Cytotoxicity of Amino-BODIPY Modulated via Conjugation with 2-Phenyl-3-Hydroxy-4(1H)-Quinolinones

The combination of cytotoxic amino-BODIPY dye and 2-phenyl-3-hydroxy-4(1H)-quinolinone (3-HQ) derivatives into one molecule gave rise to selective activity against lymphoblastic or myeloid leukemia and the simultaneous disappearance of the cytotoxicity against normal cells. Both species′ conjugation can be realized via a disulfide linker cleavable in the presence of glutathione characteristic for cancer cells. The cleavage liberating the free amino-BODIPY dye and 3-HQ derivative can be monitored by ratiometric fluorescence or by the OFF-ON effect of the amino-BODIPY dye. A similar cytotoxic activity is observed when the amino-BODIPY dye and 3-HQ derivative are connected through a non-cleavable maleimide linker. The work reports the synthesis of several conjugates, the study of their cleavage inside cells, and cytotoxic screening.     

Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins

The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin.     

Disposable Electrochemical Sensor for Food Colorants Detection by Reduced Graphene Oxide and Methionine Film Modified Screen Printed Carbon Electrode

A facile synthesis of reduced graphene oxide (rGO) and methionine film modified screen printed carbon electrode (rGO-methionine/SPCE) was proposed as a disposable sensor for determination of food colorants including amaranth, tartrazine, sunset yellow, and carminic acid. The fabrication process can be achieved in only 2 steps including drop-casting of rGO and electropolymerization of poly(L-methionine) film on SPCE. Surface morphology of modified electrode was studied by scanning electron microscopy (SEM). This work showed a successfully developed novel disposable sensor for detection of all 4 dyes as food colorants. The electrochemical behavior of all 4 food colorants were investigated on modified electrodes. The rGO-methionine/SPCE significantly enhanced catalytic activity of all 4 dyes. The pH value and accumulation time were optimized to obtain optimal condition of each colorant. Differential pulse voltammetry (DPV) was used for determination, and two linear detection ranges were observed for each dye. Linear detection ranges were found from 1 to 10 and 10 to 100 µM for amaranth, 1 to 10 and 10 to 85 µM for tartrazine, 1 to 10 and 10 to 50 µM for sunset yellow, and 1 to 20 and 20 to 60 µM for carminic acid. The limit of detection (LOD) was calculated at 57, 41, 48, and 36 nM for amaranth, tartrazine, sunset yellow, and carminic acid, respectively. In addition, the modified sensor also demonstrated high tolerance to interference substances, good repeatability, and high performance for real sample analysis.     

Synthesis of tunable core–shell nanostructures based on TiO2-graphene architectures and their application in the photodegradation of rhodamine dyes

We present the synthesis of core–shell nanostructural materials with multi-component architectures based on TiO₂ and graphitic layers. The composites have been synthesized by chemical vapor deposition with methane as the carbon source, for 5, 10, 30 and 45 min. The final products were characterized by a combination of analytical approaches which include: electron microscopy, Raman, FT-IR and UV–vis spectroscopy as well as thermogravimetric analysis. The amount of graphene shells covering the TiO₂ surfaces was found to vary linearly with the reaction time. Furthermore, the compounds were shown to have excellent stability and photocatalytic activity towards the UV degradation of rhodamine (RhB) dye solution at room temperature. These composites could have major applications in the area of environmental cleaning of various pollutants, electrochemistry or nanomedicine.     

Monitoring of the Proton Electrochemical Gradient in Reconstituted Vesicles: Quantitative Measurements of Both Transmembrane Potential and Intravesicular pH by Ratiometric Fluorescent Probes

Proteoliposomes carrying reconstituted yeast plasma membrane H⁺-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical processes involved in formation of the proton electrochemical gradient (Δμ_H ⁺) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H⁺-ATPase. Its Δψ response can be calibrated by the K⁺/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined to it.     

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems.     

Synthesis,spatial structure and spectral properties of pyrylo‐4 (thio) squaraines variously substituted in cyclobutene moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH‐acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X‐ray diffraction analysis, ¹H NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first π–π^* absorption band. The structure–property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright © 2015 John Wiley & Sons, Ltd.     

Photocatalytic degradation of azo dyes in aqueous solutions under UV irradiation using nano-strontium titanate as the nanophotocatalyst

Research on photocatalytic degradation rate of azo dyes using nano-strontium titanate in photocatalysis process was the main goal of present study. In this regard, the influence of the main operating parameters such a photocatalyst concentration, dye concentration, temperature, pH and the presence of hydrogen peroxide upon dye removal rate under UV irradiation was studied. The absorbance of samples was measured by a UV–Vis spectrophotometer. The structure and morphology of nano-powder were investigated using scanning electron microscopy and crystalline structure by X-ray diffraction spectroscopy. The results reveal that nano-strontium titanate has high and significant photocatalytic activity and in comparison with nano-titanium dioxide was superior photocatalyst.     

Single‐Molecule Sensing of Environmental pH—an STM Break Junction and NEGF‐DFT Approach

Sensors play a significant role in the detection of toxic species and explosives, and in the remote control of chemical processes. In this work, we report a single‐molecule‐based pH switch/sensor that exploits the sensitivity of dye molecules to environmental pH to build metal–molecule–metal (m‐M‐m) devices using the scanning tunneling microscopy (STM) break junction technique. Dyes undergo pH‐induced electronic modulation due to reversible structural transformation between a conjugated and a nonconjugated form, resulting in a change in the HOMO–LUMO gap. The dye‐mediated m‐M‐m devices react to environmental pH with a high on/off ratio (≈100:1) of device conductivity. Density functional theory (DFT) calculations, carried out under the non‐equilibrium Green’s function (NEGF) framework, model charge transport through these molecules in the two possible forms and confirm that the HOMO–LUMO gap of dyes is nearly twice as large in the nonconjugated form as in the conjugated form.     

Photostability of 4,4′‐Dihydroxythioindigo,a Mimetic of Indigo

The photochemical properties of indigo, a widely used industrial dye, has attracted both experimentalists and theoreticians from the beginning. Especially the high photostability of indigo has been the subject of intensive research. Recently, it was proposed that after photoexcitation an intramolecular proton transfer followed by a nonradiative relaxation to the ground state promote photostability. In indigo the hydrogen bond and the proton transfer occur between the opposing hemiindigo parts. Here, we provide experimental and theoretical evidence that a hydrogen transfer within one hemiindigo or hemithioindigo part is sufficient to attain photostability. This concept can serve as an interesting strategy towards new photostable dyes for the visible part of the spectrum.