Study on Synthesis and Binding Ability of a New Anion Receptor Containing NH Binding Sites

A new colorimetric recognition receptor 1 based on the dual capability containing NH binding sites of selectively sensing anionic guest species has been synthesized. Compared with other halide anions, its UV/Vis absorption spectrum in dimethyl sulfoxide showed the response toward the presence of fluoride anion with high selectivity, and also displayed dramatic color changes from colorless to yellow in the presence of TBAF （5 × 10^-5 mol/L）. The similar UV/Vis absorption spectrum change also occurred when 1 was treated with AcO^- while a little change with H2PO^-4 and OH^-. Receptor 1 has almost not affinity abilities to Cl^-, Br^- and I^-. The binding ability of receptor 1 to fluoride with high selectivity over other halides contributes to the anion size and the ability of forming hydrogen bonding. While the different ability of binding with geometrically triangular （AcO^-）, tetrahedral （H2PO^-4 ） and linear （OH^-） anions maybe result from their geometry configuration.     

Study on the Anion Recognition Properties of Synthesized Receptors （Ⅲ）： Convenient Synthesis and Anion Recognition Property of Bisthiosemicarbazone Derivative

A new series of bisthiosemicarbazone derivative receptors(1,2 and 3)have been synthesized by simple steps ingood yields.Their anion recognition properties were studied by UV-Vis and ~1H NMR spectroscopy.The resultshowed that the receptors 1,2 and 3 all had a better selectivity to F~-,CH_3COO~- and H_2PO_4~-,but no evidentbinding with Cl~-,Br~-,I~-,NO_3~- and HSO_4~-.Upon addition of the three anions to the receptors in DMSO,thesolution acquired a color change from colorless to dark yellow that can be observed by the naked-eyes,thus the re-ceptors can act as fluoride ion sensors even in the presence of other halide ions.The data showed that it was regularthat the three receptors had different binding ability with the three anions.For the same anion,the association con-stants followed the trend:receptor 1>3>2.The UV-Vis data indicates that a 1:1 stoichiometry complex isformed through hydrogen bonding interactions between compound 1,2 or 3 and anions.     

Crystal Structures of Fluoride and Chloride Complexes of Tris[（2-benzimidazolyl）methyl]amine

The crystal structures of fluoride and chloride complexes of tris[（2-benzimidazolyl）methyl]amine 1 were characterized by X-ray crystallography. 1 adopts （73 symmetrical geometry and cone-like conformation so as to allow its three NHs to associate with the anions through hydrogen bonds. Despite the different sizes of the anions, the two crystals are unexpectedly isostructural. The binding ability of the anions of 1 in solution was also studied by using of UV-vis spectroscopy.     

Molecular Recognition of Bases and Nucleosides by Mono－substituted Mononuclear Complexes of 1,4,7,10－Tetraaza－cyclododecane

The mononuclear macrocyclic polyamine metal complexes 5a-5e have been shown to form stable 1 : 1 complexes with bases and nucleosides. Their binding constants (K) were determined by UV-visible spectrometric titration. The results show that recognition ability of the complexes 5a--5e for uracil, U (Uridine), dT (Thymidine) is higher than that for the other bases or nucleosides (such as Cytidine, Guanosine, Adenosine). The metal ion also plays an important role for the recognition ability of complexes.     

Molecular Design of Crown Ethers. 22. Synthesis of Benzocrown Ether Derivatives and Their Solvent Extraction with Univalent／Bivalent Metal Picrates

Three novel benzocrown ether derivatives have been synthesized and their cation binding behavior with uniand bi-valent metal ions was evaluated by the solvent extraction of aqueous metal picrates. The obtained results indicate that the size-fit of crown ether and metal cation, and electron effect of the side arm attached to benzocrown ethers affect their cation binding ability and selectivity.     

Synthesis and cationic selectivity studies of novel calix[4]arene derivatives containing heteroatom at the lower rim

A series of calixarene derivatives 2―5 containing heteroatom at the lower rim have been synthesized. 1H NMR studies and crystallographic structures demonstrated that the calix[4]arene derivatives adopted cone conformations. Their cationic binding abilities and selectivities towards heavy and tran- sition metal ions have been evaluated by solvent extraction of aqueous metal picrates. The obtained results indicated that the introduction of nitrogen, sulfur, and/or phosphor atoms to the calix[4]arene framework could effectively enhance their binding ability and selectivity for heavy and transition metal ions, such as Pb2 or Ag .     

Interactions between meso-tetrakis(4-(N-methylpyridiumyl))porphyrin TMPyP4 and DNA G-quadruplex of telomeric repeated sequence TTAGGG

The binding properties between meso-tetrakis(4-(N-methylpyridiumyl))porphyrin (TMPyP4) and the parallel DNA G-quadruplex (G4) of telomeric repeated sequence 5′-TTAGGG-3′ have been characterized by means of circular dichroism,steady-state absorption,steady-state fluorescence and picosecond time-resolved fluorescence spectroscopies. The binding constant and the saturated binding number were determined as 1.29×106 (mol/L)-1 and 3,respectively,according to steady-state absorption spec-troscopy. Based on the findings by the use of time-resolved fluorescence spectroscopic technique,it is deduced that TMPyP4 binds to a DNA G-quadruplex with both the thread-intercalating and end-stacking modes and at the saturated binding state,one TMPyP4 molecule intercalates into the intervals of G-tetrads while the other two stack to the ends of the DNA G-quadruplex.     

Dynamic Assembly Inclusion Complexes of Tweezer‐type Bis(zinc porphyrin) with 5,15‐Di(4‐pyridyl)porphyrin Derivatives

Dynamic assembly inclusion complexes of tweezer-type bis(zinc porphyrin) (1) with di(4-pyridyl)porphyrin derivatives have been designed and constructed. The complexes are induced by Zn-N coordination, and the weak binding allows the large-size di(4-pyridyl)porphyrin guests in random rotation. Dynamic characteristics of these assemblies, such as ligand exchange and dynamic fluorescence quenching, have been investigated by 1H NMR, UV-Vis and fluorescence spectra. The stability of such assembly has pronounced dependence on the size-matching effect and thermal effect.     

Poly(vinylidene fluoride) separators with dual-asymmetric structure for high-performance lithium ion batteries

Dual-asymmetric poly(vinylidene fluoride)(PVDF) separators have been fabricated by thermally induced phase separation with dimethyl sulfone(DMSO2) and glycerol as mixed diluents. The separators have a porous bulk with large interconnected pores(~1.0 μm) and two surfaces with small pores(~30 nm). This dual-asymmetric porous structure endows the separators with higher electrolyte uptake amount and rapider uptake rate, as well as better electrolyte retention ability than the commercialized Celgard 2400. The separators even maintain their dimensional stability up to 160 °C, at which temperature the surface pores close up, leading to a dramatic decrease of air permeability. The electrolyte filled separators also show high ion conductivity(1.72 m S?cm―1) at room temperature. Lithium iron phosphate(Li Fe PO4)/lithium(Li) cells using these separators display superior discharge capacity and better rate performance as compared with those from the commercialized ones. The results provide new insight into the design and development of separators for high-performance lithium ion batteries with enhanced safety.     

Optical 2-benzyl-5-hydroxy-4-oxopentanoic acids against carboxypeptidase A: synthesis, kinetic evaluation and X-ray crystallographic study

<正>2-Benzyl-5-hydroxy-4-oxopentanoic acid 1 and its enantiomers were designed,synthesized and assayed for inhibitory activity against carboxypeptidase A(CPA,EC 3.4.17.1).To verify the role of the terminal hydroxyl group in 1 binding to CPA,2-benzyl-5- benzyloxy-4-oxopentanoic acid 2 was also synthesized and evaluated.The inhibition constants show that both L-1 and D-1 were shown to have strong binding affinity with L-1 being more potent than its enantiomer by 165-fold.On the other hand,the inhibition constant of 2 increases 4-fold comparing with that of 1.In order to explore the exact binding mode of the hydroxyacteyl group of 1 to the active site zinc ion of CPA,we have solved the crystal structure of CPA complexed with L-1 up to 1.85(?) resolution.In CPA·L-1 complex,the phenyl ring is fitted in the substrate recognition pocket at the S′_1 subsite,and the carboxylate forms bifurcated hydrogen bonds with the guanidinium moiety of Arg-145 and Arg-127 and a hydrogen bond with the phenolic hydroxyl of the down-positioned Tyr-248.The carbonyl oxygen of L-1 does coordinate to the active site zinc ion of CPA as expectedly.Unexpectedly,the terminal hydroxyl group of L-1 is engaged in hydrogen bonding with carbonyl oxygen of Ser-197 instead of coordinating to the active site zinc ion.     

Preferred Binding of Carboxylates by Chiral Urea Derivatives Containing α‐Phenylethyl Group

An efficient, simple protocol for the synthesis of a new family of chiral ureas 1 – 4 is described. The binding properties of 1 – 4 toward different anion (acetate, benzoate, fluoride, and chloride) have been studied by ¹H‐NMR titration and have been observed in the case of 4 is a selective receptor for acetate. The theoretical calculation M06/6‐311+G(d,p) helped us explain the binding properties observed. The most interesting observation is that this calculated structure is consistent with expected, based on the concept of allylic 1,3‐strain (A^1,3 strain). When chiral caboxylates were studied, urea 1 was the best in discriminating between enantiomers.     

Tight and Selective Caging of Chloride Ions by a Pseudopeptidic Host

The selective molecular recognition of chloride versus similar anions is a continuous challenge in supramolecular chemistry. We have designed and prepared a simple pseudopeptidic cage ( 1 a ) that defines a cavity suitable for the tight encapsulation of chloride. The interaction of the protonated form of 1 a with different inorganic anions was studied in solution by ¹H NMR spectroscopy and ESI‐MS, and in the solid state by X‐ray diffraction. The solution binding data showed that the association constants of 1 a to chloride are more than two orders of magnitude higher than to any other tested inorganic anion. Remarkably, 1 a displayed a high selectivity for chloride over other closely related halides such as bromide (selectivity=111), iodide (selectivity=719), and fluoride (selectivity >1000). Binding experiments (¹H NMR spectroscopy and ESI‐MS) suggested that 1 a has a high‐affinity (inner) binding site and an additional low‐affinity (external) binding site. The supramolecular complexes with F^?, Cl^?, and Br^? have been also characterized by the X‐ray diffraction of the corresponding [ 1 a? nHX] crystalline salts. The structural data show that the chloride anion is tightly encapsulated within the host, in a binding site defined by a very symmetric array of electrostatic H‐bonds. For the fluoride salt, the size of the cage cavity is too large and is occupied by a water molecule, which fits inside the cage efficiently competing with F^?. In the case of the bigger bromide, the mismatch of the anion inside the cage caused a geometrical distortion of the host and thus a large energetic penalty for the interaction. This minimalistic pseudopeptidic host represents a unique example of the construction of a simple well‐defined binding pocket that allows the highly selective molecular recognition of a challenging substrate.     

Exploiting the Strong Hydrogen Bond Donor Properties of a Borinic Acid Functionality for Fluoride Anion Recognition

Borinic acids have typically not been considered as hydrogen bond donor groups in molecular recognition. Described herein is a bifunctional borane/borinic acid derivative ( 2 ) in which the two functionalities are connected by a 1,8‐biphenylenediyl backbone. Anion binding studies reveal that 2 readily binds a fluoride anion by formation of a unique B?F???H?O?B hydrogen bond. This hydrogen bond is characterized by a short H‐F distance of 1.79(3) Å and a large coupling constant (¹J_HF) of 57.2 Hz. The magnitude of this interaction, which has also been investigated computationally, augments the fluoride anion binding properties of 2 , thus making it compatible with aqueous environments.     

Mesoporous Hybrid Materials Containing Nanoscopic “Binding Pockets” for Colorimetric Anion Signaling in Water by using Displacement Assays

Mesoporous solids functionalized with anion‐binding groups have proved to be suitable anion hosts and have been used in selective colorimetric displacement assays. The material UVM‐7, a mesoporous MCM41‐type support characterized by the presence of nanometric mesoporous particle conglomerates, was selected as inorganic scaffolding. Reaction of the template‐free UVM‐7 solid with 3‐aminopropyltriethoxysilane ( 1 ) yielded solid S1 , from which the derivatives S2 and S3 were obtained by reaction with 2‐methylthio‐2‐imidazoline hydroiodide ( 2 ) and butyl isocyanate ( 3 ), respectively. Solids S4 and S5 were prepared by reaction of the starting mesoporous UVM‐7 scaffolding with N‐methyl‐N′‐propyltrimethoxysilyl imidazolium chloride ( 4 ) and with 3‐(trimethoxysilyl)propyl‐N,N,N‐trimethylammonium chloride ( 5 ), respectively. The solids synthesized contain mesoporous binding pockets that can interact with anions through electrostatic attractive forces ( S1 , S2 , S4 , S5 ) and hydrogen‐bonding interactions ( S1 , S2 , S3 , S4 ). These functionalized solids were loaded with a dye ( d ) capable of interacting coordinatively with the anchored binding sites, in our case 5‐carboxyfluorescein, to yield the hybrid materials S1d, S2d , S3d , S4d and S5d . These dye‐containing solids are the signaling reporters. Their sensing ability towards a family of carboxylates, namely acetate, citrate, lactate, succinate, oxalate, tartrate, malate, mandelate, glutamate and certain nucleotides, has been studied in pure water at pH 7.5 (Hepes, 0.01 mol dm^?3). In the sensing protocol, a particular analyte may be bonded preferentially by the nanoscopic functionalized pocket, leading to delivery of the dye to the solution and resulting in colorimetric detection of the guest. The response to a given anion depends on the characteristics of the binding pockets and the specific interaction of the anion with the binding groups in the mesopores. We believe that the possibility of using a wide variety of mesoporous supports that can easily be functionalized with anion‐binding sites, combined with suitable dyes as indicators, make this approach significant for opening new perspectives in the design of chromogenic assays for anion detection in pure water.     

酰氨基硫脲类新型分子钳受体的合成及其对氟离子的识别性能研究

本文设计并高产率合成了三种新型阴离子识别受体化合物,它们对F-的识别选择性较卤素其他阴离子的高。其对F-的识别性能通过紫外—可见光谱和核磁共振氢谱进行了检测,光谱数据表明,在DMSO溶液中受体与F-通过氢键相互作用形成1:1配合物。与以前我们报道的受体化合物相比,由于此类分子钳受体化合物具有更多的阴离子识别位点,因此具有更好地阴离子识别性能。     

Voltammetric Anion Sensors based on Redox‐active Ferrocene‐bearing Macrocyclic Amides

Reactions between 5‐ferrocenylisophthalic dichloride and 1,2‐bis(o‐aminophenoxy)ethane yield 1:1‐ and 2:2‐cyclization products with amide linkages, which are marked as L1 and L2 , respectively. The crystal structure of the 2:2‐macrocycle L2 is determined by X‐ray single crystal structure analysis. Interestingly, L2 affords a folded conformation due to the intermolecular π–π interaction between two isophthaloyl groups, so as to stabilize the marcocylic conformation. The electrochemical anion sensing studies of L1 and L2 show that they have a good ability to recognize H₂PO₄^–, and the 2:2‐cyclization products ( L2 ) with two ferrocene groups, more anion binding sites, and larger cavities, give better electrochemical anion recognition results than L1 .     

Isophorone‐boronate ester: A simple chemosensor for optical detection of fluoride anion

A highly selective isophorone‐boronate ester based chemosensor, ( 1 ) , having a dicyanovinyl moiety as a convenient colorimetric probe, has been designed. Different types of anionic analyte such as CH₃COO^?, ClO₄^?, Cl^?, F^?, PF₆^?, Br^? and HSO₄^? were tested and among them only highly nucleophilic F^? anion displayed significant response towards the sensor. Addition of the fluoride anion across the boron atom disrupts the π‐conjugation thereby shifts the absorption wavelength towards the redshift region due to the decrease in the HOMO‐LUMO energy gap and a colour change from yellow to blue is observed under visible light condition. The detection limit of this probe was calculated to be 3.25 × 10^—8 M for fluoride anion. The binding constants and the detection limits of the sensor were calculated using absorption titration studies. The silica gel TLC strips dip‐coated by the chemosensor ( 1 ) revealed a colour change from yellow to brick red to naked eye.     

An electrochemical and optical anion chemosensor based on tripodal tris(ferrocenylurea)

A neutral tripodal tris(ferrocenylurea) anion receptor has been designed that can electrochemically and optically recognize sulfate and phosphate anions. The binding of the tetrahedral anion induced distinct cathodic shifts of the ferrocene/ferrocenium redox couple in chloroform, whereas the UV/Vis spectrum of the receptor showed an increase in the d–d transition band upon addition of sulfate ions. Furthermore, the anion complexes (TBA)₂ ? [SO₄?L] ? H₂O ( 1 ) and TBA[F?L] ( 2 ; TBA=tetrabutylammonium ion) were isolated. Crystal structural analyses showed that the receptor in the two 1:1 (host/guest) complexes encapsulated sulfate or fluoride ions in the tripodal cavity through multiple hydrogen bonds. ¹H NMR spectroscopic and ESI mass‐spectrometric analysis revealed strong sulfate and fluoride binding in solution.     

Anion recognition properties of the neutral receptors bearing amide macrocycle

Neutral classes of amide‐based macrocycle have been synthesized and the anion binding abilities are assessed by UV‐vis titration and ¹H nmr experiments. Results indicate that higher anion binding abilities are observed for H₂PO₄^?, F^? and AcO^?, but almost no affinity for Cl^?, Br^?, I^? and OH^?. The ¹H nmr spectra shows that the interactions between the receptors and fluoride anion depend on two factors, respectively: one is depend on hydrogen bonding, the other on deprotonation.