...Cerium （III） tetraphenylporphyrin nitrate Ce（TPP）NO3 was synthesized by using meso- tetraphenylporphyrin （TPP） and Ce（NO3）.6H20 in mixture solution of CHC13 and C2HsOH （V：V=1：1）. The complex was characterized by UV-Vis, FT-IR, conventional fluorescence, MALDI-TOF-MS, and ^1H NMR spectral techniques. The structure of complex was proposed viaSpectral analyses, in which tetraphenylporphyrin was coordinated to a cerium ion in a tetradentate fashion, while one nitrate was coordinated to the same cerium ion. After bubbling NO to the solution of Ce（TPP）NO3 in CH2Cl2, spectral analyses suggested that Ce（TPP）NO3 could interact with NO to form a novel complex of Ce（TPP）（NO）NO3, and NO was coordinated to the center cerium ion. When nitrogen was poured into the Ce（TPP）（NO）（NO3） solution, the complex could be reduced to Ce（TPP）NO3.展开更多
A microcalorimetric study on molecular recognition of p-sulfonatocalix[4]arene derivatives at selfassembled interface in comparison with in bulk water was performed,inspired by the dramatic change in physicochemical c...A microcalorimetric study on molecular recognition of p-sulfonatocalix[4]arene derivatives at selfassembled interface in comparison with in bulk water was performed,inspired by the dramatic change in physicochemical characteristics from bulk water to interface.A total of six cationic molecules were screened as model vips,including ammonium（NH_4~＋）,guanidinium（Gdm~＋）.N,N＇-dimethyl-1,4-diazabicyclo[2.2.2]octane（DMDABCO^（2＋））,tropylium（Tpm~＋）,N-methyl pyridinium（N-mPY＊） and methyl viologen（MV^（2＋））.The complexation with NH_4~＋.Gdm~＋ and DMDABCO2＊ is pronouncedly enhanced when the recognition process moved from bulk water to interface,whereas the complexation stabilities with Tpm~＋,N-mPY~＋ and MV2＊ increase slightly or even decrease to some extent.A more interesting phenomenon arises from the NH_4~＋/Gdm~＋ pair that the thermodynamic origin at interface differs definitely from each other although with similar association constants.The results were discussed in terms of differential driving forces,electrostatic,hydrogen bond as well as π-stacking interactions,originating from the unique physicochemical features of interfaces,mainly the polarity and dielectric constant.展开更多
Precision control over ligand-receptor recognition is critical in biochemistry and pharmacology.Traditional meth-ods that alter reaction environments have limitations in fine-tuning the thermodynamic and kinetic aspec...Precision control over ligand-receptor recognition is critical in biochemistry and pharmacology.Traditional meth-ods that alter reaction environments have limitations in fine-tuning the thermodynamic and kinetic aspects of biochemical reactions within biological systems.The advent of terahertz wave technology represents a significant breakthrough,providing a refined approach to modulating ligand-receptor interactions.This perspective explores the cutting-edge potential of terahertz waves in refining ligand-receptor recognition,featuring their innovative application in modulating neuronal functions.The capabilities of terahertz technology to selectively influence molecular interactions are discussed,highlighting its transformative potential for advancing therapeutic strategies and deepening our understanding of biological mechanisms.展开更多
Introduction:Fluorescent probe-based recombinase aided amplification(RAA)offers the advantages of rapidity and simplicity but is limited by the requirement for complex and lengthy probe design,restricting its widespre...Introduction:Fluorescent probe-based recombinase aided amplification(RAA)offers the advantages of rapidity and simplicity but is limited by the requirement for complex and lengthy probe design,restricting its widespread application.Methods:A novel EvaGreen dye-based RAA(EvaGreen-RAA)assay utilizing self-avoiding molecular recognition system(SAMRS)primers was developed for the detection of Pseudomonas fluorescens(PF)and Bacillus cereus(BC)in milk.Conventional RAA was used as a reference method.Sensitivity was evaluated using nucleic acids from recombinant plasmids and simulated milk specimens.Additionally,a dual EvaGreen-RAA assay was investigated for simultaneous detection of mixed BC and PF in simulated milk specimens.Results:The EvaGreen-RAA demonstrated superior sensitivity compared to conventional RAA,with detection limits of 1 copy/μL versus 10 copies/μL for both BC and PF plasmids,respectively.In simulated milk specimens,EvaGreen-RAA detected BC and PF at concentrations of 100 CFU/mL and 200 CFU/mL,respectively,compared to 400 CFU/mL and 600 CFU/mL for conventional RAA.The dual EvaGreen-RAA assay successfully detected mixed BC and PF in simulated milk specimens at concentrations of 200 CFU/mL for each pathogen.Conclusion:The EvaGreen-RAA assay demonstrated significant advantages in terms of simplicity and enhanced sensitivity compared to fluorescent probe-based RAA,offering a novel approach for developing multiplex pathogen detection systems using melting curve analysis.展开更多
Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesi...Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesized through the condensation of a phenyl-bis-naphthalene(PN)tweezer and a bisnaphthalene cleft.The naphthyls attached to the PN tweezer can rotate around the single bonds to form conformational mixtures.When substituents are present at the ortho positions of the naphthyls,four atropisomers are formed.The water-soluble HNT could recognize phenylpyrimidine,phenyltetrazine,and drug intermediates effectively by adopting a syn conformation in aqueous environments(up to 10^(5)M^(-1)).Moreover,a series of shear-induced hydrogels have been prepared with the newly developed hybridized naphthotube,PEGs,and different transition-metal ions,which showed much stronger gelation properties compared to the previously reported amide naphthotubes.展开更多
Merging tetraphenylethylene(TPE)into cyclic skeletons endows fluorescent sensing capabilities for pillar[6]arenes aggregates,but results in losing their host-vip recognition function in dilute solutions.Inspired by ...Merging tetraphenylethylene(TPE)into cyclic skeletons endows fluorescent sensing capabilities for pillar[6]arenes aggregates,but results in losing their host-vip recognition function in dilute solutions.Inspired by natural enzymes,here we describe a series of TPE-based cyclo[6]arenes(termed TPz,TDz,and TTz)with endo-functionalized cavities containing inward-directed diazine motifs(pyrazine,pyridazine,and phthalazine)that act as hydrogen-bond acceptor sites.Combining electrostatic potential analysis and host-vip binding studies reveals that subtle variations in these diazine motifs substantially affect charge distribution and hydrogen-bond interactions within the internal microenvironment.These differences translate into disparate host-vip affinities,with TTz exhibiting the optimal performance.Unlike TPz,which recognizes vips only in aggregate states,1,2-diazine-modified TDz and TTz possess dual-state recognition functionality.They enable size-selective binding for cationic vips in dilute solutions and sensitive fluorescence detection of nitrophenol pollutants in aggregate states through a photoinduced electron transfer-driven static quenching mechanism.This study underscores the potential of 1,2-diazine motifs as transformative hydrogen-bond acceptors for biomimetic host models with emergent properties.展开更多
Achieving ultrahigh-affinity molecular recognition in aqueous media remains a key challenge in supramolecular chemistry.We report the synthesis of(+)-CA-C[4]B,a water-soluble chiral macrocycle derived from enantiopure...Achieving ultrahigh-affinity molecular recognition in aqueous media remains a key challenge in supramolecular chemistry.We report the synthesis of(+)-CA-C[4]B,a water-soluble chiral macrocycle derived from enantiopure BINOL,featuring eight carboxylate groups on its rims to enhance cavity depth and binding affinity.In aqueous media,(+)-CA-C[4]B exhibits ultrahigh1:1 host-vip binding affinities up to 10^(13)M^(-1)and 1:2 binding affinities up to 10^(16)M^(-2).Notably,it supports dual-mode 1:2 binding:face-to-face for planar aromatic vips and head-to-head for spherical vips like adamantane.Combined with its high recognition affinities,superior fluorescence(quantum yield 43%) and circularly polarized luminescence(|g_(lum)| = 2.6 × 10^(-3)),(+)-CA-C[4]B offers transformative potential for chiral supramolecular materials.展开更多
Molecular recognition between nucleobases plays a crucial role in all kinds of biological processes.However,real-space investigation of the recognition capability of nucleobases in the presence of interfering compound...Molecular recognition between nucleobases plays a crucial role in all kinds of biological processes.However,real-space investigation of the recognition capability of nucleobases in the presence of interfering compounds remains unexplored.Herein,based on the combination of scanning tunneling microscopy imaging and density functional theory modeling,we report the impact of the presence of melamine(M)on the formation and chirality of guanine(G)-tetrads on Au(111).Although M can interact with G by double hydrogen bonding,the Hoogsteen base pairing of G is not compromised,forming identical individual G-tetrads as would have happened without the presence of M.G-tetrads coexist with M on the surface not only in separate domains,but also within the mixture network of G-tetrads and M-dimers.Although the adsorption orientation of G-tetrads in the mixture network diversifies into two distinct angles,all G-tetrads in the network keep the same chirality,emphasizing the high preference of homochirality in such biochemical systems.展开更多
The development of biomimetic affinity materials holds great value for scientific research and practical applications.Starting from boronic acid chemistry,we developed a series of boronate affinity materials(BAMs)with...The development of biomimetic affinity materials holds great value for scientific research and practical applications.Starting from boronic acid chemistry,we developed a series of boronate affinity materials(BAMs)with desired binding properties in aspects of binding pH,affinity and selectivity.Based on BAMs,molecularly imprinted polymers(MIPs)and aptamers capable of targeting vital biomolecules were rationally designed and prepared.Using these affinity reagents as potent tools and combining with advanced analytical techniques particularly liquid chromatography,mass spectrometry and spectrometry allowed for the construction of promising analytical methods to provide new qualitative and quantitative solutions to challenging applications including targeted proteomics analysis,single cell analysis and disease diagnostics.In addition,the targeting capability of these affinity reagents particularly nanoscale MIPs opened a unique access to develop innovative nanotherapeutics for cancer treatment.展开更多
It is widely believed that dimerization is a requirement for the yeast transcriptional activator GCN4 to recognize its specific DNA target sites. We used the basic region (226-252) of the yeast transcriptional activat...It is widely believed that dimerization is a requirement for the yeast transcriptional activator GCN4 to recognize its specific DNA target sites. We used the basic region (226-252) of the yeast transcriptional activator GCN4, as both a monomeric peptide and a disulfide-linked dimer to investigate the interaction of the peptides with the DNA target sites AP-1 and CRE. CD and ITC experiments indicate that although the monomeric peptide GCN4-M has a weaker affinity with the DNA relative to the disulfide-linked dimer peptide GCN4-D, it recognizes AP-1 and CRE target sites specifically.展开更多
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supported by the Shandong Province Natural Science Foundation(Grant No.:ZR2021LZY021)Shandong Key Laboratory of Digital Traditional Chinese Medicine,Shandong University of Traditional Chinese Medicinethe Institute of Pharmaceutical Research,Shandong University of Traditional Chinese Medicine.
文摘Traditional Chinese medicine(TCM)has become an important treasure trove of natural resources for the development of new medicines due to their diverse compositions,significant therapeutic effects,and few side effects.The screening of active ingredients in TCM represents a crucial step in elucidating the material basis and mechanism of action of TCM.At present,efficient and precise molecular recognition techniques based on intermolecular interactions have been extensively employed for the identification of active ingredients in TCM.This paper presents a review of the fundamental principles underlying solution-phase/affinity ligand fishing,solid-phase/affinity ligand fishing,molecular imprinting and molecular docking techniques,with a particular focus on their applications in the screening of active ingredients in TCM.Furthermore,the paper compares the advantages and disadvantages of the various techniques and identifies the limitations of existing techniques.In conclusion,the paper identifies the prospective trajectory of molecular recognition techniques in the domain of TCM research.This paper not only provides theoretical references for the development of new methods of active ingredient screening but also helps to promote the modernization and internationalization of TCM.
文摘Anion can be identified by pyromellitic imide-azacyclophane which is one of the host compounds.This article investigated the interaction between the host and organic pollution compounds.The host and other eight compounds were optimized by DFT（density functional theory） B3LYP/6-31G level and the energy of compounds was corrected using Boys-Bemardi method.On the basis of B3LYP/6-31G optimized geometries,the RDG function and sign（λ2（r））ρ（r） function values of space points were calculated,and color RDG isosurface map was drawn.3He chemical shift was calculated by the B3LYP/6-31G method.The results showed that the eight organic pollution molecules with the host one shaped stable configurations by hydrogen bonds,respectively.The stabilization energy of complexes 4 and 7 showed repulsion（steric effects） of cyclophane cage observably affecting the stability of the complexes.The location,intensity and the type of interaction in complex 1 were analyzed through color-filled RDG isosurface map.Aromaticity calculations showed that the weak interaction reduced the transverse induction ring current in the host rings,and deteriorated the aromaticity of compounds.
文摘This study involves initial Hartree-Fock and Density Functional theory calculations onthe molecular recognition of the cyclodextrins. The α-cyclodextrin-acetophenone complexationsystem was investigated with PM3, HF/3-21G* and B3LYP/3-21G* methods. The results indicatedthat the inclusion orientation in which the acetyl group of the acetophenone points towards thesecondary hydroxyls of the a-cyclodextrin was preferable in energy. The steric effect wassupposed as the physical reason of such a behavior Hence, the simple rule the anti-parallelarrangement of the dipoles of the host and vip molecules in the cyclodextrin complexqtion is notgenerally applicable.
文摘Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar vips especially ionic vips and monosaccharides. Electronic spectra of coordinates are computed by the INDO/SCI method. The reason of the blue-shift for UV absorption of complexes relative to that of hosts is discussed and electronic transition is theoretic- cally assigned.
基金supported by the National Natural Science Foundation of China(Nos.22271164,U20A20259)the Fundamental Research Funds for the Central Universitiesthe NCC Fund(No.NCC2020FH04).
文摘Molecular recognition in water,the biological solvent,always receives significant research focus in supramolecular chemistry.The mechanisms of molecular recognition in water is key to comprehending biological processes at the molecular level.Over the past five decades,supramolecular chemists have developed a vast array of synthetic receptors with highly diverse structures and recognition properties.Among them,cyclophanes represent an important family of macrocyclic receptors that have been extensively explored.The aromatic moieties in cyclophanes not only facilitate chemical modifications to impart water solubility but also enable forming hydrophobic cavities for vip inclusion in aqueous environments.Pioneered by Koga et al.,who reported the first inclusion complex of cyclophanes in water and solid state,numerous water-soluble cyclophanes,including derivatives of blue box,calixarenes,resorcinarenes,pillararenes,octopusarenes,biphenarenes,coronarenes,and naphthotubes,etc.,have been synthesized and subjected to investigation of the recognition capabilities in aqueous solutions.This review provides an overview of cyclophane receptors designed to bind organic vips in water.We categorize them into two classes based on the modifications made to their hydrophobic cavities:those with“exo-functionalized hydrophobic cavities”and those with“endo-functionalized hydrophobic cavities”.We introduce their distinctive features and discuss strategies to enhance recognition affinity and selectivity.This review aims to inspire the development of novel synthetic receptors with intriguing properties and foster practical applications of cyclophanes.
基金the National Natural Science Foundation of China
文摘β-Cyclodextrin (β-CD) and its cross-linked polymer (β-CDP) were known as the mimetic models. Metalloporphyrin had been widely used in the enzymatic method of analysis and molecular recognition. In present work, it was investigation that supramolecular recognition for halogenated phenols, three crosols, three nitrophenols and three aminophenols, served respectively as the substrate of the mimetic receptor, iron-5, 10, 15, 20-tetrakis (sulforphenyl)-21H, 23H-porphine (FeTPPS) or FeTPPS-β-CDP. Supramolecular complex, FeTPPS-β-CDP with function of mult i-recognition and induced-fit, was a advanced kind of mimetic peroxidase; Methyl phenol or polyphenol was the substitute of chlorophenic acid, while aminophenols and other phenols were suggested not to be utilized to enzymatic assay of H2O2. Being a mimetic enzyme mimicking the space structure of overall proteinase, beaimed by immobilized mimetic enzyme with a large number of β-CD interior cavities, chlorophenol was identified optimal substrate in the system tested.
基金the National Natural Science Foundation of China(Nos.22174059 and 22201128)Hunan Provincial Natural Science Foundation of China(Nos.2022JJ40363 and 2022JJ40365)+1 种基金the Young Science and Technology Innovation Program of Hunan Province(No.2022RC1230)China Postdoctoral Science Foundation(No.2022M721542)for financial support。
文摘Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments.By mimicking the cavity feature of bioreceptors,Prof.Wei Jiang proposed and clarified the concept of“endo-functionalized cavity”.Through situating polar binding sites into a deep hydrophobic cavity,we designed and synthesized several macrocyclic hosts,among which amide naphthotubes are the most representative.The hosts can selectively recognize various polar molecules including organic micropollutants,drug molecules,and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding.In addition,these biomimetic hosts have been applied in spectroscopic analysis,adsorptive separation and self-assembly.In this review,we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group.We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.
基金Supported by the National Natural Science Foundation of China(Nos. 50473005 and 20274015).
文摘A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM （transmission electron microscopy）. The UV-Vis spectroscopic behavior of PC/MTOAB/thymine （molar ratio = 5： 1： 1 ） and PC/MTOAB/TOTB （molar ratio = 5： 1： 1 ） of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.
文摘Assembly of carbohydrates on nickel (Ⅱ) center by utilizing N-glycosidicbond formation with a branched amine: tris(2-aminoethyl)amine (tren), an unprecedentedchiral inversion around the metal center (Co or Mn) induced by an interaction betweensugars and sulfate anions, peroxo-bridged dinuclear cobalt (Ⅲ) complex containing N-glycoside ligands from tren and D-glucose and its reversible dioxygen binding property,and novel trimanganese complexes with a linear Mn_3 (Ⅱ, Ⅲ, Ⅱ) assemblage bridged bycarbohydrates are described.
基金ACKNOWLEDGMENTS This work was supported by the ＂Western Light＂ Visiting Scholar Plan, the Program for New Century Excellent Talents in University （No.NCET-12-1017）, the Program for Grassland Excellent Talents of Inner Mongolia Autonomous Region, the Inner Mengolia Science Technology Plan, the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region （No.NJYT-12-B13）, the Natural Science Foundation of Inner Mongolia Autonomous Region （No.2011BS0601, China）, the Inner Mongolia Talented People Development Fund, and Yongfeng Boyuan Industry Co., Ltd. Jiangxi Province, China.
文摘Cerium （III） tetraphenylporphyrin nitrate Ce（TPP）NO3 was synthesized by using meso- tetraphenylporphyrin （TPP） and Ce（NO3）.6H20 in mixture solution of CHC13 and C2HsOH （V：V=1：1）. The complex was characterized by UV-Vis, FT-IR, conventional fluorescence, MALDI-TOF-MS, and ^1H NMR spectral techniques. The structure of complex was proposed viaSpectral analyses, in which tetraphenylporphyrin was coordinated to a cerium ion in a tetradentate fashion, while one nitrate was coordinated to the same cerium ion. After bubbling NO to the solution of Ce（TPP）NO3 in CH2Cl2, spectral analyses suggested that Ce（TPP）NO3 could interact with NO to form a novel complex of Ce（TPP）（NO）NO3, and NO was coordinated to the center cerium ion. When nitrogen was poured into the Ce（TPP）（NO）（NO3） solution, the complex could be reduced to Ce（TPP）NO3.
基金supported by NSFC(Nos.21322207 and 21672112)the Fundamental Research Funds for the Central Universities and Program of Tianjin Young Talents
文摘A microcalorimetric study on molecular recognition of p-sulfonatocalix[4]arene derivatives at selfassembled interface in comparison with in bulk water was performed,inspired by the dramatic change in physicochemical characteristics from bulk water to interface.A total of six cationic molecules were screened as model vips,including ammonium（NH_4~＋）,guanidinium（Gdm~＋）.N,N＇-dimethyl-1,4-diazabicyclo[2.2.2]octane（DMDABCO^（2＋））,tropylium（Tpm~＋）,N-methyl pyridinium（N-mPY＊） and methyl viologen（MV^（2＋））.The complexation with NH_4~＋.Gdm~＋ and DMDABCO2＊ is pronouncedly enhanced when the recognition process moved from bulk water to interface,whereas the complexation stabilities with Tpm~＋,N-mPY~＋ and MV2＊ increase slightly or even decrease to some extent.A more interesting phenomenon arises from the NH_4~＋/Gdm~＋ pair that the thermodynamic origin at interface differs definitely from each other although with similar association constants.The results were discussed in terms of differential driving forces,electrostatic,hydrogen bond as well as π-stacking interactions,originating from the unique physicochemical features of interfaces,mainly the polarity and dielectric constant.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450102)the National Natural Science Foundation of China(22277118)+2 种基金the STI2030-Major Projects[2021ZD0203000(2021ZD0203003)]the Science and Technology Development Plan Project of Jilin Province(20220402045GH)the Chinese Academy of Sciences(CAS)Pioneer Hundred Talents Program.
文摘Precision control over ligand-receptor recognition is critical in biochemistry and pharmacology.Traditional meth-ods that alter reaction environments have limitations in fine-tuning the thermodynamic and kinetic aspects of biochemical reactions within biological systems.The advent of terahertz wave technology represents a significant breakthrough,providing a refined approach to modulating ligand-receptor interactions.This perspective explores the cutting-edge potential of terahertz waves in refining ligand-receptor recognition,featuring their innovative application in modulating neuronal functions.The capabilities of terahertz technology to selectively influence molecular interactions are discussed,highlighting its transformative potential for advancing therapeutic strategies and deepening our understanding of biological mechanisms.
基金Supported by Shandong Province Key Research and Development Plan(Major Scientific and Technological Innovation Project,2023CXGC010711)the National Key R&D Program of China(2021YFC2301102)the National Natural Science Foundation of China(82202593,U23A20106).
文摘Introduction:Fluorescent probe-based recombinase aided amplification(RAA)offers the advantages of rapidity and simplicity but is limited by the requirement for complex and lengthy probe design,restricting its widespread application.Methods:A novel EvaGreen dye-based RAA(EvaGreen-RAA)assay utilizing self-avoiding molecular recognition system(SAMRS)primers was developed for the detection of Pseudomonas fluorescens(PF)and Bacillus cereus(BC)in milk.Conventional RAA was used as a reference method.Sensitivity was evaluated using nucleic acids from recombinant plasmids and simulated milk specimens.Additionally,a dual EvaGreen-RAA assay was investigated for simultaneous detection of mixed BC and PF in simulated milk specimens.Results:The EvaGreen-RAA demonstrated superior sensitivity compared to conventional RAA,with detection limits of 1 copy/μL versus 10 copies/μL for both BC and PF plasmids,respectively.In simulated milk specimens,EvaGreen-RAA detected BC and PF at concentrations of 100 CFU/mL and 200 CFU/mL,respectively,compared to 400 CFU/mL and 600 CFU/mL for conventional RAA.The dual EvaGreen-RAA assay successfully detected mixed BC and PF in simulated milk specimens at concentrations of 200 CFU/mL for each pathogen.Conclusion:The EvaGreen-RAA assay demonstrated significant advantages in terms of simplicity and enhanced sensitivity compared to fluorescent probe-based RAA,offering a novel approach for developing multiplex pathogen detection systems using melting curve analysis.
基金supported by the National Natural Science Foundation of China(grant no.22101125).
文摘Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials.In this research,we report two types of hybridized naphthotubes(HNT)which were synthesized through the condensation of a phenyl-bis-naphthalene(PN)tweezer and a bisnaphthalene cleft.The naphthyls attached to the PN tweezer can rotate around the single bonds to form conformational mixtures.When substituents are present at the ortho positions of the naphthyls,four atropisomers are formed.The water-soluble HNT could recognize phenylpyrimidine,phenyltetrazine,and drug intermediates effectively by adopting a syn conformation in aqueous environments(up to 10^(5)M^(-1)).Moreover,a series of shear-induced hydrogels have been prepared with the newly developed hybridized naphthotube,PEGs,and different transition-metal ions,which showed much stronger gelation properties compared to the previously reported amide naphthotubes.
基金support was provided by the National Natural Science Foundation of China(22401064 and 22161017)the Innovational Fund for Scientific and Technological Personnel of Hainan Province(KJRC2023D34)+1 种基金the Hainan Provincial Natural Science Foundation of China(224QN184)the Research Start-up Fund of Hainan University(KYQD(ZR)23037).
文摘Merging tetraphenylethylene(TPE)into cyclic skeletons endows fluorescent sensing capabilities for pillar[6]arenes aggregates,but results in losing their host-vip recognition function in dilute solutions.Inspired by natural enzymes,here we describe a series of TPE-based cyclo[6]arenes(termed TPz,TDz,and TTz)with endo-functionalized cavities containing inward-directed diazine motifs(pyrazine,pyridazine,and phthalazine)that act as hydrogen-bond acceptor sites.Combining electrostatic potential analysis and host-vip binding studies reveals that subtle variations in these diazine motifs substantially affect charge distribution and hydrogen-bond interactions within the internal microenvironment.These differences translate into disparate host-vip affinities,with TTz exhibiting the optimal performance.Unlike TPz,which recognizes vips only in aggregate states,1,2-diazine-modified TDz and TTz possess dual-state recognition functionality.They enable size-selective binding for cationic vips in dilute solutions and sensitive fluorescence detection of nitrophenol pollutants in aggregate states through a photoinduced electron transfer-driven static quenching mechanism.This study underscores the potential of 1,2-diazine motifs as transformative hydrogen-bond acceptors for biomimetic host models with emergent properties.
基金supported by the National Natural Science Foundation of China (22271164,22571167)the Fundamental Research Funds for the Central Universitiesthe Frontiers Science Center for New Organic Matter,Nankai University (NKU)。
文摘Achieving ultrahigh-affinity molecular recognition in aqueous media remains a key challenge in supramolecular chemistry.We report the synthesis of(+)-CA-C[4]B,a water-soluble chiral macrocycle derived from enantiopure BINOL,featuring eight carboxylate groups on its rims to enhance cavity depth and binding affinity.In aqueous media,(+)-CA-C[4]B exhibits ultrahigh1:1 host-vip binding affinities up to 10^(13)M^(-1)and 1:2 binding affinities up to 10^(16)M^(-2).Notably,it supports dual-mode 1:2 binding:face-to-face for planar aromatic vips and head-to-head for spherical vips like adamantane.Combined with its high recognition affinities,superior fluorescence(quantum yield 43%) and circularly polarized luminescence(|g_(lum)| = 2.6 × 10^(-3)),(+)-CA-C[4]B offers transformative potential for chiral supramolecular materials.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21473045 and 51772066)State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.2018DX04).
文摘Molecular recognition between nucleobases plays a crucial role in all kinds of biological processes.However,real-space investigation of the recognition capability of nucleobases in the presence of interfering compounds remains unexplored.Herein,based on the combination of scanning tunneling microscopy imaging and density functional theory modeling,we report the impact of the presence of melamine(M)on the formation and chirality of guanine(G)-tetrads on Au(111).Although M can interact with G by double hydrogen bonding,the Hoogsteen base pairing of G is not compromised,forming identical individual G-tetrads as would have happened without the presence of M.G-tetrads coexist with M on the surface not only in separate domains,but also within the mixture network of G-tetrads and M-dimers.Although the adsorption orientation of G-tetrads in the mixture network diversifies into two distinct angles,all G-tetrads in the network keep the same chirality,emphasizing the high preference of homochirality in such biochemical systems.
基金We acknowledge financial suport of the National Science Fund for Distinguished Young Scholars(No.21425520)and the Key Grant(No.21834003)from the National Natural Science Foundation of Chinathe National Key R&D Program of China(No.2018YFC0910301)from the Ministry of Science and Technology of Chinathe Excellent Research Program of Nanjing University(No.ZYJH004).
文摘The development of biomimetic affinity materials holds great value for scientific research and practical applications.Starting from boronic acid chemistry,we developed a series of boronate affinity materials(BAMs)with desired binding properties in aspects of binding pH,affinity and selectivity.Based on BAMs,molecularly imprinted polymers(MIPs)and aptamers capable of targeting vital biomolecules were rationally designed and prepared.Using these affinity reagents as potent tools and combining with advanced analytical techniques particularly liquid chromatography,mass spectrometry and spectrometry allowed for the construction of promising analytical methods to provide new qualitative and quantitative solutions to challenging applications including targeted proteomics analysis,single cell analysis and disease diagnostics.In addition,the targeting capability of these affinity reagents particularly nanoscale MIPs opened a unique access to develop innovative nanotherapeutics for cancer treatment.
文摘It is widely believed that dimerization is a requirement for the yeast transcriptional activator GCN4 to recognize its specific DNA target sites. We used the basic region (226-252) of the yeast transcriptional activator GCN4, as both a monomeric peptide and a disulfide-linked dimer to investigate the interaction of the peptides with the DNA target sites AP-1 and CRE. CD and ITC experiments indicate that although the monomeric peptide GCN4-M has a weaker affinity with the DNA relative to the disulfide-linked dimer peptide GCN4-D, it recognizes AP-1 and CRE target sites specifically.
