Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.     

Red shifting of absorption maxima of phenothiazine based dyes by incorporating electron-deficient thiadiazole derivatives as π-spacer

This study was carried out to design phenothiazine based dyes by incorporating electron-deficient thiadiazole derivatives as π-spacer. Density functional theory and time-dependent density functional theory calculations of the geometries, electronic structures and absorption spectra of the dyes before and after binding to titanium oxide were carried out. Effects of the electron-deficient units on the spectra and electrochemical properties have been investigated. Compared with the reference compound CS1A, Dyes 1–4 display remarkably enhanced spectral responses in the red portion of the solar spectrum. The newly designed dyes demonstrate desirable energetic and spectroscopic parameters, and may lead to efficient metal-free organic dye sensitizers for DSSCs.     

Photocatalytic decolourization of a new water-insoluble organic dye based on phenothiazine by ZnO and TiO2 nanoparticles

A new water-insoluble organic dye, namely, 2-((10-decyl-10H-phenothiazin-3-yl)methylene)malononitrile, was synthesized and fully characterized. It was envisioned that photocatalytic decolourization of a dye-containing long chain would pave the way for the photocatalytic remediation of wastewater containing toxic hydrophobic organic pollutants. Two commercially available nanoparticles, ZnO and TiO₂, were selected, and their photocatalytic decolourization of the dye from aqueous medium were compared. The black UV light irradiation of the colored samples in the presence of TiO₂ (P25) or ZnO resulted in their decolourization and the photocatalytic activity observed for TiO₂ (P25) was better than that of ZnO. The kinetic of decolourization indicated that the process was first-order from which the rate constant was calculated. Also, the effect of pHs on the kinetic of decolourization revealed a negligible effect, indicating that the pH, although it affects the catalysts but has no effect on the organic-based hydrophobic dye and thus no effect on the photocatalytic process.     

Synthesis of new di-anchoring organic sensitizer based on quinoxaline acceptor for dye-sensitized solar cells

New quinoxaline-based organic sensitizer bearing di-anchoring group for dye-sensitized solar cells (DSSCs) was synthesized from diethyl 4,5-diaminophthaltate, in which was prepared under mild condition by using Takehito’s method. The synthesized sensitizer was compared with mono-anchoring sensitizer through absorption spectra, emission spectra, J-V curve, and IPCE spectra, indicating the di-anchoring group leads to a noticeable improvement of J_sc value owing to more efficient intramolecular charge transfer and channel number increment.     

电解质对两性药物分子盐酸氯丙嗪的胶团生长的影响

The effect of electrolytes on the micellar behavior of an amphiphilic drug,chlorpromazine(CPZ)hydroehloride,was studied using cloud point(CP)and dye solubilization techniques.In the presence of KBr,increase because of deprotonation of drug molecules at high pH. The visible absorbance increased(due to dye solubilization)with the increase in pH from 6.5 to 6.9,which indicated micellar growth.At fixed pH(6.7),addition of inorganic salts(KF,KC1,effecfiveness being in the order:F-Na >K ,which Was explained by considering cognizance of their hydrated radii.Compared with anions,their effect was small.Increase in[CPZ]caused micellar growth and hence the CP as well as the visible absorbance increased.The overall behavior Was discussed in terms of electrostatic interactions and micellar growth.     

Microenvironment Effect on the Location Distribution of Phenothiazine in Cetyltrimethylammonium Bromide/<Emphasis Type="Italic">n</Emphasis>-Pentanol/H<Subscript>2</Subscript>O W/O and Bi-continuous Microemulsions

In cetyltrimethylammonium/n-pentanol/H₂O W/O (W/O = water in oil microemulsion) mixtures and bi-continuous microemulsions, phenothiazine (PTZ) molecules exist in the membrane phase of the dispersion either with the N atom or with the S atom pointed toward the polar head of cetyltrimethylammonium (CTAB). Cyclic voltammetry has been used to investigate the effects of the compositions and structures of the microemulsions, pH, and the salt on the location distribution of PTZ in the membrane phase of the dispersion in CTAB/n-C₅H₁₁OH/H₂O W/O and bi-continuous microemulsions. The results show that the location distribution of PTZ in the membrane phase of the dispersion in microemulsions is mainly dependent on the hydrogen bond between PTZ and n-C₅H₁₁OH (or the counterion), and on the electrostatic attractive interaction between the N atom in PTZ and the polar head of CTAB.     

吩噻嗪在十二烷基硫酸钠/苯甲醇/水微乳液中的定位

采用循环伏安法和荧光猝灭法研究了吩噻嗪（PTZ）在十二烷基硫酸钠（SDS）/苯甲醇（BA ）/ 水（H2O）微乳液中的定位.结果表明,吩噻嗪在十二烷基硫酸钠/苯甲醇/水体系微乳液中位于微乳液膜相中靠近表面活性剂极性头基的一侧,PTZ分子中的S原子和N原子均可朝向表面活性剂的极性头基.     

Syntheses and DNA photocleavage by mono- and bis-phenothiazinium-piperazinexylene intercalators

Chromophore systems consisting of one (compound 5) or two (compound 6) phenothiazine rings covalently attached to a bis-piperazinexylene chain were synthesized and evaluated as DNA photocleaving agents. In the presence of DNA, the compounds were shown to monointercalate in their deaggregated forms and to strongly absorb red wavelengths of light. Reactions containing micromolar concentrations of compound produced robust photocleavage of plasmid DNA under near-physiological conditions of temperature and pH (22 °C and pH 7.0). Phenothiazines 5 and 6 increased the T_m of calf thymus DNA by 17 and 19 °C, indicating that significant levels of duplex stabilization were produced.     

Synthesis of phenothiazine-functionalized porphyrins with high fluorescent quantum yields

Two porphyrins with oligo-phenothiazine arms have been synthesized by a combination of Heck and Adler reaction, and their photophysical properties have been investigated by absorption and steady-state fluorescence spectroscopy. It is found that the excitation energy transfer occurs from the phenothiazine units to the porphyrin core, and that the porphyrins can emit intense red light with high fluorescent quantum yields.     

Electrochemical Oxidation of Phenothiazine Derivatives at Glassy Carbon Electrodes and Their Differential Pulse and Square‐wave Voltammetric Determination in Pharmaceuticals

Abstract

Three 2,10‐disubstituted phenothiazines—chlorpromazine hydrochloride (CPM), thioridazine hydrochloride (TR) and propericiazine (PRC)—were electrochemically studied in various buffer systems at different pH values, using a glassy carbon electrode. The substances were electrochemically oxidized at potential range 0.55–0.75 V. The oxidation was reversible and exhibited diffusion‐controlled process. The mechanism of the oxidation process is discussed. According to the linear relation between peak current and concentration, differential pulse voltammetry (DPV) and square wave voltammetry (SWV) methods for quantitative determination of chlorpromazine and propericiazine in 0.1 M HClO₄, and thioridazine in pH 2 phosphate buffer, was applied. Both the repeatability and reproducibility of the methods were also determined for all studied substances. The developed procedures were successfully applied to the determination of chlorpromazine and thioridazine in pharmaceutical dosage forms.