Novel peptides bearing pyrene and coumarin units with or without beta-cyclodextrin in their side chains exhibit intramolecular fluorescence resonance energy transfer

Novel peptides bearing the pyrene/coumarin FRET pair in their side chains have been designed and synthesized. Peptide 1 having endogenous beta-cyclodextrin (beta-CD) in the side chain exhibits FRET in aqueous solution, indicating that coumarin, being accommodated into the CD cavity, is separated from pyrene. Guest-induced quenching of the fluorophores in 1 indicates that coumarin, being excluded from the CD cavity, comes into close contact with pyrene. Peptide 2 shows FRET only after addition of external beta-CD that again reflects the idea that beta-CD surely caps the coumarin unit in its hydrophobic cavity, and, therefore, quenching of the fluorophores can be prevented in FRET peptide probes. With this strategy, various peptide-based FRET probes can be developed that would be useful for studying biological phenomena in living cells.     

Supramolecular interaction of ethylenediamine linked beta-cyclodextrin dimer and berberine hydrochloride by spectrofluorimetry and its analytical application

The supramolecular interaction of β-cyclodextrin dimer with berberine hydrochloride was studied in aqueous KH₂PO₄-H₃PO₄ buffer solution of pH 2.00 at room temperature by spectrofluorimetry. The apparent association constant of the complex was 1.53 × 10⁴ L mol⁻¹. Based on the significant enhancement of fluorescence intensity of supramolecular sandwich complexes, a spectrofluorimetric method with high sensitivity and selectivity was developed for the determination of berberine hydrochloride in aqueous solution in presence of ethylenediamine linked β-CD dimer. The linear range of the method was 12.8-1.00 × 10⁴ ng mL⁻¹ with the detection limit 3.6 ng mL⁻¹. There was no interference from the normally used in tablets and serum constituents. The proposed method was successfully applied to the determination of berberine hydrochloride in tablets and serum. And then it has a promising potential in therapeutic drug monitoring, pharmokinetis and clinical application.     

Supramolecular synthesis of coumarin derivatives catalyzed by a coordination-assembled cage in aqueous solution

A self-assembled Pd_4L_2 cage is employed as a water-soluble molecular flask for the synthesis of functionalized coumarins from a series of salicylaldehyde derivatives and cyanoacetates/malononitrile. The catalytic reaction features mild aqueous conditions and broad substrate scope. Crystal structures of the host-guest complexes for two substrates and one analogous intermediate have been obtained, shedding light on the supramolecular reaction mechanism. Michaelis-Menten kinetic studies were performed in one typical case, revealing that the rate of product formation has been enhanced by over 23-fold in contrast to the background reaction without cage. Moreover, the same reaction catalyzed by a smaller Pd_6L_4 cage gives a mixture of products and much lower yields, suggesting that fine-tuning on the size and symmetry of the cages' cavity is crucial for their applications in supramolecular catalysis.     

Supramolecular complex formation by beta-cyclodextrin and ferrocenylnaphthalene diimide-intercalated double stranded DNA and improved electrochemical gene detection

Ferrocenylnaphthalene diimide 1 can bind to double stranded DNA (dsDNA) by the threading intercalation mode and the resulting complex was stabilized further by beta- cyclodextrin (CD) by forming a supramolecular complex. These complex formation processes were studied by spectroscopic, viscometric, and electrochemical means in the absence or presence of beta-CD. Quantitative analysis by quartz crystal microbalance (QCM) and electrochemical experiments strongly suggested a 2:1 binding stoichiometry for beta-CD to 1 threading-intercalated to the dsDNA-immobilized electrode. Owing to this supramolecular complex formation, electrochemical DNA detection based on 1 was improved considerably.     

Supramolecular catalysis of Strecker reaction in water under neutral conditions in the presence of beta-cyclodextrin

An environmentally benign and highly efficient procedure for the nucleophilic addition of trimethylsilyl cyanide to imines (Strecker reaction) has been developed under biomimetic conditions in water in the presence of beta-cyclodextrin to afford alpha-aminonitriles in quantitative yields. The use of cyclodextrin precludes the use of either acid or base, and the catalyst can be recycled a number of times without loss in activity.     

Construction of supramolecular polymers with alternating alpha-, beta-cyclodextrin units using conformational change induced by competitive guests

Supramolecular polymers having alternating alpha- and beta-cyclodextrin (CD) units have been prepared by using conformational change induced by competitive guests. Although each CD unit does not form intermolecular complexes, a mixture of an alpha-CD derivative and a beta-CD derivative formed intermolecular complexes to give supramolecular polymers having alternating CD units. This is the first example of construction of supramolecular polymers with alternating alpha-, beta-cyclodextrin units.     

Supramolecular recognition and structural elucidation of inclusion complexes of an achiral carbene precursor in beta- and permethylated beta-cyclodextrin

[structure: see text] Inclusion of achiral carbene precursor endo-8-azibicyclo[3.2.1]octan-3-ol (1) in chiral beta-cyclodextrin (7-Cy) and tri-O-methyl-beta-cyclodextrin (TRIMEB) leads to 1:1 complexes 1@7-Cy and 1@TRIMEB, respectively. The combined methods of induced circular dichroism, NMR spectroscopy, and X-ray structure determination were employed for the first time for structural elucidation of the complexes in solution and the solid state. Significantly different orientations of 1 were observed. Compared with 1@7-Cy, 1@TRIMEB exhibits a different guest orientation and an association constant one-twentieth lower.     

Construction of alpha-helix peptides with beta-cyclodextrin and dansyl units and their conformational and molecular sensing properties

In order to apply de novo peptide design to molecular sensing, we designed and synthesized a-helical peptides with beta-cyclodextrin (beta-CDx) as a binding site and a dansyl unit (Dns) as a fluorescence sensing site. The conformational and molecular sensing properties of the peptides with beta-CDx and Dns in various positions were investigated. Circular dichroism and fluorescence measurements revealed that beta-CDx and Dns form intramolecular complexes which depend on their positions in the peptides. In the 17 residual peptides named EK3 and EK3R, in which beta-CDx and Dns were introduced at the fourth and the eighth positions (EK3) or at the eighth and the fourth positions (EK3R), Dns was deeply included in the CDx cavity and formed a more stable self-inclusion complex with CDx than in the peptides EK6 and EK6R, in which these moieties were at the eighth and the fifteenth positions or at the fifteenth and the eighth positions, respectively. The stability of the self-inclusion complex between beta-CDx and Dns controlled the a-helix structure as well as the binding and sensing abilities for the exogenous guests. These results demonstrate the usefulness of peptide tertiary structure for arranging CDx and other functional units, and suggest that this approach is important in the development of a new type of CDx-based sensory system.     

Supramolecular control of two-dimensional phase behavior

We have used directed two-component self-assembly to "pattern" organic monolayers on the nanometer scale at the liquid/solid interface. The ability of the scanning tunneling microscope to investigate structural details in these adlayers was used to gain insight into the two-component two-dimensional phase behavior. The components are symmetrically alkylated bisurea derivatives (R1-urea-spacer-urea-R2; R1, R2=alkyl, spacer=alkyl or bisthiophene). The bisthiophene unit acts as a marker and its bisurea derivative (T2) is a component in all the mixtures investigated. By varying the position of the hydrogen-bond forming urea groups along the molecule and the length of the alkyl chains of the other components, the effect of 1) hydrogen bonding, 2) molecule length, 3) odd-even effects, and 4) shape complementarity on the two-dimensional phase behavior was investigated. Insight into the effect of these parameters leads to the control of the two-dimensional patterning: from randomly intermixed systems to phase separation.     

Supramolecular synthesis of selenazoles using selenourea in water in the presence of beta-cyclodextrin under atmospheric pressure

Selenazoles were synthesized from alpha-bromo ketones and selenourea in the presence of beta-cyclodextrin in water at 50 degrees C under atmospheric pressure.     

Photoinduced intermolecular electron transfer from dimethyl aniline to 7-amino coumarin dyes in the surface of beta-cyclodextrin

The photoinduced electron-transfer reaction between Coumarin dyes and N,N-dimethylaniline has been investigated using steady-state and Time-resolved fluorescence spectroscopy in the surface of beta-cyclodextrin in dimethyl formamide (DMF) solvent. The electron-transfer rate constant has been correlated with the free-energy change during the process. We have observed a diffusion-controlled ET process in pure DMF by showing a normal Marcus region. However, the picture is different in presence of cyclodextrin. Here the ET is retarded at higher free-energy region. This unusual feature in bimolecular electron-transfer reaction is assumed to be arising from the different binding possibility of the Coumarin molecules to the cyclodextrin moity.     

Synthesis and properties of novel calix[4]arene derivatives bearing fluorogenic coumarin units

Four novel calix[4]arene derivatives 5-8 bearing four fluorogenic coumarin units attached via imino group acting also as binding sites at the upper rim have been prepared and characterized by IR, IH NMR and MS. Compounds 5-8 adopt a cone conformation. Their complexation properties to different heavy and transition metal ions have been studied by UV-vis spectroscopy. Compounds 5, 6, 8 show selective recognition to Fe^3＋ and Cr^3＋.     

Complexation of adamantyl compounds by beta-cyclodextrin and monoaminoderivatives

Since the beta-cyclodextrin cavity is not a smooth cone but has constrictions in the neighborhoods of the H3 and H5 atoms, the hypothesis that bulky hydrophobic guests can form two isomeric inclusion complexes (one of them, c(p), is formed by the entrance of the guest by the primary side of the cavity, and the other one, c(s), results from the entrance by the secondary side) is checked. Thus, the inclusion processes of two 1-substituted adamantyl derivatives (rimantidine and adamantylmethanol) with beta-cyclodextrin and its two monoamino derivatives at positions 6 (6-NH2beta-CD) and 3 (3-NH2beta-CD) were studied. From rotating-frame Overhauser enhancement spectroscopy experiments, it was deduced that both guests form c(s) complexes with beta-CD and 6-NH2beta-CD but c(p) complexes with 3-NH2beta-CD. In all cases, the hydrophilic group attached to the adamantyl residue protrudes toward the bulk solvent outside the cyclodextrin cavity. The thermodynamic parameters (free energy, equilibrium constant, enthalpy, and entropy) associated with the inclusion phenomena were measured by isothermal titration calorimetry experiments. From these results, the difference in the free energy for the formation of the two complexes, c(s) and c(p), for the same host/guest system has been estimated as being 11.5 +/- 0.8 kJ mol(-1). This large difference explains why under normal experimental conditions only one of the two complexes (c(s)) is detected. It is also concluded that a hyperboloid of revolution can be a better schematic picture to represent the actual geometry of the cyclodextrin cavities than the usual smooth cone or trapezium.     

Supramolecular control of a fast and reversible Diels-Alder reaction

A new cyclophane featuring two opposite anthracene units linked in 9,10-positions has been synthesized thanks to the template effect of the Me4N(+) ion. It forms pseudorotaxane complexes with alkylviologen ions and undergoes a fast and reversible reaction with tetracyanoethylene. A quantitative analysis has been carried out of the formation of Diels-Alder adducts, whose distribution can be controlled by host-guest complexation. These findings open interesting perspectives in the field of Dynamic Covalent Chemistry.     

Synthesis of nanostructures based on 1,4- and 1,3,5-phenylethynyl units with π-extended conjugation. Carbon networks dendrimer base units

A convenient and efficient synthesis of 3,5-di(silylethynyl)phenylacetylene and p-[3,5-di(silylethynyl)phenylethynyl]phenylacetylene has been carried out. These compounds serve to prepare nanometer-sized conjugated 1,4- and 1,3,5-phenylethynyl oligomers, by means of cross-coupling with a convenient haloaryl derivative, catalysed by palladium(II), in excellent yields. The phenylethynyl homologues show fluorescence emission, the wavelength of which is displaced by approximately 20 nm by each phenylethynyl unit increasing the conjugate chain.     

Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer

The homopolymeric sequence formed by the head‐to‐head association of tetrakisporphyrin 1 is completely dissociated by the competitive association of the ditopic guest G2 , resulting in the supramolecular copolymer poly‐ 1 ? G2 with an alternatingly repeating host–guest sequence. The 1:1 stoichiometry of 1 and G2 is confirmed by a Job plot using UV/Vis titration and diffusion‐ordered NMR spectroscopy (DOSY). The solution viscometry for poly‐ 1 and poly‐ 1 ? G2 suggests that the supramolecular chain of poly‐ 1 behaves like a rod, whereas the supramolecular copolymer chain of poly‐ 1 ? G2 behaves like a swelled fat chain, which is entangled in the semi‐dilute regime. Atomic force microscopy shows that the supramolecular polymer poly‐ 1 ? G2 is highly oriented through the interdigitation of the long alkyl chains.     

Supramolecular interactions between beta-cyclodextrin and hydrophobically end-capped poly(ethylene glycol)s: a quartz crystal microbalance study

In this study, the supramolecular interactions occurring between beta-cyclodextrin-based surfaces and macromolecular chains modified at one end with naphthyl, adamantyl, or phenyladamantyl hydrophobic groups were investigated by means of a quartz crystal microbalance. beta-Cyclodextrin-functionalized gold electrodes were obtained through the amide-coupling reaction between mono-6-deoxy-6-amino-beta-cyclodextrin and 11-mercaptoundecanoic acid self-assembled monolayer allowing the reproducible preparation of densely grafted surfaces with host properties. The interaction data obtained for the three different modified poly(ethylene glycol)s are in good agreement with our previous studies performed by high performance liquid chromatography and surface plasmon resonance. This evidences that the driving force for the supramolecular interaction is based on the inclusion of the hydrophobic terminal group of the chains within the cyclodextrin cavities. The reversibility of the inclusion process was proven through the regeneration of the original host properties of the sensing surfaces using sodium dodecylsulfate as a competitor for the desorption of the poly(ethylene glycol) chains.     

Destruction of perfluoroalkyl surfactant aggregates by beta-cyclodextrin

A water 1H NMRD and 19F NMR spectroscopy study has proved, for the first time, that perfluoroalkyl surfactant micelles can be completely destroyed upon addition of beta-cyclodextrin to form successively 1:1 and 2:1 (beta-CD:R(F)) inclusion complexes.