Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C—H bond activation

BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. An overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework have been provided.     

A facile synthesis of solid-emissive fluorescent dyes: dialkylbenzo[b]naphtho[2,1-d]furan-6-one-type fluorophores with strong blue and green fluorescence emission properties

A new type of organic fluorophores, dialkylbenzo[b]naphtho[2,1-d]furan-6-one-type fluorophores, exhibiting strong blue and green emission in the solid state has been easily synthesized by an one-step reaction. The X-ray crystal structure demonstrated that the structural form with a chair-shape with the sterical hindered dialkyl substituents and the 9-dibutylamino group prevents the fluorophores from forming short intermolecular contacts and produces intense solid-state fluorescence emission.     

Flexibility and Rigidity of Proteins and Protein–Pigment Complexes

Proteins may be rigid or flexible to various degrees as required for optimal function. Flexibility of large parts of a protein, which rearrange or move, is particularly interesting and will be discussed in this article. We differentiate between several categories, although the boundaries between them are diffuse: flexibility of peptide segments, order–disorder transitions of spatially contiguous regions, and domain motions. The domains may be flexibly linked to allow rather unrestricted motions or the motions may be constrained to certain modes. The various categories of large-scale flexibility will be illustrated with the following examples: (1) Small protein proteinase inhibitors are rather rigid molecules which provide binding surfaces complementary to their cognate proteases but show also limited segmental flexibility and adaptation. (2) Large plasma proteinase inhibitors exhibit large conformational changes after interaction with proteases probably for regulatory purposes. (3) Pancreatic serine proteases employ a disorder–order transition of their activation domain as a means to regulate enzymic activity. (4) Immunoglobulins show rather unrestricted and also hinged domain motions in different parts of the molecule probably to allow binding to antigens in different arrangements. (5) Citrate synthase adopts open and closed forms by a hinged domain motion to bind substrates and release products and to perform the catalytic condensation reaction, respectively. (6) Riboflavin synthase, a bifunctional multienzyme complex, catalyzes two consecutive reactions by means of two subunits, α and β. The β-subunits form a shell, in which the α-subunits are enclosed. Diffusional motion of the catalytic intermediates is therefore restricted. In addition, rearrangement of the N-terminal segment occurs during the assembly of the β-subunit. In contrast, rigidity is dominant in the structures of the light-harvesting complexes and the photosynthetic reaction centers involved in photosynthetic light reactions. These are large protein–pigment complexes in which the proteins serve as matrices to hold the pigments in the appropriate conformation and relative arrangement. Since motion would contribute to deactivation of the photoexcited states of the pigments and diminish the efficiency of light-energy and electron transfer, the functional role of rigidity is easy to rationalize for these proteins.     

Separation of Dyes from Aqueous Solutions by Paper Adsorption

Separation of the dyes methyl violet, methylene blue, and congo red from aqueous solutions by paper capillary permeation adsorption method was studied using paper. Nearly 100% of the investigated dyes could be separated under the optimum conditions. The effect of pH on the separation efficiency was studied in particular. At pH 5–9, 1.3–11, and 7–11, the maximum separation was achieved for methyl violet, methylene blue and congo red, respectively. The effects of dye concentration and some foreign ions on the separatability were examined. Moreover, the selective separation of some dyes was attempted by elution with chemical reagents.     

Photophysical studies of some dyes in aqueous solution of triton X-100

The spectral (both absorption and fluorescence) and photoelectrochemical studies of a few selective dyes, namely, anionic erythrosin B, neutral riboflavin and cationic safranin O have been carried out in aqueous solution of triton X-100, a neutral surfactant. The results show that the ionic dyes, erythrosin B and safranin O form 1:1 electron donor-acceptor (EDA) or charge-transfer (CT) complexes with triton X-100 both in the ground and excited states, whereas neutral dye riboflavin in its excited state forms 1:1 complex with triton X-100. In these complexes, the dyes act as electron acceptors whereas triton X-100 acts as an electron donor. The fluorescence spectra of erythrosin B and safranin O in presence of triton X-100 show enhancement of fluorescence intensity with red and blue shifts respectively while riboflavin shows normal quenching of fluorescence. A good correlation has been found among photovoltage generation of the systems consisting of these dyes and triton X-100, spectral shift due to complex formation and thermodynamic properties of these complexes.     

Highly selective and efficient separations of a wide range of acidic species in capillary electrophoresis employing non-aqueous media

Summary The novel application of CE using non-aqueous media has been studied for the separation of a range of acidic compound types. This enabled the first quantitative assay by CE employing non-aqueous media to be performed. Separation selectivity manipulation for closely related species was achieved through variation of organic solvent types and composition, ionic strength changes, alteration of pH^* values and the addition of cyclodextrin additives soluble in organic solvents. This offers a greater range of possibilities during method development than use of aqueous buffer. The generation of low operating currents permitted rapid, highly efficient and selective separations to be achieved by applying high field strengths across short capillaries. Optimised rinsing and capillary regenerating procedures were devised which allowed highly repeatable separations to be achieved with migration time repeatability below 1% RSD. Use of internal standards also allowed 1% RSD values to be obtained for injection precision. Routine operating effects were assessed and it was observed that stacking effects remain important in non-aqueous CE. Also, optimal separations are obtained when the samples are diluted in the pure solvent used to prepare the electrolyte. The application range of non-aqueous CE was appreciably extended to include acidic drugs, dyes, surfactants and preservatives.     

Dipolar and V-shaped structures incorporating methylenepyran and diazine fragments

Thirteen novel dipolar and V-shaped chromophores with pyranylidene electron-donating part, diazine electron-withdrawing part and various π-linkers were synthesized. The extent of intramolecular charge transfer, structure-property relationships and optical properties were further investigated by UV/Vis absorption, electrochemistry, and DFT calculations.     

Atlas of Fluorescence Spectra and Lifetimes of Dyes Attached to Protein

Abstract

Fluorescence spectra and lifetimes of ovalbumin labeled with a variety of fluorescent reagents have been measured. The peak positions of the emission spectrum and the long wavelength band of the excitation spectrum as well as the fluorescence lifetimes, are tabulated. Heterogeneity of binding sites is shown by the broadness of some emisison spectra and the presence of multiexponential decay. The atlas may serve as a guide to the properties of these dyes attached to proteins in general.     

Novel triazene dyes from N-heterocyclic carbenes and azides: syntheses,stability, and spectroscopic properties

A series of substituted triazene dyes were synthesized by coupling functionalized imidazol-2-ylidenes with various azides (alkyl, vinyl, aryl, and heteroaryl), in moderate to excellent yields. Their structures were confirmed by spectroscopic studies (IR, NMR, UV–vis, and HRMS). Additionally, the solid-state structure of triazene dye 7 was secured by single crystal X-ray diffraction. Electron delocalization between the two coupled components was studied using UV–vis spectroscopy. The respective triazenes were found to exhibit λ_max values ranging between 294 and 450 nm.     

Wells–Dawson polyoxometelates [HP2W18–nMonO62]Fe2.5, xH2O; n = 0, 6: Synthesis,spectroscopic characterization and catalytic application for oxidation of dyes

The synthesis, IR, ³¹P NMR and cyclic voltammetry characterizations of new Wells–Dawson-type heteropolyanions that contain iron, HFe_2.5P₂W₁₈O₆₂, 23H₂O and HFe_2.5P₂W₁₂Mo₆O₆₂, 22 H₂O, are reported. The catalytic activity of these compounds was evaluated through the oxidation of methyl violet dye, by hydrogen peroxide. The influence of different parameters such as the initial pH, the initial H₂O₂ concentration, the catalyst mass, and the initial dye concentration have been studied.