Optical and electrical study of chromogenic calix[4]arene derivatives

New chromogenic calix[4]arene derivatives proved many applications in optical and electrical fields. Organic diodes formed by sandwiching azo-calix[4]arene layers between indium-thin oxide (ITO) and (Al) contacts have been elaborated and measured. In this paper, studies of devices by current–voltage characteristics I(V) and electrical impedance spectroscopy measurements in a wide frequency range have been reported. The electrical characteristics follow a space charge limited conduction behaviour (SCLC). Therefore, the Cole–Cole plots were modelled by an equivalent circuit. Relaxation processes have been identified too from the impedance spectroscopy. The optical excitation of the organic structure revealed enhancement in electrical properties.     

Photoluminescence and thermoanalytical studies of complexes based on 5-Cl-8-hydroxyquinoline and calix[4]arene ligands

A innovative 5-Cl-8-oxyquinolinepropoxycalix[4]arene ligand (2) have been prepared, exhibiting, at room temperature, blue fluorescent light emission and resulting in shift band to green fluorescent light (fluorescence mode) in the presence of coordinated Eu(III) and Tb(III) ions. Terbium complex presented phosphorescence emission as noted by typical bands at 490 nm, 545 nm and 585 nm. TG/DTG data exhibited typical thermal behavior for these compounds, however DSC curves showed the melting temperature near 300 °C for the samples, demonstrating an unusual thermal stability when quinoline derivatives are attached to calix[4]arene matrix. This fact strongly suggests an effective approach to preparing the photoluminescent compound associating high chemical and thermal stability.     

Fabrication of calix[4]pyrrole nanofilms at the glassy carbon surface and their characterization by spectroscopic, optic and electrochemical methods

meso-Octamethylcalix[4]pyrrole (CP) and meso-heptaethylcalix[4]pyrrole-meso-4-aminophenyl (4APCP) modified glassy carbon (GC) electrodes were prepared by the electrochemical oxidation in acetonitrile solution. Binding of the calix[4]pyrroles with the glassy carbon surface was investigated that it is through the etheric linkage revealed from the reflection-absorption infrared spectroscopy (RAIRS). Surface films of CP and 4APCP were investigated by cyclic voltammetry (CV), ellipsometry, X-ray photoelectron spectroscopy, RAIRS and the contact angle measurements. The thicknesses of the films were determined by ellipsometry which confirmed that the film was multilayer and homogeneous over the surface. Ellipsometric measurements also provided that the CP and 4APCP film thicknesses were 2.49 nm and 4.58 nm for 6 CV cycle modification, corresponding to 66 μF/cm² and 106 μF/cm² capacitances obtained by CV. The wetting behavior was examined by contact angle measurements and found that the hydrophobicity of the GC-4APCP surface was higher than that of GC-CP, probably due to the aromatic meso substituent present in the former.     

Complexation of higher fullerenes by calix[5]arene-based host molecules

The binding abilities of calix[5]arene-based host molecules for higher fullerenes (C76, C78, and C84) were investigated in organic solvents. The binding abilities of double-calix[5]arenes to higher fullerenes are high. In particular, their association constants to C76 and C78 in toluene reached at the order of 10(5) M(-1). In contrast, the binding abilities of simple calix[5]arenes decreased as increasing the size of the fullerenes. Accordingly, linking two calix[5]arenes with the covalent bonds creates the large cavities, complementary to higher fullerenes. The structure of the host-guest complex of double-calix[5]arene and C76 was discussed. The carbons of the polar end of C76 characteristically shifted upfield more than the other carbons in the host-guest complex, indicating that these polar carbons reside most deeply inside the cavity of the calix[5]arene.     

Grafting of calix[4]arene derivative on activated carbon surface

A new material has been synthesised by reaction between a calix[4]arene amine derivative and an oxidized activated carbon in DMF. Each reactant was characterized by thermogravimetric analysis (TGA) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS). In addition, the BET surface area of activated carbon, oxidized carbon and calixarene-modified carbon, were measured and are equal to 737, 519 and 351 m²/g, respectively. Results show that calixarene is linked to superficial oxygen functional groups through a covalent bond. A percentage of grafted calixarene of the order of 35% have been calculated from the results of elemental analysis.     

The extraction of thorium by calix[6]arene columns for urine analysis

Thorium is a natural alpha-emitting element occurring in various ores and has numerous industrial applications. Routine monitoring of potentially exposed workers is generally achieved through radiobioassay (urine and faeces). The procedures currently used for analysing actinides such as thorium in urine require lengthy chemical separation associated with long counting times by alpha-spectrometry due to low activity levels. Thus, their main drawback is that they are time-consuming, which limits the frequency and flexibility of individual monitoring. In this context, this study developed new radiochemical procedures based on the use of tertbutylcalix[6]arenes bearing three carboxylic acid groups or three hydroxamic acid groups. These previous works demonstrated that these macrocyclic molecules immobilised on an inert solid support are excellent extractants for uranium, plutonium and americium. In this study, the authors investigated the thorium extraction by calix[6]arene columns. Experiments were performed on synthetic solutions and on real urine samples. The influence of various parameters, such as the thorium solution pH and the column flow rate on thorium extraction, was studied. The results showed that both calix[6]arenes are efficient to extract thorium. Thorium extraction is quantitative from pH = 2 for synthetic solution and from pH = 3 for real urine samples. This study has demonstrated that the column flow rate is a crucial parameter since its value must not be too high to achieve the steady-state complexation equilibrium. Finally, these results will be compared with those obtained for other actinides (U, Pu and Am) and the conditions of actinides' separation will be discussed.     

Ionic interactions and multilayer structures on self-assembled surfaces of calix[4]resorcinarene

The ionization of a self-assembled monolayer of tetrathiol calix[4]resorcinarene, which is a synthetic host in guest-host recognition phenomena, was investigated. Using surface plasmon resonance measurements, it was found that ionization of the self-assembled surface occurred in water at a pH of approximately 11.5. These ionized surfaces of calix[4]resorcinarene were used to bind ionic guests such as metallic copper ions that were further exploited in the formation of supramolecular ionic assemblies of calix[4]resorcinarene. The structure of the molecular assemblies was characterized using polarization modulation infrared reflection absorption spectroscopy. The use of ionic interactions to attach molecules such as 11-mercapotundecanoic acid to the upper rim of the calix[4]resorcinarene host was also investigated as a method for simple and non-covalent modification of the host cavity.     

Preparation and characterization of calix[6]arene Langmuir-Blodgett thin film

Calix[6]arene monolayer/multilayer was prepared on a glass substrate and the behavior of monolayer properties investigated at the air-water interface by taking Langmuir isotherm graph. UV-visible, wettability measurements, atomic force microscopy and quartz crystal microbalance measurements were used to monitor the deposition quality of this Langmuir-Blodgett film. Our results showed that a uniform and high quality film with a transfer ratio of approximately 0.99 occurred using the calix[6]arene material at a deposition pressure of 21 mN/m. The surface free energy was determined to be 25.86 mN/m based on contact angle measurements.     

Chemical selectivity of self-assembled monolayers of calix[4]resorcinarene

Selective molecular interactions at an interface formed by self-assembly of a macrocyclic synthetic host, calix[4]resorcinarene with four thiol groups (R4SH), are investigated. The recognition of guest adsorbates from aqueous solutions is monitored using surface plasmon resonance (SPR) and the orientation of the guest-molecule is probed using polarization modulation infrared absorption spectroscopy (PM-IRRAS). The experiments reported here demonstrate that the chemical selectivity of self-assembled monolayers (SAMs) of host molecules such as calix[4]resorcinarenes extends to isomers of several different guest molecules. By using structural isomers of guest molecules such as bipyridine and nitrophenol that are multidentate hydrogen bond acceptors, it is shown that geometric match between guest and host molecules is an integral aspect of the recognition phenomena. Results from SPR and PM-IRRAS experiments reported here highlight the interplay between steric size and forces such as hydrogen bonding and hydrophobic interactions. Competitive and sequential adsorption of guest molecules such as -hydroxy-γ-butyrolactone and 4,4′-bipyridine shows that these guests compete for the same binding sites on the surface and that the interplay between steric size and molecular forces underlies the preferential selectivity of one guest molecule over another.     

Pyroelectric and conduction properties of Z-type calix[4] acid Langmuir-Blodgett films

Non-centrosymmetric Z-type Langmuir-Blodgett (LB) films were prepared by transferring a calix[4] acid monolayer from a subphase of Millipore water (18 Momegacm(-1)) onto aluminised glass substrates. Electrical measurements were performed at room temperature on LB films with a sandwich structure comprising a 50 nm thick thermally evaporated aluminium film. A pyroelectric figure of merit of 2.23 microC m(-2)K(-1) is reported for this LB system. The low voltage value of conductivity is 1.82 x 10(-12) Sm(-1). The electrode-limited Schottky effect is responsible for the conduction mechanism at a relatively high field due to the dc bias and the barrier potential height is determined to be 1.72 eV. The ac conductance for both samples shows a typical power law dependence with a value of approximately 0.86 for the exponent.     

Observation by atomic force microscopy of calix[n]arene thin films and their thermal rearrangement

Vapor deposited thin films of various calix[n]arenes have been investigated by contact mode atomic force microscopy. Two classes of thin films have been defined. For para-H-calix-4-arene, para-H-calix-6-arene, and para-iso-propyl-calix-4-arene pre-organized structures are observed on deposition. For para-iso-propyl-calix-6-arene, para-tert-butyl-calix-4-arene, para-tert-butyl-calix-6-arene, para-tert-butyl-calix-8-arene glassy unordered systems are obtained on deposition. Annealing of para-iso-propyl-calix-6-arene, para-tert-butyl-calix-4-arene, para-tert-butyl-calix-6-arene at 100°C leads to crystallization either directly from the glass or by migration of nano-crystallites to form microstructures.     

杯[4]芳烃乙酸/TiO2的制备及其光催化活性

以Ti(OBu)4和杯[4]芳烃乙酸为前驱体,采用溶胶-凝胶法制备了不同TiO2含量的杯[43芳烃乙酸/TiO2(CA/TiO2)材料.通过FT-IR测试表明,材料中有机无机两相间存在着化学键,并通过XRD对材料的结构进行表征.为了测试材料的光催化性能,以甲基橙溶液为模拟水样,进行了光催化降解的对比实验.结果表明:当T...     

Single-molecule spectroscopic study of enhanced intrinsic phycoerythrin fluorescence on silver nanostructured surfaces

In this paper, we report on steady-state and time-resolved single-molecule fluorescence measurements performed on a phycobiliprotein, R-phycoerythrin (RPE), assembled on silver nanostructures. Single-molecule measurements clearly show that RPE molecules display a 10-fold increase in fluorescence intensity, with a 7-fold decrease in lifetime when they are assembled on silver nanostructured surfaces, as compared to control glass slides. The emission spectrum of individual RPE molecules also displays a significant fluorescence enhancement on silver nanostructures as compared to glass. From intensity and lifetime histograms, it is clear that the intensities as well as lifetimes of individual RPE molecules on silver nanostructures are more heterogeneously distributed than that on glass. This single-molecule study provides further insight on the heterogeneity in the fluorescence intensity and lifetimes of the RPE molecules on both glass and SiFs surfaces, which is otherwise not possible to observe using ensemble measurements. Finite-difference time-domain calculations have been performed to study the enhanced near-fields induced around silver nanoparticles by a radiating excited-state fluorophore, and the effect of such enhanced fields on the fluorescence enhancement observed is discussed.     

Evaluation of the performance of calix[8]arene derivatives as liquid phase extraction material for the removal of azo dyes

This paper presents a study on the removal of azo dyes (Reactive Black 5, Trapaeolin 000, Methyl Orange and Direct Violet 51) with calix[n]arene derivatives from aqueous solution into the organic phase in order to explore the potential use of calixarenes as low-cost efficient extractants for wastewater dye removal. The carboxylic acid derivative of calix[8]arene shows highest affinity towards the azo dyes. The influence of NaCl (present in the solution) on extraction process was also studied. The extent of the dye removal increased with the addition of NaCl. The proposed extraction mechanism involves several kinds of interactions: electrostatic repulsion between carboxylic acid groups of calix[8]arenes and sulfonate groups of azo dyes, hydrogen bonding and formation of an inclusion complex due to three dimensional cavity type calix[n]arene molecules through host-guest interactions.     

A model study of artificial linker system using self-assembled calix[4]arene derivative monolayers for protein immobilization

The attachment of biomolecules, in particular proteins, onto solid supports is fundamental in the development of advanced biosensors, biochips, bioreactors, and many diagnostic techniques. In addition, the effective investigation of biomolecular structure and function with chip-based modern instruments often requires effective attachment of the biomolecule to a substrate. For this reason, it is very important to construct well-characterized linker system that can immobilize protein efficiently. Here, we investigate the formation of self-assembled monolayers (SAMs) with calix[4]arene ethylester and carboxylic acid derivatives that can serve as a model system for protein immobilization at solid surfaces. The calix[4]arene derivative monolayers were formed on Au surface and carefully characterized by atomic force microscopy (AFM), Fourier transform infrared reflection absorption spectroscopy (FTIR-RAS) and surface plasmon resonance (SPR). Immobilization process of protein using bovine serum albumin (BSA) on the artificial linker layer was measured by SPR. The surface concentration of BSA was calculated by simulation of experimental SPR data. The surface concentration of BSA on the carboxylic acid form was higher than that of the ethylester. These results can help in modeling and understanding of protein immobilization on the linker layer.     

Surface-enhanced micro-Raman detection and characterization of calix[4]arene-polycyclic aromatic hydrocarbon host-guest complexes

Surface-enhanced micro-Raman spectroscopy (micro-SERS) was used to detect traces of the hazardous pollutant polycyclic aromatic hydrocarbons (PAHs) pyrene and benzo[c]phenanthrene deposited onto a calix[4]arene-functionalized Ag colloidal surface. High spectral reproducibility and very low molecular detection limits (10(-8) M) were obtained by using 25,27-carboethoxy-26,28-hidroxy-p-tert-butylcalix[4]arene as host molecule. Films of immobilized aggregated Ag nanoparticles, obtained by chemical reduction with hydroxylamine, were prepared by direct adhesion on a glass surface. The influence of the aggregation degree of the initial Ag nanoparticles on the micro-SERS detection effectiveness was checked. Different relative concentrations of the host (calixarene receptor) and the guest (PAHs) were attempted in order to optimize detection of the pollutant. The obtained results indicated that the detection limit is much lower in the case of benzo[c]phenanthrene than in pyrene when exciting with the 785 nm line of a diode laser. A detailed interpretation of the Raman spectra was accomplished in order to obtain more information about the interaction mechanism of the host-guest complex, which could be useful in the future for the design of powerful detection systems.     

Preparation and application of calix[4]arene-grafted magnetite nanoparticles for removal of dichromate anions

Magnetic Fe₃O₄ nanoparticles were prepared by the chemical co-precipitation of Fe(III) and Fe(II) ions. Then, the nanoparticles were modified directly by 3-aminopropyltrimethoxy silane (APTMS) to introduce reactive groups onto the particles' surface, and diester derivative of calix[4]arene was immobilized onto the surface of modified-Fe₃O₄ nanoparticles by aminolysis reaction. The prepared magnetite nanoparticles (Calix-GM) were characterized by a combination of IR, TGA and TEM analyses. The extraction properties of the new material toward dichromate anions were also studied. It was observed that the prepared magnetite nanoparticles were an effective extractant for the removal of dichromate anions at pH 2.5–4.5.     

Synthesis and application of calix[4]arene based resin for the removal of azo dyes

The present study describes a novel synthetic method for the immobilization of calix[4]arene (II) onto the surface of modified Amberlite XAD-4 resin (4), which does not require the derivatization of calixarene moiety. The novel calix[4]arene based resin (C4 resin) 5 was used as sorbent for the removal of azo dyes. Batch-wise sorption study was carried out and observed that the C4 resin (5) is more effective as compared to compound II as well as pure Amberlite XAD-4 resin (1) to remove the selected dyes [i.e. Reactive Black-5 (RB-5), Reactive Red-45 (RR-45) and Congo Red (CR)]. The effect of sorbent dosage and pH on % sorption was studied. During the extraction process, various kinds of interactions such as electrostatic repulsion, deprotonation of the hydroxyl groups of C4 resin, dissociation of reactive dyes into anions/cations and structural variations were monitored and found that they are highly pH dependent.     

Molecular recognition of protonated polyamines at calix[4]crown-5 self-assembled monolayer modified electrodes by impedance measurements

Molecular recognition of protonated aliphatic polyamines has been studied at calix[4]crown-5 self-assembled monolayer modified gold electrodes by electrochemical impedance spectroscopic (EIS) experiments. The energy of complex formation between the calix [4]crown-5 molecule and a series of alkyl ammonium ions was shown by molecular modeling and EIS experiments to depend on the number of amine groups in the alkyl chain as well as the number of methylene groups between the amine groups. The structures of complexes formed between the crown ether on the lower rim of calix[4]arene and protonated amines were determined by minimizing the complex formation energies. The adducts thus formed on the SAM rendered the electron transfer from the electrode to the probe (Fe(CN)63-/4- pair) easier or more difficult depending on the number of ammonium groups and their arrangement in linear alkyl chains. Analytical procedures have been developed to detect protonated spermidine (a recognized cancer marker) in simulated urine, blood, erythrocyte, and cerebrospinal fluids.