Photochromism of phenazine-2,3-diol derivatives through excited state intermolecular proton transfer based on keto-enol tautomerization.

Photochromism through excited-state intermolecular proton transfer (ESInterPT) processes based on keto-enol tautomerization was found in phenazine-2,3-diol PD1 and its monoalkoxy derivative PD2 in a glassy matrix at 77 K: the colorless solutions of enol forms PD1-E and PD2-E at 298 K transformed into orange-colored solutions of keto forms PD1-K and PD2-K upon photoirradiation ( = 385 nm) at 77 K. Furthermore, this report is the first to achieve the single-crystal X-ray structural analyses of phenazine-2,3-diol PD1 and its monoalkoxy derivative PD2, since the report on the synthesis of PD1 70 years ago. Indeed, it was found that PD1 and PD2 molecules exist in the keto form (PD1-K) and the enol form (PD2-E), respectively, in the crystal, and the neighboring PD1-K and PD2-E molecules are linked by one-dimensional intermolecular NH⋯O and OH⋯N hydrogen bonding, respectively.

Wireless Electrochemical Gel Actuators.

Soft actuators generate motion in response to external stimuli and are indispensable for soft robots, particularly future miniature robots with complex structure and motion. Similarly to conventional hard robots, electricity is suitable for the stimulation. However, previous electrochemical soft actuators require a tethered connection to a power supply, limiting their size, structure, and motion.

Thermally Stable Photomechanical Molecular Hinge: Sterically Hindered Stiff-Stilbene Photoswitch Mechanically Isomerizes.

Molecular photoswitches are extensively used as molecular machines because of the small structures, simple motions, and advantages of light including high spatiotemporal resolution. Applications of photoswitches depend on the mechanical responses, in other words, whether they can generate motions against mechanical forces as actuators or can be activated and controlled by mechanical forces as mechanophores. Sterically hindered stiff stilbene (HSS) is a promising photoswitch offering large hinge-like motions in the / isomerization, high thermal stability of the isomer, which is relatively unstable compared to the isomer, with a half-life of ca.

Development of water-soluble phenazine-2,3-diol-based photosensitizers for singlet oxygen generation.

Phenazine-2,3-diol-based dyes, KY-1Na and KY-2Na bearing one and two carboxylic acid sodium salts, respectively, have been newly developed as water-soluble photosensitizers (PSs) possessing the ability to generate singlet oxygen (O). In order to evaluate the solubility of KY-1Na and KY-2Na in water, the hydrophobicity/hydrophilicity of the two PSs was investigated by experimental measurement of the logarithms (log ) of the 1-octanol/water partition coefficient () for the PS. The log  values of both KY-1Na and KY-2Na were determined to be -0.

Aggregation-induced emission of a bis(imino)acenaphthene zinc complex with tetraphenylethene units.

Using bis(imino)acenaphthene (BIAN) zinc(II) and palladium(II) complexes with tetraphenylethene (TPE) units as bulky aryl groups, Zn-2 and Pd-2 have been designed and developed, and their photophysical properties in solution and in the solid state have been investigated. Both in solution and in the solid state Zn-2 and Pd-2 show two photoabsorption bands in the ranges of 300 nm to 350 nm and 450 nm to 600 nm, which are assigned to the π-π* transition originating from both the TPE units and naphthalene units and the intraligand charge transfer (ILCT) between the TPE units and the BIAN unit, respectively. Density functional theory (DFT) calculations demonstrated that for Zn-2 the highest occupied molecular orbitals (HOMO) are localized on the TPE units, while the lowest unoccupied molecular orbitals (LUMO) are localized on the BIAN unit, leading to the appearance of a photoabsorption band on the ILCT.

Thermoelectric Properties of Conductive Freestanding Films Prepared from PEDOT:PSS Aqueous Dispersion and Ionic Liquids.

In this study, freestanding poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films modified with an ionic liquid (IL) were synthesized assuming modulization. These films were easily peeled off the glass substrate in water, producing hydrophobic and flexible freestanding films that exhibited extremely high mechanical strengths. The thermoelectric properties of the IL-doped PEDOT:PSS films depended on the amount of IL incorporated.

Fluorescence Turn-on of Tetraphenylethylene Derivative by Transfer from Cyclodextrin to Liposomes, HeLa Cells, and E. coli.

Herein, trimethyl-β-cyclodextrin (TMe-β-CDx) and γ-cyclodextrin (γ-CDx) could dissolve a tetraphenylethylene derivative (TPE-OH ) in water through high-speed vibration milling. The fluorescence intensity of the TMe-β-CDx-TPE-OH complex was much higher than that of the γ-CDx-TPE-OH complex, as the rotation of the central C=C double bond of TPE-OH after photoactivation was inhibited in a smaller TMe-β-CDx cavity in comparison with the γ-CDx cavity. In contrast, the fluorescence intensity of the γ-CDx-TPE-OH complex was very weak; nevertheless, it increased after the addition of liposomes due to the transfer of TPE-OH from the γ-CDx cavity to the lipid membrane as a "turn-on" phenomenon.

Sterically Hindered Stiff-Stilbene Photoswitch Offers Large Motions, 90% Two-Way Photoisomerization, and High Thermal Stability.

Molecular photoswitches have been widely used as molecular machines in various fields due to the small structures and simple motions generated in reversible isomerization. However, common photoswitches, as represented by azobenzene (AB), cannot combine both large motions and high thermal stability, which are critically important for some practical applications in addition to high photoisomerization yields. Here, we focus on a promising photoswitch, stiff stilbene (SS), and its derivative, sterically hindered SS (HSS).

Fluorescent polymer films based on photo-induced electron transfer for visualizing water.

As fluorescent materials for visualization, detection, and quantification of a trace amount of water, we have designed and developed a PET (photo-induced electron transfer)-type fluorescent monomer SM-2 composed of methyl methacrylate-substituted anthracene fluorophore-(aminomethyl)-4-cyanophenylboronic acid pinacol ester (AminoMeCNPhenylBPin) and achieved preparation of a copolymer poly(SM-2--MMA) composed of SM-2 and methyl methacrylate (MMA). Both SM-2 and poly(SM-2--MMA) exhibited enhancement of the fluorescence emission with the increase in water content in various solvents (less polar, polar, protic, and aprotic solvents) due to the formation of the PET inactive (fluorescent) species SM-2a and poly(SM-2--MMA)a, respectively, by the interaction with water molecules. The detection limit (DL) of poly(SM-2--MMA) for water in the low water content region below 1.

Synthesis, optical and electrochemical properties of (D-π)-type and (D-π)Ph-type fluorescent dyes.

The (D-π)-type fluorescent dye with two (diphenylamino)carbazole-thiophene units as D (electron-donating group)-π (π-conjugated bridge) moiety and the (D-π)Ph-type fluorescent dye with the two D-π moieties connected through a phenyl ring were derived by oxidative homocoupling of a stannyl D-π unit and Stille coupling of a stannyl D-π unit with 1,3-diiodobenzene, respectively. Their optical and electrochemical properties were investigated by photoabsorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, cyclic voltammetry (CV) and molecular orbital (MO) calculations. In toluene the photoabsorption and fluorescence maximum wavelengths (λ and λ) of appear in a longer wavelength region than those of .

Acrodysostosis and pseudohypoparathyroidism (PHP): adaptation of Japanese patients with a newly proposed classification and expanding the phenotypic spectrum of variants.

Objective: This study aimed to report on 15 Japanese patients with acrodysostosis and pseudohypoparathyroidism (PHP) and analyze them using the newly proposed classification of the EuroPHP network to determine whether this classification system is suitable for Japanese patients.

Design: We divided the patients into three groups based on hormone resistance, the number of fingers with short metacarpals, the existence of cone-shaped epiphyses and gene defects.

Methods: We carried out clinical, radiological and genetic evaluations of two patients in group A (iPPSD5), six patients in group B (iPPDS4) and seven patients in group C (iPPSD2).

Mechanofluorochromism of (D-π-)A-type azine-based fluorescent dyes.

Bathochromic or hypsochromic shift-type mechanofluorochromism (b-MFC or h-MFC) was found for (D-π-)A-type azine-based fluorescent dyes OUY-2, OUK-2, and OUJ-2 possessing intramolecular charge-transfer (ICT) characteristics from two (diphenylamino)carbazole-thiophene units as D (electron-donating group)-π (π-conjugated bridge) moieties to a pyridine, pyrazine, or triazine ring as A (electron-withdrawing group): grinding of the recrystallized dyes induced red or blue shifts of the fluorescent colors, that is, bathochromic or hypsochromic shifts of the fluorescence maximum wavelengths (λ ). The degrees of MFC evaluated by the absolute value of differences (Δ ) in λ before and after grinding of the recrystallized dyes increased in the order of OUY-2 (+7 nm) < OUK-2 (-17 nm) < OUJ-2 (+45 nm), so that OUJ-2 exhibits obvious b-MFC, but OUK-2 exhibits h-MFC. X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) demonstrated that the recrystallized dyes were in the crystalline state but the ground dyes were in the amorphous state.

Polymer films doped with fluorescent sensor for moisture and water droplet based on photo-induced electron transfer.

Anthracene-(aminomethyl)phenylboronic acid pinacol ester (AminoMePhenylBPin) OF-2 acts as a PET (photo-induced electron transfer)-type fluorescent sensor for determination of a trace amount of water: the addition of water to organic solvents containing OF-2 causes a drastic and linear enhancement of fluorescence emission as a function of water content, which is attributed to the suppression of PET. Indeed, detection limits (DLs) for OF-2 were as low as 0.01-0.

Synthesis, optical and electrochemical properties of 4,4'-bibenzo[]thiophene derivatives.

We designed and synthesized unsubstituted 4,4'-bibenzo[]thiophene 4,4'-BBT and its silyl-substituted derivatives 1,1'-Si-4,4'-BBT and 1,1',3,3'-Si-4,4'-BBT with one or two -butyldimethylsilyl groups on each thiophene ring, as new π-building blocks in emitters, photosensitizers and semiconductors for organic optoelectronic devices. The characterization of 4,4'-BBT, 1,1'-Si-4,4'-BBT and 1,1',3,3'-Si-4,4'-BBT was successfully determined by FTIR, H and C NMR measurements, high-resolution mass spectrometry (HRMS) analysis, photoabsorption and fluorescence spectroscopy, cyclic voltammetry (CV) and density functional theory (DFT) calculations. Moreover, a single-crystal X-ray structural analysis was successfully made for 1,1'-Si-4,4'-BBT and 1,1',3,3'-Si-4,4'-BBT.

Development of optical sensor for water in acetonitrile based on propeller-structured BODIPY-type pyridine-boron trifluoride complex.

A propeller-structured 3,5,8-trithienyl-BODIPY-type pyridine-boron trifluoride complex, ST-3-BF, which has three units of 2-(pyridin-4-yl)-3-(thiophen-2-yl)acrylonitrile at the 3-, 5-, and 8-positions on the BODIPY skeleton, was designed and developed as an intramolecular charge transfer (ICT)-type optical sensor for the detection of a trace amount of water in acetonitrile. The characterization of ST-3-BF was successfully determined by FTIR, H and B NMR measurements, high-resolution mass spectrometry (HRMS) analysis, thermogravimetry-differential thermal analysis (TG-DTA), photoabsorption and fluorescence spectral measurements, and density functional theory (DFT) calculations. ST-3-BF showed a broad photoabsorption band in the range of 600 to 800 nm, which is assigned to the S → S transition of the BODIPY skeleton with the expanded π-conjugated system over the 2-(pyridin-4-yl)-3-(thiophen-2-yl)acrylonitrile units at the 3-, 5-, and 8-positions onto the BODIPY core.

Direct comparison of dithienosilole and dithienogermole as π-conjugated linkers in photosensitizers for dye-sensitized solar cells.

Dithienosilole (DTS) and dithienogermole (DTG) are useful building units of π-conjugated organic materials. In the present work, donor-π-acceptor (D-π-A) dyes with bis(dihexyloxyphenyl)aminophenyl, DTS or DTG, and pyridine or cyanoacrylic acid as the donor (D), the π-conjugated linker (π), and the acceptor (A) units, respectively, were prepared and their optical properties were investigated. The D-π-A dyes exhibited strong absorption in the visible region, indicating efficient intramolecular donor-acceptor interaction.

Development of an intramolecular charge transfer-type colorimetric and fluorescence sensor for water by fusion with a juloidine structure and complexation with boron trifluoride.

An optical sensor with the ability to detect and determine water over a wide concentration range is highly desirable in the laboratory and industry. Here the sensitivity and spectral responses of an intramolecular charge transfer-type colorimetric and fluorescence sensor with β-carboline structure are tuned and improved significantly over various water contents in the organic solvent by fusion with an electron-donating juloidine structure and complexation with boron trifluoride (BF). The sensors, ET-1 and ET-1-BF, developed in this study can respond differently depending on water content.

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-π-)A fluorescent dyes.

The donor-acceptor-π-conjugated (D-π-)A fluorescent dyes -, and with two (diphenylamino)carbazole thiophene units as D (electron-donating group)-π (π-conjugated bridge) moiety and a pyridine, pyrazine or triazine ring as electron-withdrawing group (electron-accepting group, A) have been designed and synthesized. The photophysical and electrochemical properties of the three dyes were investigated by photoabsorption and fluorescence spectroscopy, Lippert-Mataga plots, cyclic voltammetry and density functional theory calculations. The photoabsorption maximum (λ) and the fluorescence maximum (λ) for the intramolecular charge-transfer characteristic band of the (D-π-)A fluorescent dyes show bathochromic shifts in the order of < < .

Fluorescent sensor for water based on photo-induced electron transfer and Förster resonance energy transfer: anthracene-(aminomethyl)phenylboronic acid ester-BODIPY structure.

An anthracene-(aminomethyl)phenylboronic acid ester-BODIPY (DJ-1) was designed and developed as a fluorescent sensor based on photo-induced electron transfer (PET) and Förster resonance energy transfer (FRET) for the detection of a trace amount of water in solvents, where the anthracene skeleton and BODIPY skeleton are the donor fluorophore and the acceptor fluorophore in the FRET process, respectively. It was found that the addition of water to organic solvents containing DJ-1 causes both the suppression of PET in the anthracene-(aminomethyl)phenylboronic acid ester as the PET-type fluorescent sensor skeleton and the energy transfer from the anthracene skeleton to the BODIPY skeleton through a FRET process, thus resulting in the enhancement of the fluorescence band originating from the BODIPY skeleton. This work demonstrates that the PET/FRET-based fluorescent dye composed of the donor fluorophore possessing PET characteristics and the acceptor fluorophore in the FRET process can act as a fluorescent sensor with a large SS for the detection of a trace amount of water in solvents.

Colorimetric and ratiometric fluorescence sensing of water based on 9-methyl pyrido[3,4-b]indole-boron trifluoride complex.

In this work, 9-methyl pyrido[3,4-b]indole-boron trifluoride complex, 9-MP-BF3, was designed and developed as a colorimetric and ratiometric fluorescent sensor for the detection of water in the low- and high-water-content regions in solvents. In the low-water-content region, a new photoabsorption band at around 360 nm and a fluorescence band at around 370 nm gradually appeared due to the dissociation of 9-MP-BF3 into 9-methyl pyrido[3,4-b]indole (9-MP) by water molecules with a simultaneous decrease in the photoabsorption band at around 390 nm and the fluorescence band at around 460 nm originating from 9-MP-BF3. In the moderate-water-content region, the photoabsorption band at around 360 nm and the fluorescence band at around 370 nm gradually shifted to a longer wavelength region with an increase in the fluorescence intensity, which could be ascribed to the formation of a hydrogen-bonded complex (9-MP-H2O) with water molecules.

A colorimetric and fluorescent sensor for water in acetonitrile based on intramolecular charge transfer: D-(π-A)-type pyridine-boron trifluoride complex.

A D-(π-A)2-type pyridine-boron trifluoride complex composed of a carbazole skeleton and two pyridine-boron trifluoride units was designed and developed as a colorimetric and fluorescent sensor based on intramolecular charge transfer (ICT) for the detection of water over a wide range from low water content to high water content in solvents.

Mitochondria-Targeting Polyamine-Protoporphyrin Conjugates for Photodynamic Therapy.

Two polyamine derivatives of protoporphyrin IX (PPIX) were tested as photodynamic therapy (PDT) agents in HT29 colorectal cancer and HEP3B liver cancer cell lines. These compounds exhibit excellent singlet oxygen quantum yields and show strong in vitro PDT efficacy after 660 nm laser irradiation, whereas exogenous PPIX itself exhibits much weaker PDT effects. Confocal microscopy imaging studies reveal that a protoporphyrin derivative with eight amine moieties has excellent water solubility, and localizes mainly in the mitochondria of both HT29 and HEP3B cells, whereas the cellular distribution of a protoporphyrin derivative with four amine moieties is not as specific.

Synthesis and optical and electrochemical properties of a phenanthrodithiophene (fused-bibenzo[c]thiophene) derivative.

We designed and developed a fused-bibenzo[c]thiophene, namely, 2,9-bis(tert-butyldimethylsilyl)phenanthro[9,8-bc:10,1-b'c']dithiophene (PHDT-Si), as a new π-building block in the emitters, photosensitizers and semiconductors for organic optoelectronic devices. Based on photophysical (photoabsorption, fluorescence and time-resolved fluorescence spectroscopy) and electrochemical measurements (cyclic voltammetry), and density functional theory (DFT) calculations, this work reveals that the fused-bibenzo[c]thiophene PHDT-Si, which is prepared by an efficient synthesis method, has a rigid, high planar and expanded π-conjugation structure, and possesses intense photoabsorption and fluorescence properties (λ = 598 nm (ε = 41 000 M cm) and λ = 613 nm (Φ = 0.74) in toluene) in the long-wavelength region and undergoes an electrochemically reversible oxidation process, compared to non-fused 1,1'-bis(tert-butyldimethylsilyl)-4,4'-bibenzo[c]thiophene (BBT-Si).

Synthesis and optical and electrochemical properties of julolidine-structured pyrido[3,4-b]indole dye.

The julolidine-structured pyrido[3,4-b]indole dye ET-1 has been newly designed and developed as a small D-A fluorescent dye. ET-1 showed bathochromic shifts of the fluorescence band upon changing from aprotic solvents to protic solvents, as well as positive fluorescence solvatochromism. Moreover, it was found that ET-1 can form a 1 : 1 Py(N)-B complex with boron trifluoride and a hydrogen-bonded proton transfer (Py(N)-H) complex with trifluoroacetic acid, which exhibit photoabsorption and fluorescence bands at a longer wavelength region than the pristine ET-1.