Amplified quenching of a conjugated polyelectrolyte by cyanine dyes

The conjugated polyelectrolyte PPESO3 features a poly(phenylene ethynylene) backbone substituted with anionic 3-sulfonatopropyloxy groups. PPESO3 is quenched very efficiently (KSV > 10(6) M(-1)) by cationic energy transfer quenchers in an amplified quenching process. In the present investigation, steady-state and picosecond time-resolved fluorescence spectroscopy are used to examine amplified quenching of PPESO3 by a series of cyanine dyes via singlet-singlet energy transfer. The goal of this work is to understand the mechanism of amplified quenching and to characterize important parameters that govern the amplification process. Steady-state fluorescence quenching of PPESO3 by three cationic oxacarbocyanine dyes in methanol solution shows that the quenching efficiency does not correlate with the Forster radius computed from spectral overlap of the PPESO3 fluorescence with the cyanines' absorption. The quenching efficiency is controlled by the stability of the polymer-dye association complex. When quenching studies are carried out in water where PPESO3 is aggregated, changes observed in the absorption and fluorescence spectra of 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HMIDC) indicate that the polymer templates the formation of a J-aggregate of the dye. The fluorescence dynamics in the PPESO3/HMIDC system were probed by time-resolved upconversion and the results show that PPESO3 to HMIDC energy transfer occurs on two distinctive time scales. At low HMIDC concentration, the dynamics are dominated by an energy transfer pathway with a time scale faster than 4 ps. With increasing HMIDC concentration, an energy pathway with a time scale of 0.1-1 ns is active. The prompt pathway (tau < 4 ps) is attributed to quenching of delocalized PPESO3 excitons created near the HMIDC association site, whereas the slow phase is attributed to intra- and interchain exciton diffusion to the HMIDC.     

Ethyl N‐[2‐(hydroxy­acetyl)­phenyl]­carbamate,ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]­carbamate and ethyl N‐[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]­carbamate

In ethyl N‐[2‐(hydroxy­acetyl)phenyl]carbamate, C₁₁H₁₃NO₄, all of the non‐H atoms lie on a mirror plane in the space group Pnma; the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond. The mol­ecules of ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]carbamate, C₁₁H₁₂INO₄, are linked into sheets by a combination of O—H⋯I and C—H⋯O hydrogen bonds and a dipolar I⋯O contact. Ethyl N‐­[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]carbamate, C₁₂H₁₅NO₄, crystallizes with Z′ = 2 in the space group P; pairs of mol­ecules are weakly linked by an O—H⋯O hydrogen bond and these aggregates are linked into chains by two independent aromatic π–π stacking inter­actions.     

Anomalous thermal hysteresis in the SmC* phase of 10FHBBBM7*, revealed by dielectric measurements

The SmC* phase of (R)-4-(1-methylheptyloxycarbonyl)phenyl 4'-(4-decyloxy-3-fluorobenzoyloxy)-benzoate, 10FHBBBM7*, shows an anomalous thermal hysteresis that is reflected in the values of the measured dielectric constant. When the cooling-heating cycle is repeated, a memory effect occurs. In this work, we present a detailed study and a tentative interpretation of this unusual effect.     

DIC Strain Measurements at the Micro-Scale in a Semi-Crystalline Polymer

To improve physical motivation of mechanical modeling for semi-crystalline polymers, a better understanding of micro-mechanisms and a quantification of the mechanical response at the microstructure scale are needed. Strain field evolutions during deformation would be useful information but experimental techniques are still lacking for these materials. In this paper, an in-situ Digital Image Correlation (DIC) technique in the Scanning Electron Microscope (SEM) was developed to access strain fields at the spherulitic scale of a polypropylene. The evolution of strain heterogeneities during deformation were analyzed and correlated to the microstructure.     

Oxidation with DMF/HIO4: A Convenient Preparation of Juglone

As part of an ongoing program directed toward the preparation of antraciclinones¹ and aryl substituted lapachones², which are important anticancer and antibiotic³ agents, we became interested in a efficient synthesis of substituted 1,4-naphthoquinones, such as juglone (3). This compound has received some attention due its activity as an allelophatic compound⁴. An extensive analysis of the literature procedures indicated that several methods are available starting from 1,5-dihydroxynaphthalene (1). All the procedures explored the oxidation of carbon four of the naphthyl ring by several known reagents, such as, chromium trioxide-piridine⁵, thallium trinitrate⁵, chromic acid⁶, peracetic acid⁷, dichromate⁸, iron (III) chloride⁹ and mercuric oxide¹⁰. None of the several known methods for the preparation of (3) proceeded in satisfactory yield (except for the thallium trinitrate method which gave 642 yield) and most of them gave a mixture of 1,2 and 1,4-naphthoquinone.     

Thermal degradation mechanism for citalopram and escitalopram

Journal of Thermal Analysis and Calorimetry - Citalopram, [(R,S)-1-[3-(dimethylamino)propyl]-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran-5-carbonitrile] hydrobromide and its S-isomer, escitalopram...