Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface

Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?_f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?_f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm⁻²). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity.     

Switching of energy transfer reaction by the control of orientation factor between porphyrin derivatives on the clay surface

Photochemical energy transfer was examined on the flat clay surface. By the change of surrounding atmosphere, the molecular adsorption orientation angle of dyes can be modulated. It is turned out that the energy transfer efficiency between dyes can be controlled by the relative orientation change between dyes. The change of orientation factor and spectral overlap factor was the main factor to affect the energy transfer efficiency. This technique would be useful to construct the photo-functional materials such as chromic and light harvesting system.     

Fast transfer process of pyrene between oil-in-water miniemulsion droplets

Recently phase formation mechanisms have been estimated by using various fluorescent probes. In this report, the mixing process between internal phases of oil-in-water miniemulsions is discussed for two-dimensional color graphics data (two-dimensional fluorescence images) based on the excimer formation of pyrene as a hydrophobic fluorescent probe. Just after miniemulsion solution B (water, oil, and nonionic surfactant) was gradually added to miniemulsion A (water, oil, surfactant, and trace amount of pyrene) with gentle and careful stirring, the fluorescence spectra and the two-dimensional image of pyrene were measured. The decreasing of the excimer peak of pyrene was observed as soon as miniemulsion solution B was added. The result showed that pyrene initially located in miniemulsion droplets was smoothly diluted by the addition of miniemulsion droplets which contain only oil in the internal phase. The internal phases of miniemulsion droplets are miscible without changing the droplet diameter, and it is declared that pyrene transfers smoothly to the interface between droplets stabilized by the nonionic surfactant because the droplet diameter showed no significant difference throughout this mixing process. Received: 7 December 1999 Accepted: 11 April 2000     

A novel fluorescent guanine derivative distinguishable of three structures, single strand, duplex, and quadruplex

We have constructed a pyrene-labeled guanine base, ^8PyG. ^8PyG is a novel fluorescent probe for monitoring the secondary structure of G-rich DNA. The fluorescence emitted from ^8PyG-labeled oligodeoxynucleotide clearly distinguished three structural states, single strand-duplex-quadruplex. Thus, the technique, which monitors the fluorescence of ^8PyG-labeled oligodeoxynucleotide, is a powerful tool for the investigation of DNA structural changes.     

Study of the diffusion of pyrene in silicone polymer coatings by steady state fluorescence technique: effects of pyrene concentration

The concentration dependence of the diffusion coefficient of pyrene in single component and two-component room temperature curing silicone polymer coatings is investigated by the steady state fluorescence technique by measuring the pyrene excimer fluorescence intensity. At pyrene concentrations lower than 10 mM, the intensity of excimer fluorescence is proportional to the concentration and at higher concentrations it deviates from this trend due to concentration quenching. Thermal aging studies show that this concentration quenching can be removed by thermal annealing and the excimer emission intensity approaches the value expected from the trend at lower concentrations. The diffusion coefficient of pyrene at low concentrations in silicone polymer coatings is obtained using the approximate solution of one-dimensional diffusion equation. A modified approach is employed to estimate the diffusion coefficient at higher pyrene concentrations. In this method, the excimer intensity and time scale are shifted, respectively to I_max the maximum value of excimer intensity attained during annealing and t_max, the time taken to reach this. The estimated diffusion coefficients at different pyrene concentrations show a negligible dependence on pyrene concentration in both types of polymers. These results are attributed to the high structural mobility of silicone polymer chains due to their molecular structure.     

Growth and characterization of pyrene crystals on carbon nanofibers

Pyrene crystals were grown on carbon nanofibers (CNFs) by dispersing pyrene polycrystals and CNFs in water during ultrasonic irradiation, and they were characterized by scanning electron microscopy, X-ray diffractometry (XRD) and spectroscopy. The XRD measurements indicated that the orientation and size of the pyrene crystals on the CNF aggregates were different from that of the added pyrene polycrystals. Based on the spectroscopic properties of the pyrene crystals on the CNFs, the pyrene crystals on the CNF aggregates and on the individual CNFs were determined to be polycrystals and single crystals, respectively. These results indicate that pyrene crystals are produced on the CNFs by recrystallization of the added pyrene polycrystals and their crystal states depend on the aggregation state of the CNFs.     

Active species transfer-type artificial light harvesting system in the nanosheet – Dye complexes: Utilization of longer wavelength region of sunlight

A novel light harvesting system that captures long-wavelength light of sunlight by the use of hole transfer was newly investigated. Ga phthalocyanine(Ga^IIITMAPc⁴⁺(D)) and Ru porphyrin(Ru^IIDMPyMP²⁺(A)) co-adsorbed reaction system on the synthetic nanosheet was examined as an artificial light harvesting system. By irradiating 660?nm light, where Ga^IIITMAPc⁴⁺(D) absorbs, to the system under a presence of PtCl₆^2? as an electron acceptor, cation radical of Ru^IIDMPyMP²⁺(A) was produced despite that Ru porphyrin adsorbs only 413 and 533?nm light. The efficient hole transfer reaction from Ga^IIITMAPc⁴⁺(D)⁺, that is generated from its excited state, to Ru^IIDMPyMP²⁺(A) takes place on the nanosheet.     

Investigations of the effect of viscosity of resin on the diffusion of pyrene in silicone polymer coatings using steady state fluorescence technique

The diffusion phenomenon of pyrene in silicone coatings prepared from various commercial silicone resins with different viscosities was investigated using steady state excimer fluorescence technique. The amount of pyrene lost from the coatings by diffusion at different temperatures ranging from 25 to 70 °C was estimated from the excimer emission intensity. The diffusion coefficients (D) and activation energy of diffusion of pyrene in silicone coatings were determined. It was found that the kinetic parameters of pyrene were comparable in all the four silicone coatings and independent of the viscosity of the resin. The D values were lower than those expected for pyrene in PDMS resins in the corresponding viscosity range. This may be attributed to restricted mobility of pyrene due to cross-linking of polymer chains in the cured silicone coatings.     

Effect of urea on the conformational behavior of poly(N-isopropylacrylamide)

The effect of urea on the conformational behavior of poly(N-isopropylacrylamide) (PNIPAM) in dilute aqueous solution has been investigated using fluorescence spectroscopy, fluorescence quenching and fluorescence anisotropy measurements via pyrene (Py) probe and acenaphthylene (ACE) label studies. It was demonstrated that urea promotes the partitioning of the hydrophobic probe, Py, towards the bulk aqueous phase at temperatures above the lower critical solution temperature (LCST) of the polymer due to swelling of the compact coil conformation. However, the compact coil structure of the polymer at temperatures greater than its LCST is not completely destroyed, even for urea concentrations up to 3 M, at which the phase transition is hardly observed. As expected, urea has little effect on the conformational behavior of PNIPAM at temperatures below its LCST. Received: 9 February 2000/Accepted: 13 June 2000     

Facile synthesis and characterization of a novel thiophene-fused polycyclic aromatics based on pyrene

A novel large thiophene-fused polycyclic aromatics 1 based on pyrene 5 has been synthesized,and its structure was confirmed by ¹H NMR,¹³C NMR,MS,UV -vis and elemental analysis.The key steps of the synthesis involved the Stille cross-coupling reaction and followed by selectiveβ-βoxidative cyclization of pendant thienyl rings by FeCl₃ under mild conditions.     

Cucurbit[6]uril nanocavity as an enhanced spectrofluorimetric method for the determination of pyrene

The effect of the addition of macrocyclic host cucurbit[6]uril (CB6) on the photophysical properties of polycyclic aromatic hydrocarbon pyrene (PYR) was analyzed. The fluorescence emission spectra of the aromatic compound were determined at 25.0 °C in different acidic media (HCl 18%, w/v, or HCOOH 55%, w/v) with and without CB6. A significant enhancement in the fluorescence signals in the presence of CB6 was observed. The average values of the association constant (K_A) for the 1:1 stoichiometry complex and the relative fluorescence quantum yield ratio between the complexed and free PYR (?^PYR–CB6/?^PYR) in acidic media were (4.0 ± 0.5) × 10² M⁻¹ and (5.7 ± 0.2), respectively.The analytical parameters improved in the presence of CB6. The relative decrease in the limit of detection was 92%. The matrix effect was evaluated in fortified samples of tap water and tea extracts. Apparent recoveries obtained by the proposed method in tap water and tea extracts were (82–103)% and (89–99)%, respectively. Selectivity studies with inorganic and organic species were performed. The method is rapid, direct, selective and simple.     

The variable role of clay on the crystallization behavior of DMDBS-nucleated polypropylene

The effect of clay on the nucleating behavior of 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol(DMDBS) in cryatallization of isotactic polypropylene(iPP) was investigated by means of differential scanning calorimetry(DSC), dynamic rheology and polarized light microscopy(PLM).It is interesting to note that the incorporation of layered clay nanoparticles into DMDBS-nucleated iPP may induce a synergetic nucleation effect while the DMDBS content is below 0.1 wt%,otherwise it restricts the crystallization rate prominently as the DMDBS content increases up to 0.3 wt%,which has exceeded the content threshold to yield a nucleating agent(NA) network.As shown by dynamic rheological investigations, the clay nanoparticles demonstrate an obstructive effect of disturbing the consistency of DMDBS fibrils network.Moreover, to further demonstrate the importance of NA network formation in the crystallization of iPP,we used another NA named HPN-20e,which can not form network structure at all over the concentration studied,for comparison.In this case,the nucleated-crystallization rate is independent on the addition of clay nanoparticles,as the nucleating mechanism is an individual nuclei manner without NA network forming.     

Influence of clay surface modification with urethane groups on the crystallization behavior of in situ polymerized poly(butylene succinate) nanocomposites

The crystallization behavior and fine structure of poly(butylene succinate) (PBS) nanocomposites with intercalation (30B20) and exfoliation (30BM20) morphologies, respectively, were investigated via isothermal crystallization testing and synchrotron small-angle X-ray scattering (SAXS). The dynamic viscosity of 30BM20 was markedly increased due to favorable interactions between the PBS matrix and the urethane group on the clay surface. However, 30BM20 showed similar crystallization rates to that of homo PBS because the surface urethane modification for 30BM20 precluded PBS matrix from the metallic group into clay to difficult in contact with each other, resulting in a reduced nucleation activity for the metallic group. SAXS profiles revealed that the long period and amorphous region size for 30B20 drastically decreased during isothermal crystallization. Meanwhile, 30BM20 was similar to those of homo PBS. This result also supports the above explanation for isothermal crystallization behavior. Considering all results in total, the introduction of a urethane modification considerably enhanced the physical properties of PBS but caused delayed crystallization rates.     

Spectroscopic effects of organized media on a cyanine dye/pyrene derivative

The absorption and fluorescence spectra of a cyanine dye/pyrene derivative are studied in the presence of-cyclodextrin, Brij 35, cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). Benesi-Hildebrand type equations are used to estimate the apparent association constant of the dye/cyclodextrin complex. In addition, an estimate of the dimerization constant for the dye is examined.     

Study on fluorescent switching of naphthopyran with carbazole and pyrene dyad immobilized on SBA-15

A naphthopyran-bridge-carbazole dyad (CzNP), which exhibits both fluorescence and photochromism was synthesized. Then the CzNP was grafted into SBA-15-NH₂, with particular focus on how the SBA-15-NH₂ affects the photoswitching fluorescence change properties. A double fluorescence photochromic material, which was prepared by reacting 1-Pyrenecardboxaldehyde(PY-CHO):naphthopyran-carbazole(CzNP)=1:1 (molar ratio) with SBA-15-NH₂ was also synthesized. Naphthopyran in this two systems displayed excellent photochromic performance. The fluorescent emission was modulated between ‘on’ and ‘off’ via the photoisomerization of naphthopyran in high-degree, especially in PY-CzNP-SBA-15-NH₂ (>90%) due to the photoinduced energy transfer from pyrene excimers to the opened-form naphthopyran and the photoinduced electron transfer between carbazoles and the opened-form naphthopyran moiety. Both the fluorescence photoswitching CzNP-SBA-15-NH₂ and PY-CzNP-SBA-15-NH₂ in CH₃CN/H₂O (v/v, 1:1) solution displayed excellent fatigue resistance. The structural characteristics of CzNP-SBA-15-NH₂ and PY-CzNP-SBA-15-NH₂ were measured by FTIR spectra, X-ray diffraction (XRD), and Elemental analysis.     

Studies on Hybrid Organic/Inorganic Nanocomposite Gels Using Photoluminescence Techniques

Summary.  Transparent nanocomposite gels made of hybrid organic/inorganic polymers, synthesized through the sol-gel method, composed of poly-(ethylene oxide) or poly-(propylene oxide) chains, and grafted on silica through urea bridges, have been studied by steady-state and time-resolved photoluminescence techniques. These nanocomposite materials consist of two distinguished subphases, an organic and an inorganic one. The volume fraction of the organic (polyether) subphase is larger than that of the inorganic (silica) subphase, and it increases with increasing polyether chain size. The condensation of the silica subphase provides luminescent entities emitting light by electron-hole recombination on delocalized states associated with the active chemical species of the urea bridges. Materials with smaller polyether chains are more luminescent than such with longer polyether chains. Divalent or trivalent cations introduced into these materials enhance the luminescence intensity by solubilization close to the silica cluster surface and thus by decreasing surface defects and the ensuing quenching mechanism. Received June 23, 2000. Accepted (revised) July 18, 2000     

The effect of pyrene labelling on the thermal stability of actin filaments

The ability of actin to form filaments is fundamental to its biological function and often characterised by various methods in vitro. One of the most frequently used methods capitalises on the observation that the fluorescence emission of a pyrene label on the Cys-374 residue of actin is enhanced by a factor of ∼20 during polymerisation. This method inherently involves the chemical modification of actin monomers with pyrene. It was reported earlier that the pyrene labelling of actin monomers has only small effect on the polymerisation and depolymerisation rates of actin, indicating that the method is suitable to characterise the effect of actin-binding proteins or peptides on the polymerisation kinetics.In our present work we tested the effect of the pyrene labelling on the thermal denaturation of actin filaments by using the method of differential scanning calorimetry (DSC). By recording the heat denaturation profiles of unlabelled and pyrene labelled actin filaments we observed that pyrene labelling shifted the melting point (T_m) of actin filaments from 66 to 68 °C. A similar effect was detected in the presence of equimolar concentration of phalloidin where the T_m shifted from 79 to 82 °C. We concluded that the observed pyrene labelling induced differences of the thermal denaturation of actin filaments were small. The DSC results, therefore, confirmed that the methods based on the measurements of pyrene intensity during actin polymerisation are suitable to characterise the polymerisation kinetics of actin under in vitro conditions.     

An insight to the filtration mechanism of Pb(II) at the surface of a clay ceramic membrane through its preconcentration at the surface of a graphite/clay composite working electrode

The use of cyclic voltammetry (CV) and linear scan anodic stripping voltammetry (LSASV) to predict the selectivity of microfiltration ceramic membranes made from a lump of local clay towards Pb(II) ions filtration is described. The membranes were characterized by different techniques followed by CV analysis of the Fe(CN)₆^3-/Fe(CN)₆^4- redox couple and Pb(II) on bare graphite, raw clay, and clay-modified carbon paste electrode (clay-modified CPE). The effect of clay loading in the range of 1–10 % (w/w) on the electrodes is studied, where an enhanced peak current is observed for 5 % w/w clay. Moreover, a decrease in the peak current can be seen for bare graphite electrodes, suggesting that the clay mineral had played a substantial role in the sieving of heavy metal ions through the ceramic membrane. The electroactive surface area of 5% w/w raw clay towards Fe(II) ions was found to be in the order of 3.07 × 10^-2 cm² and higher than 5% w/w clay sintered to 1000 °C and bare graphite. CV analysis shows that both, 5 % w/w raw clay and 5 % w/w clay sintered to 1000 °C exhibited high peak currents towards Pb(II) ions. The mobility of the Pb(II) ions is found to increase when 5% w/w clay sintered to 1000 °C is utilized as membrane/electrode, leading to an increase in the amount of reduced Pb(II) ions on the surfaces of the clay membranes/electrodes. The study suggests successful filtration of Pb(II) ions through the proposed membrane/electrode and a much better accumulation than Fe(II) at the surface of the membrane/electrode before being subjected to filtration.     

Effect of clay surface on aldehyde-diol equilibrium

The effect of clay surface on the equilibrium between aldehyde and diol was examined by using 4-formyl-1-methylpyridin-1-ium chloride (MPy⁺) as a substrate. MPy⁺ exists as diol (DHMPy⁺) and aldehyde (FMPy⁺) in water and acetonitrile, respectively. It was turned out that FMPy⁺ was clearly observed in the presence of clay nanosheet even in water. This indicates that clay nanosheet surface acts as unique chemical reaction field, affecting the potential energy surface between FMPy⁺ and DHMPy⁺.