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.     

Molecular Engineering of Push–Pull Porphyrin Dyes for Highly Efficient Dye‐Sensitized Solar Cells: The Role of Benzene Spacers

Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3‐benzothiadiazole (BTD) as a π‐conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75 % power‐conversion efficiency under simulated one‐sun illumination (AM1.5G, 100 mW cm^?2). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power‐conversion efficiencies. Time‐resolved fluorescence, transient‐photocurrent‐decay, and transient‐photovoltage‐decay measurements were employed to determine the electron‐injection dynamics and the lifetime of the photogenerated charge carriers.     

Fine‐Tuning Dual Emission and Aggregation‐Induced Emission Switching in NPI–BODIPY Dyads

Three new NPI–BODIPY dyads 1 – 3 (NPI=1,8‐naphthalimide, BODIPY=boron‐dipyrromethene) were synthesized, characterized, and studied. The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges, and the compounds only differ structurally with respect to methyl substituents on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in molecular dyads 1 – 3 . Dyads 1–3 show dual emission in solution originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibilities of the systems. Dyads 1 – 3 , depending on their molecular flexibilities, show considerably different spectral shapes and dissimilar intensity ratios of the two emission bands. The dyads also show significant aggregation‐induced emission switching (AIES) on formation of nano‐aggregates in THF/H₂O with changes in emission color from green to red. Whereas the flexible and aggregation‐prone compound 1 shows AIES, rigid systems with less favorable intermolecular interactions (i.e., 2 and 3 ) show aggregation‐induced quenching of emission. Correlations of the emission intensity and structural flexibility were found to be reversed in solution and aggregated states. Photophysical and structural investigations suggested that intermolecular interactions (e.g., π–π stacking) play a major role in controlling the emission of these compounds in the aggregated state.     

Lysosomal pH Rise during Heat Shock Monitored by a Lysosome‐Targeting Near‐Infrared Ratiometric Fluorescent Probe

Heat stroke is a life‐threatening condition, featuring a high body temperature and malfunction of many organ systems. The relationship between heat shock and lysosomes is poorly understood, mainly because of the lack of a suitable research approach. Herein, by incorporating morpholine into a stable hemicyanine skeleton, we develop a new lysosome‐targeting near‐infrared ratiometric pH probe. In combination with fluorescence imaging, we show for the first time that the lysosomal pH value increases but never decreases during heat shock, which might result from lysosomal membrane permeabilization. We also demonstrate that this lysosomal pH rise is irreversible in living cells. Moreover, the probe is easy to synthesize, and shows superior overall analytical performance as compared to the existing commercial ones. This enhanced performance may enable it to be widely used in more lysosomal models of living cells and in further revealing the mechanisms underlying heat‐related pathology.     

Efficient Solar Cells Sensitized by Porphyrins with an Extended Conjugation Framework and a Carbazole Donor: From Molecular Design to Cosensitization

Porphyrin dyes containing the carbazole electron donor have been designed and optimized by wrapping the porphyrin framework, introducing an additional ethynylene bridge to extend the wavelength range of light absorption, and further suppression of the dye aggregation by introducing additional alkoxy chains. Application of a cosensitization approach results in improved current density (J_sc) and open‐circuit voltage (V_oc) values, thus achieving the highest cell efficiency of 10.45 %. This work provides an effective combined strategy of molecular design and cosensitization for developing efficient dye‐sensitized solar cells (DSSCs). In addition, carbazole has been demonstrated to be a promising donor for porphyrin sensitizers.     

Interaction of Fluorescently Labeled Triethyleneglycol and Peptide Derivatives with β‐Cyclodextrin

A triethyleneglycol (TEG) chain, a linear peptide, and a cyclic peptide labeled with 7‐methoxycoumarin‐3‐carboxylic acid (MC) and 7‐diethylaminocoumarin‐3‐carboxylic acid (DAC) were used to thoroughly study Förster resonance energy transfer (FRET) in inclusion complexes. ¹H NMR evidence was given for the formation of a 1:1 inclusion complex between β‐cyclodextrin (β‐CD) and the fluorophore moieties of model compounds. The binding constant was 20 times higher for DAC than for MC derivatives. Molecular modeling provided additional information. The UV/Vis absorption and fluorescence properties were studied and the energy transfer process was quantified. Fluorescence quenching was particularly strong for the peptide derivatives. The presence of β‐CDs reduced the FRET efficiency slightly. Dye‐labeled peptide derivatives can thus be used to form inclusion complexes with β‐CDs and retain most of their FRET properties. This paves the way for their subsequent use in analytical devices that are designed to measure the activity of matrix metalloproteinases.     

Impact of Positional Isomerism on Pathway Complexity in Aqueous Media

Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly.     

The Identification of Cotton Fibers Dyed with Reactive Dyes for Forensic Purposes

Some of the most common microtraces that are currently collected at crime scenes are fragments of single fibers. The perpetrator leaves them at a crime scene or takes them away, for example, on their clothing or body. In turn, the microscopic dimensions of such traces mean that the perpetrator does not notice them and therefore usually does not take action to remove them. Cotton and polyester fibers dyed by reactive and dispersion dyes, respectively, are very popular within clothing products, and they are hidden among microtraces at the scene of a crime. In our recently published review paper, we summarized the possibilities for the identification of disperse dyes of polyester fibers for forensic purposes. In this review, we are concerned with cotton fibers dyed with reactive dyes. Cotton fibers are natural ones that cannot easily be distinguished on the basis of morphological features. Consequently, their color and consequently the dye composition are often their only characteristics. The presented methods for the identification of reactive dyes could be very interesting not only for forensic laboratories, but also for scientists working in food, cosmetics or pharmaceutical/medical sciences.     

Sterically Shielded Heptamethine Cyanine Dyes for Bioconjugation and High Performance Near‐Infrared Fluorescence Imaging

The near‐infrared window of fluorescent heptamethine cyanine dyes greatly facilitates biological imaging because there is deep penetration of the light and negligible background fluorescence. However, dye instability, aggregation, and poor pharmacokinetics are current drawbacks that limit performance and the scope of possible applications. All these limitations are simultaneously overcome with a new molecular design strategy that produces a charge balanced and sterically shielded fluorochrome. The key design feature is a meso‐aryl group that simultaneously projects two shielding arms directly over each face of a linear heptamethine polyene. Cell and mouse imaging experiments compared a shielded heptamethine cyanine dye (and several peptide and antibody bioconjugates) to benchmark heptamethine dyes and found that the shielded systems possess an unsurpassed combination of photophysical, physiochemical, and biodistribution properties that greatly enhance bioimaging performance.