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.     

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.     

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.     

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.     

Stabilization and translation of immobilized mRNA on latex beads for cell-free protein synthesis system

The stability of immobilized mRNA against ribonucleases was investigated in a cell-free protein synthesis system. The plasmid-encoding protein A with the 20-mer poly(A) tail under the control of T7 promoter was constructed, and the corresponding mRNA was synthesized by T7 RNA polymerase reaction. The resulting mRNA was immobilized on oligo(dT)-immobilized latex beads by hybridization utilizing the poly(A) tail of mRNA at the 3'-terminus. The mRNA was stabilized against three types of nucleases (3'-OH exonuclease, 5'-OH exonuclease, and endonuclease) by immobilization. Translation of immobilized mRNA with a continuous-flow cell-free protein-synthesizing system from Saccharomyces cerevisiae was ascertained. Reusability of the immobilized mRNA as genetic information was also examined.     

Synthetic and analytical studies on colour reagents-IX The reactions of phthaleinazo compounds with the alkaline earths

Some new phthaleinazo compounds-o,o'-dihydroxyazo compounds-have been prepared by coupling chromotropic acid, R-acid, and 2-hydroxy-3-naphthoic acid with bis-diazotized diaminophthaleins. These compounds have been found to be very sensitive colour reagents for alkaline earths in alkaline media, and in particular, bis(chromotropeazo)phenolphthalein is the most sensitive yet found.     

ACTION SPECTRA FOR SUPEROXIDE GENERATION AND UV AND VISIBLE LIGHT PHOTOAVOIDANCE IN PLASMODIA OF Physarum polycephalum

Abstract— The initial photochemical process leading to photoavoidance by plasmodia of an albino strain of Physarum Plasmodium was studied. Superoxide (O), detected as superoxide dismutase (SOD)-inhibitable electron spin resonance (ESR) signal of a spin trap (tBN), was formed upon irradiation. The amount of O formed increased linearl) with log fluence rate above the threshold. The photoavoidance to radiation at wavelengths between200–800 nm also showed the similar linear relationship in log fluence rate-response curves. Thresholds for photoavoidance and O generation agreed with each other and the action spectra showed peaks at about 260, 370, and 460 nm. Thus, active oxygen generated by photosensitization seems to trigger the UV and blue light photoavoidance.     

Structural Change in Dextran: Mechanism of Insolubilization by Adsorption on the Air-Liquid Interface

To clarify the insolubilization mechanism of water-soluble dextran, the association of dextran in water was studied by dynamic light scattering measurements and a surface chemical approach. Dynamic light scattering measurements indicated that insolubilization of dextran is accompanied by a structural change in dextran. Surface tension data for dextran molecules revealed a structural change in dextran molecules at the air-liquid interface. These results suggest that insolubilization of dextran molecules occurred through an adsorption process at the air-liquid interface. Insolubilization of dextran molecules can be reduced by inhibition of this structural change in dextran molecules. The presence of boron as an impurity was found to trigger precipitation based on inductively coupled plasma mass spectrometry measurements and precipitation tests. Copyright 1999 Academic Press.     

Synthesis and photoisomerization of dithienylethene-bridged diporphyrins

Dithienylethene-bridged diporphyrins 1-6 were prepared as photochemical switching molecules. Porphyrin and dithienylethene are directly linked in 1, and linked, respectively, through a 1,4-phenylene spacer in 2, through a 4-ethynylphenylene spacer in 3, and through a di-4-phenylethynylene spacer in 4, while meso-ethynylated porphyrin and dithienylethene are directly connected in 5 and linked through a 1,4-phenylene spacer in 6. Compounds 1, 2, and 5 do not undergo any photochemical isomerization, probably due to efficient quenching of the excited dithienylethene by the attached porphyrin moiety via intramolecular energy transfer. Compounds 4 and 6 undergo open-to-closed and closed-to-open photoisomerizations in quantum yields of 4.3 x 10(-)(2) and 1.8 x 10(-)(3), and 2.6 x 10(-)(3) and 7.5 x 10(-)(4), respectively, by irradiation with 313 and 625 nm light, which are considerably smaller than quantum yields of 0.52 and 3.8 x 10(-)(3) for reference dithienylethene molecule 7. The fluorescence of 4 was regulated in a reversible manner by the photoisomerization of the dithienylethene moiety. In addition, the absorption properties of the porphyrin in 6 changed in response to the photochromic reaction of the dithienylethene bridge.