Studies on the Solvation Dynamics of Coumarin 153 in 1‐Ethyl‐3‐Methylimidazolium Alkylsulfate Ionic Liquids: Dependence on Alkyl Chain Length

Steady‐state and time‐resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1‐ethyl‐3‐methylimidazolium alkylsulfate ([C₂mim][C_nOSO₃]) ionic liquids differing only in the length of the linear alkyl chain (n=4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady‐state absorption and emission maxima of C153 on going from the C₄OSO₃ to the C₈OSO₃ system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time‐zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes–Einstein–Debye (SED), Gierer–Wirtz (GW), and Dote–Kivelson–Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity.     

DNA Photocleavage by a Cationic BODIPY Dye through Both Singlet Oxygen and Hydroxyl Radical: New Insight into the Photodynamic Mechanism of BODIPYs

Two new NIR‐absorbing BODIPY dyes, each bearing two pyridinium groups, are synthesized and their DNA‐binding affinities and DNA photocleavage abilities examined in depth. While one BODIPY dye photocleaves DNA mainly through singlet oxygen, the other photocleaves DNA through both singlet oxygen and hydroxyl radical. To the best of our knowledge, this is the first example of a hydroxyl radical being involved in the photodynamic behavior of BODIPY‐type dyes. EPR experiments confirm the ability of these and several related BODIPYs to generate superoxide anion radical and hydroxyl radical. This finding may shed light on the mechanism of BODIPY‐based photodynamic therapy (PDT) and open a new avenue for development of more efficient BODIPY‐type PDT agents.     

Referenced Dual Pressure‐ and Temperature‐Sensitive Paint for Digital Color Camera Read Out

The first fluorescent material for the referenced simultaneous RGB (red green blue) imaging of barometric pressure (oxygen partial pressure) and temperature is presented. This sensitive coating consists of two platinum(II) complexes as indicators and a reference dye, each of which is incorporated in appropriate polymer nanoparticles. These particles are dispersed in a polyurethane hydrogel and spread onto a solid support. The emission of the (oxygen) pressure indicator, PtTFPP, matches the red channel of a RGB color camera, whilst the emission of the temperature indicator [Pt^II(Br‐thq)(acac)] matches the green channel. The reference dye, 9,10‐diphenylanthracene, emits in the blue channel. In contrast to other dual‐sensitive materials, this new coating allows for the simultaneous imaging of both indicator signals, as well as the reference signal, in one RGB color picture without having to separate the signals with additional optical filters. All of these dyes are excitable with a 405 nm light‐emitting diode (LED). With this new composite material, barometric pressure can be determined with a resolution of 22 mbar; the temperature can be determined with a resolution of 4.3 °C.     

Hydrophilicity Control of Visible‐Light Hydrogen Evolution and Dynamics of the Charge‐Separated State in Dye/TiO2/Pt Hybrid Systems

Visible‐light‐driven H₂ evolution based on Dye/TiO₂/Pt hybrid photocatalysts was investigated for a series of (E)‐3‐(5′‐{4‐[bis(4‐R¹‐phenyl)amino]phenyl}‐4,4′‐(R²)₂‐2,2′‐bithiophen‐5‐yl)‐2‐cyanoacrylic acid dyes. Efficiencies of hydrogen evolution from aqueous suspensions in the presence of ethylenediaminetetraacetic acid as electron donor under illumination at λ>420 nm were found to considerably depend on the hydrophilic character of R¹, varying in the order MOD (R¹=CH₃OCH₂, R²=H)≈ MO4D (R¹=R²=CH₃OCH₂)> HD (R¹=R²=H)> PD (R¹=C₃H₇, R²=H). In the case of MOD /TiO₂/Pt, the apparent quantum yield for photocatalyzed H₂ generation at 436 nm was 0.27±0.03. Transient absorption measurements for MOD ‐ or PD ‐grafted transparent films of TiO₂ nanoparticles dipped into water at pH 3 commonly revealed ultrafast formation (<100 fs) of the dye radical cation (Dye^.+) followed by multicomponent decays, which involve minor fast decays (<5 ps) almost independent of R¹ and major slower decays with significant differences between the two samples: 1) the early decay of the major components for MOD is about 2.5 times slower than that for PD and 2) a redshift of the spectrum occurred for MOD with a time constant of 17 ps, but not for PD . The substituent effects on H₂ generation as well as on transient behavior have been discussed in terms substituent‐dependent charge recombination (CR) of Dye^.+ with electrons in bulk, inner‐trap, and/or interstitial‐trap states, arising from different solvent reorganization.     

Tuning the Spectroscopic,Electrochemical, and Photovoltaic Properties of Triaryl Amine Based Sensitizers through Ring‐Fused Thiophene Bridges

The ring‐fused thiophene derivatives benzo[c]thiophene and its precursor bicyclo[2.2.2]octadiene (BCOD) have been introduced as π‐conjugated spacers for organic push–pull sensitizers with dihexyloxy‐substituted triphenylamine as donor and cyanoacrylic acid as acceptor ( OL1 , OL2 , OL3 , OL4 , OL5 , OL6 ). The effects of the fused ring on the spectroscopic and electrochemical properties of these sensitizers and their photovoltaic performance in dye‐sensitized solar cells have been evaluated. Introduction of a binary benzo[c]thiophene and ethylenedioxy thiophene as π bridge caused a significant red shift of the characteristic intramolecular charge‐transfer band to 642 nm. It is found that the sensitizer OL3 , which contains one benzo[c]thiophene unit as π linker, gives the highest overall conversion efficiency of 5.03 % among all these dyes.     

氧化石墨：制备及去除阳离子染料的性能

以石墨粉为原料按Hummers氧化法制备氧化石墨,借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱法(FTIR)和低温氮吸附-脱附对氧化石墨的结构和形貌进行了表征。结果表明,氧化石墨是不平整的、具有一定层状结构的褶皱片状,在其表面存在着许多含氧的官能团如:环氧基、羟基、羧基。此外还研究了氧化石墨对阳离子染料的吸附性能,结果表明:吸附过程的等温模型符合Langmuir等温式,对甲基紫、甲基绿、中性红这3种阳离子染料的最大饱和吸附量分别为:741,446和368 mg.g-1;对阳离子染料的吸附过程符合二级动力学方程。氧化石墨作为一种吸附剂能有效的去除阳离子染料与其较高的比表面积和与阳离子染料的静电吸引有关。     

Preconcentration of Uranium in Seawater with Heterocyclic Azo Dyes Supported on Silica Gel

Abstract

The chelating adsorbents, heterocyclic azo dyes supported on silica gel, were prepared and their adsorption behaviors of metal ions were investigated. The 1-(2-pyridylazo)-2-naphthol(PAN)-SG and 2-(2-thiazolylazo)-p-cresol(TAC)-SG show greater affinity for UO₂(II) and ZrO(II), compared with the other metal ions like Cu, Cd, Fe and alkaline earths. Trace uranyl can be quantitatively retained on the column of the gels at neutral pH region and flow-rate 3–4 ml/min. The uranyl retained is easily eluted from the column bed with a mixture of acetone and nitric acid(9:1 v/v) and determined by spectrophotometry using Arsenazo-III. Matrix components in seawater do not interfere and the spiked recovery of uranyl in artificial seawater was found to be average 98.6 %, with the relative standard deviation of 1.08 %. Both gels were applied to the determination of uranium in seawater with satisfactory results.     

Biosupramolecular nanowires from chlorophyll dyes with exceptional charge-transport properties

Conductive tubes: Self-assembled nanotubes of a bacteriochlorophyll derivative are reminiscent of natural chlorosomal light-harvesting assemblies. After deposition on a substrate that consists of a non-conductive silicon oxide surface (see picture, brown) and contacting the chlorin nanowires to a conductive polymer (yellow), they show exceptional charge-transport properties.     

Comparison of the electronic structure of different perylene‐based dye‐aggregates

Aggregates of functionalized polycyclic aromatic molecules like perylene derivatives differ in important optoelectronic properties such as absorption and emission spectra or exciton diffusion lengths. Although those differences are well known, it is not fully understood if they are caused by variations in the geometrical orientation of the molecules within the aggregates, variations in the electronic structures of the dye aggregates or interplay of both. As this knowledge is of interest for the development of materials with optimized functionalities, we investigate this question by comparing the electronic structures of dimer systems of representative perylene‐based chromophores. The study comprises dimers of perylene, 3,4,9,10‐perylene tetracarboxylic acid bisimide (PBI), 3,4,9,10‐perylene tetracarboxylic acid dianhydride (PTCDA), and diindeno perylene (DIP). Potential energy curves (PECs) and characters of those electronic states are investigated which determine the optoelectronic properties. The computations use the spin‐component‐scaled approximate coupled‐cluster second‐order method (SCS‐CC2), which describes electronic states of predominately neutral excited (NE) and charge transfer (CT) character equally well. Our results show that the characters of the excited states change significantly with the intermolecular orientation and often represent significant mixtures of NE and CT characters. However, PECs and electronic structures of the investigated perylene derivatives are almost independent of the substitution patterns of the perylene core indicating that the observed differences in the optoelectronic properties mainly result from the geometrical structure of the dye aggregate. It also hints at the fact that optical properties can be computed from less‐substituted model compounds if a proper aggregate geometry is chosen. © 2012 Wiley Periodicals, Inc.