Solvent effect of fluorescence on/off switching of diarylethene linked to excited-state intramolecular proton transfer fluorophore

Efficient fluorescence on/off switching of a dyad consisting of a photochromic diarylethene and a fluorescence dye based on excited state intramolecular proton transfer (ESIPT) was designed and demonstrated. Diarylethenes linked to (2-(2-methoxy-5-methylphenyl)benzothiazol-6-yl)- and (2-(2-hydroxy-5-methylphenyl)benzothiazol-6-yl)-9,9-dioctylfluorene moieties (1a and 2a, respectively) exhibited fluorescence on/off switching upon alternating irradiation with ultraviolet and visible light in various solvents. The fluorescence on/off contrast of 2a was found to be higher than that of 1a in n-hexane because the overlap integral between the absorption spectrum of the diarylethene closed-ring form and the fluorescence spectrum of 2a is larger than that of 1a. Diarylethene 2a exhibited green fluorescence with large Stokes shift in n-hexane, which is ascribed to the ESIPT process from the enol form to the keto form. In contrast, the fluorescence of 2a in N,N-dimethylsulfoxide (DMSO) was mainly observed as blue fluorescence from enol form, while diarylethene 1a exhibited blue fluorescence in n-hexane and DMSO. The fluorescence on/off contrast of 2a in n-hexane was higher than that in DMSO because of the difference in the spectral overlaps in n-hexane and DMSO.     

Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time-resolved absorption spectroscopies in the visible to near-infrared and mid-infrared regions. The time-domain vibrational data in the visible region show that the initially formed Franck-Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low-frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time-resolved mid-infrared spectroscopy directly detected the formation of the open-ring isomer with the same time constant as the decrease of the closed-ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed-ring isomer and the open-ring isomer in the ground state.     

Targeted Delivery using Immunoliposomes with a Lipid-Modified Antibody-Binding Protein

A recombinant antibody-binding protein originating from streptococcal protein G was modified with lipid in a site-directed manner by genetic engineering. The resulting lipoprotein was incorporated into the surface of liposomes by simple mixing. Immunoliposomes were then prepared by binding anti-IgG antibodies molecules onto the surface of proteoliposome via the lipid-anchored streptococcal protein G. Either small fluorophores or fluorescently labeled proteins were encapsulated into prepared immunoliposomes, and these molecular tracers could be delivered into cells whose surfaces were marked with specific antibodies.     

Successive chelatometric titration of calcium and magnesium

A simple procedure for the successive chelatometric titration of calcium and magnesium in natural waters, with 3',3'-bis(2-hydroxy-3-carboxy-naphthaleneazo)phenolphthalein as indicator, is described.     

Kinetic study of transmembrane electron transport by the hinkle process

Trans-membrane redox reactions mediated by t-amylferrocene (one-electron carrier) were studied kinetically in a liposome system separating two redox pairs (ferricyanide/ferrocyanide and dehydroascorbate/ascorbate). In order to eliminate the membrane potential generated, which suppressed the rate of the reaction, the rate was measured in the presence of carbonylcyanide m-chlorophenylhydrazone. The reaction rate was independent of concentrations of ascorbate and dehydroascorbate. Ferricyanide also had virtually no effect on the rate, but addition of ferrocyanide decreased it. The results were analysed on the basis of rate equations derived from the possible reaction mechanism, and it was concluded that the rate-determining step of the trans-membrane redox reaction was the process of diffusion of the mediator in the membrane.     

Multicolor photochromism of two- and three-component diarylethene crystals

Novel photochromic single crystals composed of three different kinds of diarylethenes, 1,2-bis(3,5-dimethyl-2-thienyl)perfluorocyclopentene (1a), 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene (2a), and 1,2-bis(2-methyl-5-p-methoxyphenyl-3-thienyl)perfluorocyclopentene (3a), have been prepared. The three-component crystals turned yellow, orange, red, purple, blue, green, or black upon irradiation with light of appropriate wavelengths. The colors of the crystals were thermally stable in the dark and completely bleached by irradiation with visible light. Such multicolored photochromic crystals have potential for the application to optoelectronic devices, such as multifrequency three-dimensional optical memory media or full-color displays.     

Selection of DNA aptamers recognizing small cell lung cancer using living cell-SELEX

We applied Systematic Evolution of Ligands by EXponential enrichment using Small Cell Lung Cancer (SCLC) cells. A DNA aptamer was identified and evaluated by fluorescent confocal microscopy and flow cytometry. Our results showed that the DNA aptamer binds to molecules that exist predominantly on target SCLC cell surfaces compared with other types of SCLC cells.     

Limits of detection and selectivity coefficients of liquid membrane electrodes

An equation has been derived theoretically describing the emf of a liquid membrane electrode: E = E(0) - (RT/F) ln[(C + radicalC (2) + A (x))/2]. Experimental data are in good agreement with this equation. The parameter A(x) is related to the limit of detection. When the ion-exchanger dissociates completely in the membrane phase, A(x) is given by 4sigma(2)/b(x). Here sigma represents the concentration of the ion-exchanger in the liquid membrane and b(x) is a quantity related to the ion-selectivity.     

Oscillating frequency of piezoelectric quartz crystal in solutions

Oscillating frequencies of a piezoelectric crystal were measured in various solutions. One side of the crystal surface was coated with a silicon sealant. This coating was useful for measuring the oscillation of crystals in solutions for a wide range of products of density (?) and viscosity (η) and in electrolyte solutions. For measurement in solutions, the frequency change depended on the circuit used, whereas for measurements in air the circuit did not influence the frequency change. All experimental data showed that the frequency change from pure water, ΔF_w, followed ΔF_w = ? K(√?η ? √?_wη_w) except for electrolyte and polymer solutions, where K is a proportionality constant, η_w the density of pure water and η_w the viscosity of water.